BCR2

Chapter 4
Molecular Computations of Adsorption

in Nanoporous Materials
Ravichandar Babarao and Jianwen Jiang
Abstract Adsorption lies at the heart of many industrially important applications

such as purification, separation, ion exchange, and catalysis. As the number of
nanoporous materials synthesized to date is extremely large, rationally choosing
a high-performance material from discovery to specific application is a substantial challenge. Computational approaches at the molecular scale can provide microscopic insight into adsorption behavior from the bottom-up, complement and secure
correct interpretation of experimental results, and are imperative to new material
design and advanced technological innovation. We review the recent computational
studies of adsorption in nanoporous materials with a wide variety of building blocks
and physical topologies, ranging from zeolites, carbonaceous materials to hybrid
frameworks.
4.1 Introduction
Nanoporous materials play a pivotal role in many engineering processes and industrial applications, for instance, the separation of impurities from natural gas to
improve energy efficiency, the catalytic cracking of hydrocarbons, and the removal
of toxic heavy metals from wastewater [1]. An overwhelmingly large number of
porous materials have been and are being synthesized and characterized in the laboratory; consequently, theoretical guidelines are highly desired to properly choose
a material for specific use. Due to the spatial confinement and surface interactions, fluids in nanodomain behave significantly different from bulk phases. A clear
mechanistic understanding of fluid behavior in nanoporous materials is not only
of fundamental interest but also of central importance for practical use. In the past,
analytical approaches like density-functional theory (DFT) based on the advances in
J. Jiang (B)
Department of Chemical and Biomolecular Engineering, National University of Singapore,
Singapore 117576, Singapore
e-mail: chejj@nus.edu.sg
L.J. Dunne, G. Manos (eds.), Adsorption and Phase Behaviour in Nanochannels
and Nanotubes, DOI 10.1007/978-90-481-2481-7_4,

C Springer Science+Business Media B.V. 2010
69
70
R. Babarao and J. Jiang
statistical mechanics have been developed to examine the equilibrium properties of

fluids in simple slit-like and cylindrical pores [24]. With an appropriate weighting
function, DFT can accurately predict the density profiles, isotherms, configurations,
layerings, etc. [57]. However, the extension of DFT to three-dimensional complex
geometries is formidable. With ever-growing computational power, the state-of-theart molecular simulation has increasingly become a versatile tool to investigate the
underlying properties of fluids confined in porous materials [8]. Simulation provides
microscopic insight from the bottom-up that is otherwise experimentally inaccessible or difficult, if not impossible. In addition, simulation can be used to complement and secure fundamental interpretation of experimental results and establish
the structurefunction relations based on molecular description. Therefore, molecular simulation is indispensable in the rational design of novel materials of increasing
complexity for new applications.
In this chapter, we review the recent simulation studies of adsorption in zeolites, carbonaceous structures, and hybrid organicinorganic frameworks. They represent three classes of fascinating nanoporous materials that are being widely used
in chemical industries and/or exhibit unique properties for emerging applications.
Experimental studies of adsorption in these materials have been comprehensively
addressed; however, simulation studies are relatively less. Due to page limitation,
the technical details of simulation principles are not described here, which are well
documented elsewhere [9, 10]. Nevertheless, the commonly used simulation methods for adsorption in porous media are briefly introduced below.
Stochastic Monte Carlo (MC) instead of deterministic molecular dynamics (MD)
method is most frequently used for adsorption studies [11]. The reason is that
MD is not straightforward to simulate adsorption isotherm as a function of bulk
pressure, which is considered as one of the most important adsorption properties
because isotherm can be readily determined from experiment. MD motion mimics the natural behavior of molecules through Newtons equation of motion, that is,
molecules diffuse into a porous material before adsorption equilibrium is reached.
This is a slow process particularly for large molecules, such as alkanes and aromatics. In contrast, MC does not need to follow the natural pathway and thus
allows random trial move so that a successful move may correspond to a large
jump in phase space, thereby reaching equilibrium rapidly. Most MC simulation
studies of adsorption are carried out in canonical or grand-canonical ensemble. In
canonical ensemble, temperature, volume, and number of adsorbate molecules are
fixed. MC simulation in canonical ensemble is usually used to simulate the distribution and energetics of adsorption sites, isosteric heat, and Henrys constant. In
grand-canonical ensemble, temperature, volume, and chemical potential of adsorbate are fixed. Grand-canonical Monte Carlo (GCMC) simulation permits adsorbate
molecules to exchange between adsorbed phase and bulk fluid reservoir, and can
provide adsorption isotherm easily. To compare GCMC results with experimental
data, the chemical potential has to be converted into pressure using an equation
of state or additional simulation. Widely used to simulate phase equilibria, Gibbs
ensemble Monte Carlo (GEMC) method [12] has recently been used to simulate
adsorption at a given pressure. GEMC is performed in two microscopic cells, one
Molecular Computations of Adsorption in Nanoporous Materials
71
cell with the adsorbent and the other with the bulk fluid. At a given pressure, the
volume of the bulk fluid is allowed to change. The total number of molecules is
fixed, but molecules can be transferred from one cell to the other. In the studies
reviewed here, these simulation techniques have been used to elucidate adsorption
phenomena at the molecular level in zeolites, carbonaceous materials, and hybrid
frameworks.
4.2 Zeolites
Zeolites are three-dimensional crystalline aluminosilicate materials [13, 14]. The
primary building blocks in zeolites are tetrahedral oxides SiO4 and AlO4 that connect together via corner-sharing oxygen atoms to form well-defined open pores. The
pores are precisely uniform, which distinguishes zeolites from many other porous
materials. Figure 4.1 shows three typical structures: MFI, FAU, and LTA. Some zeolites are not stable upon removing nonframework species, and the stability varies
with topology and composition. Zeolites have been extensively used in industrial
applications such as molecular sieving, catalysis, and ion exchange. Progress till
2001 in the computation of thermodynamic properties of guest molecules in zeolites was reviewed [15].
(a)
(b)
(c)
Fig. 4.1 Zeolites: (a) MFI, (b) FAU, and (c) LTA. Color code: red, O; yellow, Si; pink, Al
4.2.1 Light Gases

N2 , O2 , and Ar in zeolites LTA, X-, and Y-FAU were studied using GCMC simulation; the predicted N2 /O2 selectivity in LTA was in accordance with experiment
[16]. With the appropriate force field parameters, experimentally determined isosteric heats of NH3 adsorption in MOR, MFI, and Y-FAU were reproduced by simulation [17]. Adsorption of CH4 and CF4 in silicalite was measured and simulated
as a function of phase composition, total pressure, and temperature; the simulated
isotherms and isosteric heats were in good agreement with experiments [18]. A hierarchical modeling approach combining atomistic and coarse-grained simulations
72
was proposed to predict adsorption thermodynamics of single components and

binary mixtures in silicalite. The results agreed well with full atomistic simulation, but the hierarchical approach saved an order of magnitude of computational
effort [19]. Long-range corrections were evaluated for simulation of CH4 and SF6
in silicalite at 298 K. A consistent use of cutoff radius was shown to be more important than the inclusion or the neglect of long-range corrections to potential energy
[20]. Nonpolar (Ar and CH4 ) and quadrupolar gases (N2 and CO2 ) in pure siliceous
FAU were investigated both experimentally and theoretically at ambient temperature and high pressures [21]. A systematic simulation study was reported for H2
in 12 purely siliceous zeolites, in which the cell parameters and framework flexibility were allowed to vary upon progressive filling of gas molecules, and then the
maximum H2 adsorption capacity in each framework was examined [22]. CO2 and
N2 both as single component and as binary mixture were studied in MFI, ITQ-3,
and ITQ-7. The CO2 /N2 selectivity varies strongly with the crystal structure. Simulated binary adsorption agrees well with prediction by the ideal adsorbed solution
theory (IAST) based on single-component adsorption [23]. Thermodynamics and
siting of CO2 , CH4 , and their mixtures were studied in ITQ-1 which consists of
two independent pores of different geometry. At the three temperatures considered,
a preferential adsorption of CO2 over CH4 was found. The equilibrium selectivity
was distinctly higher in its sinusoidal channel pore system than in the large cavity system over a wide range of pressures starting from the Henry law regime. A
maximum in selectivity was observed at low temperature, high pressure, and CH4 rich gas-phase composition [24]. H2 O adsorption in X- and Y-FAU as well as in
silicalite was computed. The isotherms and heats of adsorption were in good agreement with available experiments. The existence of cyclic H2 O hexamers located in
the 12-ring windows of NaX, recently disclosed by neutron diffraction experiments,
was observed [25]. A joint experimental and simulation study of H2 O adsorption
in silicalite was reported. The simulation qualitatively reproduced experimentally
observed condensation thermodynamic features. A shift and a rounding in the condensation transition were found with an increasing hydrophilicity of the local defect,
but the condensation transition was observed above the saturation pressure of H2 O
[26]. Simulation of H2 O in MFI by reducing the dipole moment of H2 O matched
well with the experimental isotherm at 300 K. The work suggests that the effective
intermolecular potential parameterized for bulk water is insufficient to describe the
ultraconfined water molecules [27].
4.2.2 Alkanes and Alkenes

With the development of configurational-bias Monte Carlo (CBMC) algorithm
[2830], adsorption of alkanes has been studied efficiently. Instead of inserting a
molecule at a random position, a molecule in CBMC is grown atom-by-atom biasing toward the energetically favorable configurations while avoiding overlap with
other atoms, and the bias is then removed by adjusting the acceptance rules [10].
Using the united-atom (UA) model for alkanes, Smit et al. observed an inflection
73
in the adsorption isotherms of n-hexane and n-heptane in MFI, but not of shorter
or longer alkanes. This inflection was attributed to the commensurate freezing
effect as the size of the zigzag channel in MFI is commensurate with the size of
n-hexane and n-heptane [31, 32]. Apart from MFI, alkanes were also simulated in
other zeolites such as FER, MTW, TON, and DON using the same force field as for
MFI and good agreement with experiments was found [33]. Linear alkanes ranging in length from C2 to C7 in AlPO4 -11 were examined and the isosteric heats
at infinite dilution matched well with experimental data [34]. The UA model was
also used to study adsorption of alkenes and their mixtures in silicalite-1, theta-1,
and deca-dodecasil. For C3 H6 /C3 H8 mixture in Na-LTA, adsorption isotherm from
simulation agrees well with experimentally measured results in cation-free LTA,
but not in Na+ -exchanged LTA [35, 36]. The anisotropic united-atom (AUA) potential for hydrocarbons was adopted to calculate the adsorption isotherms of linear
and branched alkanes in MFI; good agreement was observed with experiments and
other simulation results [37]. Also, with the AUA potential, adsorption isotherms of
pure alkenes and alkane/alkene mixtures in MFI were found to be closely consistent with experimental results [38]. Adsorption of n-pentane and n-hexane in FER
showed that the prediction of UA potential is inconsistent with experiment, whereas
the AUA potential can reproduce the subtle change in adsorption site occupancies
of n-alkanes (n = 37) [39]. Simulation isotherms of cycloalkanes like cyclopentane, -hexane, and -heptane in MFI reproduced most features in experiments and
revealed an inflection for cyclopentane but not for cyclohexane [40]. Comparing
measured and simulated adsorption properties, a decrease in the Gibbs free energy
of formation and adsorption was observed. Based on this observation, the selective
production and adsorption of the most compact, branched paraffins in n-hexadecane
hydroconversion in molecular sieves with pore diameters of ~0. 75 nm was satisfactorily elucidated [41]. Krishna et al. screened different zeolites for the separation of
CH4 /CO2 mixture and of hexane isomers. The linear n-hexane has a longer footprint and occupies a longer segment in the zeolite channel; 2,2-dimethylbutane is
the most compact isomer and has the smallest footprint. Consequently, a greater
number of 2,2-dimethylbutane molecules were observed to be located within the
MOR channels, in which the length entropy effect dictates [42, 43].
4.2.3 Aromatics
Adsorption of aromatic molecules that fit tightly into zeolite frameworks has been
investigated by simulations. Different guesthost force fields including all-atom,
UA, and AUA models were used to simulate the adsorption of benzene, xylene,
and cyclohexane. The force field considerably affects the locations of benzene and
cyclohexane. This suggests that care should be taken in choosing the force field, particularly when the guesthost ratio is near the value defined for the levitation effect
[44]. Benzene adsorption in different ORTHO silicalite structures was analyzed to
determine the origin of a surprising factor of 3.1 difference in Henrys constants.
The results indicate that a slight change in the lattice oxygen atom positions can
74
reposition the sorbates enough to sizably affect the electrostatics. The small shifts
are magnified by the partial cancellation of large electrostatic terms on the hydrogen
and carbon atoms [45]. Binary adsorption was simulated in silicate for benzene/CH4
and benzene/cyclohexane mixtures. Benzene and cyclohexane display preferred siting in the channel intersections, while CH4 adsorbs preferentially in the channels. In
benzene/cyclohexane mixture, cyclohexane adsorbs in the intersections and benzene
is pushed to the zigzag channels [46]. Adsorption in silicalite from binary mixtures
of p-xylene, m-xylene, and toluene was investigated using simulation. Experimental
isotherms can be well reproduced if MFI is modeled in the para form, but not in
the native ortho form. This reveals that zeolite structure undergoes a transition from
ortho to para in the presence of aromatic molecules [47]. Using a nine-site model
for benzene, adsorption isotherms of benzene, propene, and their mixture in zeolites MOR, FAU, BEA, MFI, and MCM-22 were computed and in excellent accordance with measured results [48]. Benzene and benzene/thiophene mixtures were
studied in FAU, MFI, MOR, and Na-FAU using energy-biased GCMC, and the calculated isotherms and heats in Na-FAU were consistent with experiments [49, 50].
Adsorption properties of xylenes in X- and Y-FAU were reproduced by simulation
using a potential derived from Pellenq and Nicholson scheme. m-Xylene was found
to be adsorbed preferentially and the p-xylene/m-xylene selectivity predicted from
simulation was in good agreement with experiment [5153]. Preferential adsorption of o-xylene over p-xylene in AlPO4 -11 was predicted by simulations, agreeing
with experimental data. The selective adsorption comes from the smaller length of
o-xylene along the crystallographic c-axis in AlPO4 -11 compared to p-xylene, different from the case in AlPO4 -5 and AlPO4 -8 [54].
4.2.4 Cation-Exchanged Zeolites

A large number of simulation studies have been reported for adsorption in cationexchanged zeolites. Isotherms of H2 adsorption in Na-, Ni-, and Rh-exchanged XFAU were calculated at different temperatures and compared with measured data
[55]. Adsorption of alkanes in two different Na-MOR zeolites from simulation was
found to agree with experiment with the adequate inclusion of cations and realistic
charges in Al atoms [56]. CH4 , C2 H6 , and C3 H8 in Na-exchanged MFI and MOR
were simulated. The predicted positions of nonframework Na+ cations are in agreement with those determined by X-ray diffraction and so are the computed isotherms
and Henrys constants. Adsorption of alkanes is largely influenced by the position
and the density of nonframework ions [57]. For a given type of cation, adsorption
of alkanes in ZSM-5 was found to increase with decreasing density of the nonframework cations; for a given Si/Al ratio, adsorption increases with decreasing
atomic weight of the cation [58]. Isotherm and enthalpy of N2 adsorption in X-FAU
were simulated at ambient temperature, and qualitative agreement was observed
with experiments for a series of monovalent and divalent cations [59]. Adsorption
of CH4 in X- and Y-FAU was investigated using a newly derived force field in which
the Lennard-Jones parameters between CH4 and FAU were obtained by fitting the
75
potential energies from ab initio cluster calculations. The calculated isotherms and
enthalpies were in good agreement with those experimentally obtained [60]. Redistribution of nonframework cations was observed to occur upon adsorption of water
and aromatics in NaY, and in turn the selectivity of p-xylene over m-xylene was
enhanced by a fact of 4 [61].
Single- and binary-component adsorption of CO2 , N2 , and H2 in dehydrated
Na-4A was examined, and the strong selectivity for CO2 over both N2 and H2
was observed and also compared with that in MFI [62]. Supercritical CO2 adsorption in NaA and NaX was studied using GEMC, and the adsorption isotherms and
enthalpies were discussed in detail and compared with available measured data [63].
Combining experimental and simulation techniques, adsorption of N2 , O2 , and Ar
in Mn-exchanged zeolite-A and -X was studied. It was observed that the selectivity
of O2 over Ar was higher in both zeolite-A and -X [64]. Ar, N2 , and O2 in Naand Ca-exchanged LTA were studied both experimentally and theoretically. The
predicted isotherms match well with measured data and the extent of adsorption
increases with increasing Ca ions in LTA [65]. Selectivity of CO2 over N2 in flue
gas was found to rise remarkably in Na-ZSM-5, particularly at low pressures. This
is because CO2 has a large quadrupolar moment and its adsorption is enhanced due
to the electric field of cations [66]. Adsorption and enthalpy of CO2 in various types
of FAU including purely siliceous DAY, NaY, and NaLSX were simulated. Typical
arrangements of CO2 molecules were identified from low to high pressures [67].
Figure 4.2 shows that Na+ ions interact with a few CO2 molecules at a low pressure.
With increasing pressure, Na+ ions are more and more solvated by the surrounding CO2 molecules. Consequently, CO2 /NaY interaction slightly decreases due to
the solvation process, whereas CO2 /CO2 interaction increases. The combination of
these two contributions leads to a relatively constant value of adsorption enthalpy as
pressure rises [67]. CO2 adsorption was further simulated in LiY and NaY at various temperatures with Li+ CO2 interaction derived from ab initio calculations. The
results revealed two different types of adsorption behavior in NaY and LiY at 323
and 373 K, respectively [68].
Table 4.1 summarizes the simulation studies of adsorption for a wide variety of
guest molecules in different zeolites.
Fig. 4.2 Typical arrangements of CO2 molecules in NaY at (a) 0.1 bar, (b) 1 bar, and (c) 25 bar.
Na+ cations are represented in green, and the typical distances of NaOz and OOz are in .
Reproduced with permission from [67]. Copyright (2005) American Chemical Society
76

Table 4.1 Simulation studies of adsorption in zeolites
Guests
MFI
X-FAU
Y-FAU
Other zeolites
Computed
quantities
Rare gases
N2
[6976]
[74, 90]
[16, 7880]
[16, 78]
[8189]
[16, 77]
P, I, Q, K, S
P, I, Q, K, S
O2
[90]
[16, 77, 78]

[16, 78,
9193]
[16, 78,
9193]
[92]
[78]
CO
CO2
SF6
NH3
H2 O
Methane
Ethane
Propane
n-Butane
i-Butane
n-pentane
n-Hexane
Cyclohexane
n-Heptane
[94]
[76]
[17]
[26, 95]
[31, 70, 76, 90,
98101]
n-Octane
n-Nonane
[109, 110, 118]
n-Decane
[109112, 118]
Ethane/butane [106]
CF4
[76]
CF3 Cl
CF2 Cl2
CFCl3
CHF3
CHCl3
Isopropylamine
Acetonitrile
Benzene
[45, 125, 126]
o-Xylene
m-Xylene
p-Xylene
[125]
P, I, Q, K, S
[78]
[17]
[96]
[80]
[31, 32, 105,

106]
[31, 32, 105]
[32, 105,
109113]
[111, 114, 115]
[105, 109, 110,
116]
[32, 105, 109,
110, 114, 116]
[32, 105,
109111, 114,
116]
[109, 110, 118]
[16, 78]
[17]
[96, 97]
[76, 81, 83, 84,
86, 88, 98,
102104]
[103]
[103, 107, 108]

[87, 109, 110] [87, 103,
107110]
[109, 110]
[103, 107110]
P, I, Q, K, S
P, I, Q, K, S
P, I, Q, K, S
P, I, Q, K, S
P, I, Q, K, S
[87, 109, 110] [87, 107110,

114]
[117]
[87, 109, 110] [87, 107110,
114]
P, I, Q, K, S
[109, 110,
118]
[109, 110,
118]
[109, 110,
118]
[109, 110, 118]
P, I, Q, K, S
[109, 110, 118]
P, I, Q, K, S
[109, 110, 118]
P, I, Q, K, S
[119]
[76]
P, I, S
P, I, Q, S
P, Q, S
P, Q, S
P, Q, S
P, Q, S
P, Q, S
Q, S
P, S
P, I, Q, K, S
P, S
P, I, Q, S
[122]
[17]
[120]
[120]
[120, 121]
[120]
[120]
[122, 123]
[17]
[122, 127]
[127, 128]
[53]
[51, 52, 80,

128, 129]
[51, 52, 80,
128, 129]
[17]
[124]
[54, 128]
[53]
P, I, Q, K, S
P, I, Q, K, S
P, I, Q, K, S
Q, S
P, I, Q, K, S
P, I, Q, K, S
[54]
P, I, Q, K, S
P, I, Q, K, S
P, I, Q, S
77
Table 4.1 (continued)

Guests
Other alkylbenzenes
m-Dinitrobenzene
Phenol
Pyridine
MFI
X-FAU
Y-FAU
Other zeolites
Computed
quantities
[17]
P, I, Q, K, S
P, S
P, I, Q, K, S
Q, S
[130]
[126]
[17]
[17]
P : interaction energy, I: adsorption isotherm, Q: heat of adsorption, K: Henrys constant, S: structure of adsorbed phase.
4.3 Carbonaceous Materials

Carbon atoms can possess different extents of aromatic sp2 or aliphatic sp3
hybridization and have different bonding and ring structures. As a consequence,
there are several stable carbon forms ranging from naturally occurring bulk structures such as graphite, diamond, activated carbons [131] to discrete structures such
as fullerenes and nanotubes [132]. Among these, activated carbons and nanotubes
have been extensively studied as adsorbents for gas purification and separation.
4.3.1 Activated Carbons

Activated carbon is a synthetic carbonaceous material, constructed by thermal
decomposition and activation at elevated temperature. Activated carbon consists
of elementary graphitic crystallites and amorphous structures. In many theoretical
studies, the simplified carbon slit-like pores have been used to mimic activated carbons. Simulation of pure and mixed CH4 and CO2 adsorption in slit pores gave
results close to the measured data in A35/4 activated carbon [133]. CO2 /CH4 /N2
mixtures in slit pores showed that CO2 is preferentially adsorbed and the simulation results are consistent with the predictions from DFT at various temperatures
and pressures [134]. Adsorption of alkanes in slit pores was studied over a wide
range of temperature, pressure, alkane chain length, and slit width to evaluate their
effects. The behavior of long alkanes at high temperatures was found to be similar
to short alkanes at lower temperatures [135]. The performance of 1- and 5-site models of CH4 adsorption in slit pores was evaluated. Although the two models yield
comparable pore densities, the number of particles predicted by the 1-site model
is always greater, regardless of whether temperature is subcritical or supercritical
[136]. Adsorption and desorption of H2 O in a platelet model for activated carbon
were simulated. The model included the effects of structural disorder which are
missing in the slit pore model. Hysteresis observed was in good agreement with
experimental results [137]. Simulation of pentane isomers and their ternary mixtures
in a series of carbon nanoslits demonstrated competitive adsorption. With decreasing slit width, first shape selective adsorption occurs due to the configurational
78
entropy effect, followed by inverse-shape selective adsorption that occurs due to

the area entropy effect, and finally no adsorption occurs [138]. Using hypothetical C168 schwarzite to represent an amorphous nanoporous carbon, N2 , O2 , and
their mixtures were investigated by GCMC and GEMC simulations [139, 140]. In
addition to six-member rings, C168 schwarzite has some seven-member rings rather
than five-member rings as in buckyball C60 . The curvatures of C168 and amorphous
nanoporous carbon are similar; therefore, C168 may provide a similar environment
for adsorbates as that found in real samples. The predictions of mixture adsorption
using IAST based solely on the adsorption of pure gases agree well with simulation results. The energetic effect, by itself, cannot explain the large difference in the
permeation rates of O2 and N2 observed experimentally. The entropic effect, which
arises due to the size difference, is the dominant factor for the large selectivity favoring O2 over N2 [141].
4.3.2 Carbon Nanotubes

A carbon nanotube (CNT) can be envisaged as a cylinder rolled from a graphene
sheet and exists in three types, namely armchair, zigzag, and chiral. In 1991, Iijima
discovered the first CNT [142] and has ever since triggered extensive interest in
CNTs for a variety of applications. A number of earlier simulation studies were
carried out in CNTs for the adsorption of N2 , O2 , CO2 , Ar, Kr, Xe, CH4 , etc. The
adsorption isotherms of N2 [143], Xe [144], CH4 , and C2 H6 [145] were found to be
of type I regardless of temperature, inconsistent with experimentally observed type
II at subcritical temperatures. This is because the infinite periodic CNT bundles
were used in these simulations; however, real CNT samples have finite diameters.
As a result, the external surface of the finite CNT bundle was not included, which
is available for gas adsorption as evidenced experimentally by gas adsorption on
closed-ended CNTs.
A handful of simulations were carried out to examine the role of external surface
of CNT bundle on adsorption. Gas molecules were observed to form a quasi-onedimensional phase in the grooves at low pressures, whereas a three-stripe phase
parallel to the grooves at high pressures, followed by monolayer and bilayer phases.
The adsorption isotherms were predicted to be type II, consistent with experiment
[146148]. This suggests that the external surface must be accounted for to correctly
predict adsorption in CNTs. The role of external surface was thoroughly exploded
for N2 adsorption in two types of single-walled CNT bundles, as shown in Fig. 4.3
[149]. In the infinite periodic bundle, adsorption follows type I at both sub- and
supercritical temperatures and occurs inside CNTs, first at the annuli and then at the
centers. In the finite isolated bundle, adsorption follows type II at subcritical temperatures, as observed experimentally. Adsorption occurs first at the annuli and then
at the grooves. At high pressures, adsorption also occurs at the ridges surrounding
CNTs and at the centers, and on the external surface at still higher pressures. As
temperature increases from sub- to supercritical, adsorption in the finite isolated
bundle changes from type II to type I [149]. Adsorption of N2 and O2 mixture was
79
Fig. 4.3 Energy contours of a nitrogen atom along the xy plane in (a) periodic infinite bundle and
(b) isolated finite bundle. The vdW gap between CNTs is 3.2 . Adapted with permission from
[149]. Copyright (2003) American Physical Society
further studied in the two types of CNT bundles mentioned above. The selectivity
depends strongly on temperature but only weakly on the type of the bundle, and air
might be separated by competitive adsorption in CNT bundles [150].
Simulation of CO2 trapped in CNT bundles showed a sequential filling of adsorption sites in CNT with the interstitial sites preceding endohedral sites. The drastic
changes predicted from simulation in the binding energy distributions and density
profiles qualitatively explained the frequency shifting, broadening, and integrated
intensity changes in experimental infrared spectra [151]. Adsorption of an equimolar CO2 /CH4 mixture was determined in five CNTs with various diameters to investigate the effects of temperature, pressure, and pore size. The results revealed that
pressure and temperature have little effect, in contrast to the pore size [152]. CH4
adsorption was examined in triangular bundles of armchair CNTs with the vdW gap
varying from 0.335 to 1.0 nm. The results demonstrated that (15,15) CNT bundle
with the vdW gap of 0.8 nm is optimal for CH4 storage at 300 K [153]. Adsorption
and separation of linear and branched alkanes in CNTs were studied at room temperature. The results suggested the possible separation of alkane mixtures based on
difference in either size or configuration, as a consequence of competitive adsorption [154]. Shape and inverse-shape selectivity were observed for C5 isomers in
CNTs and the tube size was identified to be crucial as to which type of selective
adsorption might occur. In (7,7) CNT, inverse-shape selective adsorption occurs due
to the length entropy effect, whereas in large-size CNT, shape selective adsorption
occurs due to the configurational entropy effect [155].
Real CNT samples consist of heterogeneous rather than homogeneous bundle.
Shi and Johnson proposed an optimization method to construct a heterogeneous
CNT bundle with different diameters, as illustrated in Fig. 4.4. At low coverages,
simulated isosteric heats in the heterogeneous bundle were consistent with experimental data. In contrast, the isosteric heats in the homogeneous bundle were about
25% lower. Therefore, an accurate description of adsorption in CNT bundle must
80
(a)
(b)
Fig. 4.4 (a) A heterogeneous CNT bundle. (b) Isosteric heat for Ar. Circles and triangles are
experiments, diamonds (squares) are simulations in the heterogeneous (homogeneous) bundles.
Reproduced with permission from [156]. Copyright (2003) American Physical Society
account for the heterogeneity [156]. Displacement of CO2 by Xe was simulated in

the heterogeneous bundle also. The spectral information constructed from simulation qualitatively reproduced experimental intensity. The good agreement between
simulation and experiment suggested that the adsorption sites associated with the
intensity peaks and changes upon Xe exposure are the consequence of CO2 being
displaced from the sites [157].
4.3.3 H2 Storage
High-capacity H2 storage is an essential prerequisite for the widespread deployment of next-generation fuel cells, particularly in portable devices and future automobiles. Considerable research has been undertaken over the past two decades to
determine H2 capacity in different carbon structures like activated carbons, carbon nanofibers, and CNTs. Experimental studies have been reviewed recently by
a few researchers [158161]. H2 storage in primitive, gyroid, diamond, CNT, and
quasi-periodic icosahedral nanoporous carbons was examined by simulation. None
of these satisfies storage target, except the quasi-periodic icosahedral nanoporous
carbon, which could accommodate 6 wt% H2 at 3.8 MPa and 77 K but the volumetric density does not exceed 24 kg/m3 [162]. It is clear from this work that the
geometry of carbon surface can enhance capacity only to a limited extent, and the
combination of most effective structure with appropriate additives should be incorporated to improve capacity. H2 adsorption in CNTs was simulated at 293 K and
77 K with an effective quantum potential derived from the FeynmanHibbs perturbative approach [163, 164]. The capacity at 298 K predicted by quantum simulation
is several percent smaller than that by classical simulation, and the quantum effect
contributes 1520% of adsorption amount at 77 K. Carbon nanohorn (CNH) is a
81
tube of typically 26 nm in diameter and 4050 nm long and has a conical cap at
one end. H2 isotopes in CNHs were simulated at 77 K, and the adsorption, incorporating quantum effect through the FeynmanHibbs potential, was predicted to be
in good agreement with experimental results [165]. This indicates that the quantum effect at 77 K is accurately represented by the FeynmanHibbs potential. The
effects of size, vdW gap, and CNT arrangement were investigated on H2 adsorption. Interestingly, it was observed that the size of CNT has significant influence
on the amount adsorbed inside CNT and distribution in the vicinity of CNT wall,
regardless of the type of CNT and vdW gap [166].
To enhance H2 storage capacity in CNTs, several approaches such as element
doping [167], incorporating defects, spilling over [168], changing the size and gap
of CNTs [166], introducing heteroatoms [169] as well as using silicon nanotubes
(SiNTs) [170] were proposed. Both N and B doping in single-walled CNTs decrease
H2 adsorption energy. The effect of alkali doping on H2 adsorption was simulated by
incorporating K or Li ions into CNT arrays. H2 capacity was found to be 3.95 wt%
with K doping and 4.21 wt% with Li doping, in fairly good agreement with the
experimental data determined at room temperature and 100 atm [171]. There is a
considerable increase in H2 binding energy by a factor of 50% in the presence of
structural defects in CNTs, which in turn enhances capacity [172]. H2 adsorption in
SiNTs was studied at 298 K over pressure range from 1 to 10 MPa. SiNTs exhibit
a stronger attraction to H2 both inside and outside the tube compared to the isodiameter CNTs; consequently, the capacity in SiNTs is enhanced [170]. Carbon nanoscroll (CNS) structure is formed by jelly roll-like wrapping of a graphene sheet.
H2 adsorption in CNSs was found to reach 5.5 wt% at 150 K and 1 MPa. Doping
alkali in CNSs leads to H2 capacity of 3 wt% at ambient temperature and pressure
[173, 174]. Recent analysis of thermodynamic constraints for H2 adsorption with a
focus on porous carbon suggested that an optimal adsorption enthalpy of 15 kJ/mol
is required to meet H2 storage target at room temperature. The enthalpy in most
carbon structures is about 46 kJ/mol, too weak to satisfy the desired goal for H2
storage at ambient temperature. Structural modification of carbon revealed the complex relationship between adsorption enthalpy, pore volume, and the amount of H2
stored. It was observed that increasing adsorption enthalpy might reduce storage as
well as delivery [175].
Numerous studies investigated the interaction of H2 with CNTs using quantum mechanics methods. Periodic DFT calculations of H2 chemisorption in CNTs
showed two chemisorption sites, one inside and the other outside. H2 capacity in
an empty space increases linearly with CNT diameter, and the maximum capacity
is limited by the repulsive energies between H2 molecules inside CNT and those
between H2 molecules and CNT wall [176]. Ab initio calculations in a cleaved cluster model revealed that boron nitride nanotubes are preferable to CNTs for H2 storage due to their heteropolar binding nature of their atoms. In addition, more efficient
binding energy can be achieved by increasing nanotube diameter or equivalently
decreasing the curvature [177]. H2 physisorption inside and outside achiral CNTs
was examined with the CNTs modeled as curved coronene-like (C24 H12 ) graphene
sheets. It was found that physisorption depends mainly on CNT diameter being
82
virtually independent of chirality [178]. Another commonly used method is the

two-level quantum mechanics/molecular mechanics (QM/MM) approach, in which
a system is divided into two different sections; the inner section is treated by a
high-level QM method and the outer section by MM method. With this method, H2
binding to the side of a (10,0) CNT was studied, in which B3LYP hybrid functional
was used for the accurate calculation of reaction sites, while the universal force field
(UFF) was used to describe the neighboring atoms [179]. This approach was also
applied to a (4,4) CNT with 200 atoms by treating 64 carbon atoms and 32 hydrogen atoms in the inner section with a high-level theory and the outer section with a
low-level theory. This study was focused on H2 coverage in CNT and the intercalation of H2 inside CNT [180]. Recently, Froudakis reviewed the existing theoretical
literature on H2 adsorption in CNTs, in which the importance of simulations for
understanding H2 adsorption mechanism and for improving storage capacity was
underlined, and the advantages and disadvantages of both statistical and quantum
mechanics modeling were discussed [181].
4.4 Hybrid Frameworks

Novel hybrid inorganicorganic porous materials have been recently developed,
most notably, the metalorganic frameworks (MOFs) synthesized by Yaghi and
coworkers [182]. The primary building blocks in MOFs (also known as coordination
networks or coordination polymers) are metal-oxide clusters and organic linkers.
MOFs possess extremely high porosities (up to 90%) and large surface areas (from
500 to 6500 m2 /g). The controllable length of organic linker and the variation of
metal oxide allow for tailoring the functionality, pore volume, and size over a wide
atomic-scale range, as shown in Fig. 4.5 [183]. In contrast to the spherical or slitshaped pores usually observed in carbon and zeolite materials, MOFs incorporate
crystallographically well-defined pores including squared, rectangular, triangular,
and window-connected cages. Therefore, MOFs provide a wealth of opportunities
for engineering new functional materials with tunable properties [184].
4.4.1 Light Gases

In conjunction with experiment, simulation was performed to investigate the porefilling mechanism of Ar in Cu-BTC. The results agreed quantitatively with experimental isotherm up to almost complete filling of the pore network [185]. Similarly,
the predicted positions and occupancies of Ar adsorption in IRMOF-1 were found
to match well with experiments [186]. Binding energies of Ar, N2 , O2 , CH4 , C2 H6 ,
and C3 H8 were computed separately. The most preferred site is near the metaloxide cluster in the cavity where the organic linker points outward, the second preferred site is where the linker points inward, and the least preferred site is above
and beneath the linker [186]. Adsorption of nonpolar gases like CH4 , N2 , and O2
was extensively studied in MOFs, particularly IRMOF-1. Different MOFs were
83
Fig. 4.5 IRMOF-n (n = 16) structures. Zn (blue polyhedra), O (red spheres), C (black spheres),
Br (green spheres in 2), amino groups (blue spheres in 3). The large yellow spheres represent
the largest vdW spheres that would fit into the cavities without touching the frameworks. Reproduced with permission from [183]. Copyright (2002) American Association for the Advancement
of Science
characterized for CH4 storage and compared with MCM-41, zeolites, and CNTs.
The complex interplay of various factors that affect CH4 adsorption was uncovered
and new, not yet synthesized, MOFs were proposed [187]. Adsorption of He, Ar, H2 ,
and CH4 was examined in various MOFs, including Cu-BTC, IRMOF-1, IRMOF6, IRMOF-8, IRMOF-14, MOF-2, MOF-3, and Cu-MMOM, and good agreement
was observed between simulations and experiments for a number of cases and very
poor agreement in other cases [188]. Simulation was performed on CH4 adsorption
in a series of MOFs. The accessible surface area and the free volume were found to
play a major role in adsorption at 298 K and moderate pressures [189]. From simulated adsorption isotherms of N2 , the BET surface areas of microporous MOFs were
found to agree very well with the accessible surface areas estimated in a geometric fashion directly from the experimental crystal structures. In addition, the surface
areas matched well with experimental reports in the literature. These results provide
a strong validation that BET theory can be used to obtain surface areas of MOFs
[190].
Mixture separation of CH4 and nC4 in IRMOFs was investigated to study the
influence of organic linkers. The predicted selectivity was as good as or better than
experimentally observed selectivity in other adsorbents, suggesting that IRMOFs
are promising for hydrocarbon separation [191]. Adsorption of a mixture of pentane isomers in IRMOF-1 was simulated. Each isomer exhibits increased extent
of adsorption with rising pressure, though there is less adsorption of the branched
isomer due to the configurational entropy effect. Compared to CNT bundle and MFI,
84
the adsorption selectivity in IRMOF-1 is smaller [192]. Gas mixtures containing

CO2 , CH4 , C2 H6 in Cu-BTC were studied, and it was observed that the selectivity
of CO2 over CH4 increases due to the electrostatic interaction between CO2 and
the framework [193]. Mixture adsorption of CO2 and CH4 , H2 simulated in CuBTC and IRMOF-1 showed that the geometry, the pore size, and the electrostatic
interaction in MOFs largely affect separation efficiency [194].
4.4.2 CO2 Storage

The combustion of fossil fuels such as coal and petroleum has generated a huge
amount of greenhouse gas CO2 . This has substantially led to severely adverse
impacts on environment like air pollution and global warming. One of the technically feasible approaches for CO2 sequestration is to use porous media, and CO2
storage in MOFs has been explored using molecular simulations. Adsorption in
three different types of materials silicalite, C168 schwarzite, and IRMOF-1
revealed that IRMOF-1 has the largest adsorption capacity for CO2 [195]. A different class of MOFs, based on the assembly of presynthesized molecular building
units, were produced and named as MIL (Material Institut Lavoisier) series. Simulation of CO2 in MIL-53 and MIL-47 confirmed that there is a structural interchange between large and narrow pore forms of MIL-53, but not in MIL-47 [196].
CO2 adsorption was simulated in IRMOF-1 at five different temperatures and in
IRMOF-3 and MOF-177 at 298 K. The results matched well with experimental data
and suggested that the attractive electrostatic interactions between CO2 molecules
are responsible for inflections and steps observed in the adsorption isotherms [197].
A computational study of CO2 storage was reported in MOFs with various linkers,
pore sizes, and topologies. The capacity was a complex interplay of these structural
properties, and the suitable pore size was found to be between 1.0 and 2.0 nm [198].
CO2 storage in a series of MOFs was simulated systematically and compared with
those in CNT and Na-exchanged ZSM-5 [199]. Figure 4.6 (left) shows the snapshot
for CO2 adsorption in IRMOF-1 and Fig. 4.6 (right) shows the adsorption isotherms
in different MOFs. The organic linkers play a critical role in tuning the free volume and accessible surface area, which largely determine the CO2 adsorption at
high pressures. As a combination of the high capacity and low framework density,
IRMOF-10, IRMOF-14, and UMCM-1 were identified to be the best among those
studied and even surpass the experimentally reported highest capacity in MOF-177.
The simulation showed that the larger the surface area and pore volume, the higher
the storage capacity achieved. Various factors like surface area, free volume, porosity, and framework density were found to correlate well with CO2 capacity near
saturation [199].
4.4.3 H2 Storage
H2 adsorption in MOFs has been extensively simulated toward the development of
new storage media. A study of H2 in IRMOF-1, IRMOF-8, and IRMOF-18 showed

IRMOF-1
Mg-IRMOF1
Be-IRMOF1
IRMOF1-(NH2)4
IRMOF10
IRMOF13
IRMOF14
UMCM-1
40
Nex(mmol/g)
85
30
20
10
0
1000
2000
3000
P(kPa)
4000
5000
Fig. 4.6 (left) Snapshot of CO2 adsorbed in IRMOF-1 at 300 K and 2000 kPa. (right) Excess
adsorption isotherms of CO2 in different MOFs versus bulk pressure. Reproduced with permission from [199]. Copyright (2008) American Chemical Society
that metal-oxide clusters are the preferential adsorption sites for H2 and the effect of
organic linkers becomes evident with increasing pressure [200]. Simulation of H2
in 10 noninterpenetrating MOFs revealed that H2 uptake correlates well with isosteric heat at low pressures and with the surface area and free volume at intermediate
and high pressures [201]. In interpenetrating MOFs, the small pores generated by
catenation play a primary role in densely confining H2 molecules so that the capacity is higher in interpenetrating frameworks than in noninterpenetrating frameworks
[202]. The interactions between H2 and MOFs were artificially increased in simulation to learn the degree to which the isosteric heat must be increased to meet
the current target for H2 storage. H2 density within the free volume of materials
provided a useful insight and yielded a graph for the required isosteric heat as a
function of the free volume to meet the storage target at room temperature and
120 bar [203].
A number of theoretical studies on the interactions between H2 and MOFs based
on quantum mechanics have been reported. Generally, metal-oxide sites bind H2
more strongly (78 kJ/mol) than do organic linkers (45 kJ/mol). But as the available volume of the metal-oxide sites is small, they tend to be saturated quickly, while
organic linkers play a more crucial role at higher pressures [204]. The stronger H2
binding observed at the metal-oxide sites can be attributed to the electrostatic and,
possibly, orbital donation interactions, while the vdW interactions dominate at the
organic linkers [205]. Several polar aromatic linkers of MOFs were examined to predict H2 binding using DFT theory, and the computed binding energies were in good
agreement with experiments [206]. With the approximate resolution of identity MP2
(RI-MP2) and triple-zeta valence basis set, H2 binding energies were calculated with
various substituted benzenes like C6 H6 , C6 H5 F, C6 H5 OH, C6 H5 NH2 , C6 H5 CH3 ,
and C6 H5 CN, in which the substituted benzenes were treated as simplified subunits of the organic linkers in MOFs. The interaction energy with C6 H5 NH2 was
86
found to be the strongest (4.5 kJ/mol) [207]. Similarly, the binding energies were
estimated by MP2 with the metal oxide and organic linker in IRMOF-1. GCMC
simulation identified a high-energy binding site at the corner that quickly saturated with 1.27 H2 molecules at 78 K, whereas a broad range of binding sites were
observed at 300 K [208]. Various IRMOFs such as IRMOF-1, IRMOF-3, IRMOF4NH2 , IRMOF-6, IRMOF-8, IRMOF-12, IRMOF-14, IRMOF-18, and IRMOF-993
were studied using RI-MP2. The highest binding energy was found in IRMOF4NH2 , even higher than in polybenzoid structures such as IRMOF-14 and IRMOF993 [209]. A significant enhancement of H2 uptake in Li-decorated IRMOF-1 was
revealed with 2.9 wt% at 200 K and 2.0 wt% at 300 K. Two Li atoms strongly adsorb
on the surfaces of six-carbon rings, one on each side. Each Li atom can cluster three
H2 molecules with a binding energy of 12 kJ/mol [210]. Using both DFT theory and
MP2 calculations, the interaction energies of H2 adsorption with benzenoid molecular linkers in MOFs were computed. Both the local-density and the generalizedgradient approximated DFT methods were inaccurate in predicting binding energy
but gave a qualitatively correct prediction [211]. A strong correlation was demonstrated between H2 surface density and coordinatively unsaturated metal centers
in MOFs. Quantum mechanical calculations were performed to estimate the shortest distance achievable between H2 molecules, thereby defining the surface area
requirements for MOFs that can reach the target for H2 storage [212].
Table 4.2 summarizes the simulation studies of adsorption for a wide variety of
guest molecules in different MOFs.
4.4.4 New Hybrid Frameworks

A recent breakthrough in the development of hybrid frameworks is the crystalline,
porous, covalent organic frameworks (COFs) [220223]. Solely synthesized from
light elements like B, C, O, and H, COFs consist of the organic linkers covalently
bonded with boron-oxide clusters and have high thermal stability, large surface area,
and porosity. These boron-oxide clusters can be regarded as analogous to the metaloxide clusters in MOFs. Composed of light elements, however, COFs have even
lower density than MOFs. Currently, very few simulation studies have been reported
for COFs. Adsorption isotherms of Ar, CH4 , and H2 in COF-102, -103, -105, and
-108 were simulated, in which COF-102 and COF-103 showed greater affinity for
CH4 due to the compact atomic structures [223]. CO2 storage in various 3D, 2D,
and 1D COFs structures was simulated, and exceptionally high capacity in COF-105
and -108 was observed. The gravimetric and volumetric capacities at 30 bar correlated well with various factors such as framework density, free volume, porosity,
and surface area [224]. Another breakthrough is the invention of zeolitic imidazolate frameworks (ZIFs) [225]. ZIFs have high thermal and chemical stability like
zeolites and also high porosity and pore functionality like MOFs. Similar to MOFs,
ZIFs showed promising storage and separation capacity [226, 227]. At the time of
preparing this chapter, we were not aware of any reported simulation work in ZIFs.
87
Table 4.2 Simulation studies of adsorption in MOFs

Computed
quantitiesb
References
P, I, S
P, I, Q, S
P, I, S
P, I, Q, K, S, A, F
[186, 188, 213]

[186, 214]
[214]
[193197, 199, 214, 215]
P, I, Q, K, S
[187, 191193, 195, 216]
P, I, Q, K, S
P, I, Q, K, S
P, I, Q, K, S
[192]
[192, 217]
[191, 192, 217]
P, I, Q, K, S
P, I
P, I
P, I
P, I
P, I, S
P, I, S
P, I, S
P, I, Q, S
P, I, S
P, I, S
P, I, S
[192]
[218]
[218]
[218]
[218]
[191]
[194]
[193, 195]
[214]
[192]
[192]
[219]
M1, M4
P, I, S
[219]
M1, M4
P, I, S
[219]
Guests
Hostsa
Ar
N2
O2
CO2
M1, Cu-BTC, MI
M1, Cu-BTC
Cu-BTC
M1-10, MOF-177,
Cu-BTC,
UMCM-1,MI, ML1,
ML2, ML3, ML4,
F-MOF1
M1, M3, M5, M6, M9,
M10, ML1, Cu-BTC,
CPL-2, CPL-5, MI,
CU1, CU2
M1
M1, MM1
M1, M5, M6, M7, M8,
MM1
M1
M1
M1
M1
M1
M1, M4, M5, M8, M9
M1, Cu-BTC
M1, Cu-BTC
Cu-BTC
M1
M1
M1, M4
Methane
Ethane
Propane
n-Butane
i-Butane
n-Pentane
n-Hexane
Cyclohexane
n-heptane
Methane/butane
CO2 /CH4 /H2
CO2 /CH4
CO2 /N2 /O2
C1 C5 alkanes
C5 isomers
n-Butane/2methylpropane
n-Pentane/2methylbutane
n-Hexane/2methylpentane
a M1: IRMOF-1, M2: IRMOF-3, M3: IRMOF-4, M4: IRMOF-6, M5: IRMOF-8, M6: IRMOF10, M7: IRMOF-11, M8: IRMOF-13, M9: IRMOF-14, M10: IRMOF-16, MI: manganese formate,
ML1: MIL-53, ML2: MIL-47, ML3: MIL-100, ML4: MIL-101, MM1: Cu (hfipbb) (H2 hfipbb),
CU1: Cu(SiF6 )(bpy)2 , CU2: Cu(GeF6 )(bpy)2 .
b I: adsorption isotherm, Q: heat of adsorption, K: Henrys constant, A: accessible surface area, F:
free volume, P: interaction energy, S: structure in adsorbed phase.
4.5 Outlook
We have reviewed the recent simulation studies of adsorption for a wide variety
of guest molecules in three important classes of nanoporous materials zeolites,
carbons, and hybrid frameworks. The contents reviewed are representative rather
than exhaustive. From simulations, useful adsorption properties, such as binding
88
sites, interaction energies, isosteric heats, isotherms, and separation factors, can be
obtained and compared with available experimental data. It is important to note that,
given a material, the accuracy of simulation is primarily determined by the guest
framework interactions [228]. In a large number of simulation studies, the empirical
force fields have been used. For example, classical Kiselev [78] and Steele [229]
potentials are commonly used for zeolites and carbon materials, respectively. For
MOFs, the universal [230] and Dreiding [231] force fields are often used. These
force fields were constructed by fitting to some experimental data over a limited
range of conditions with certain empirical rules. Their semiempirical nature may
lead to inaccurate predictions. A more rational way is to calculate guestframework
interactions from the first-principles methods. DFT has been widely used in solidstate materials; however, it fails to describe the weak physisorption interactions
because the dispersion forces are not properly accounted for in the DFT theory.
A major obstacle to calculate the guestframework interactions is that high-level
methods are usually required, but they are computationally very expensive, particularly for large structures. Consequently, cost-effective hierarchical approaches are
adopted as a compromise of accuracy and speed.
Most simulation studies on adsorption have used rigid frameworks. This allows
the use of grid-interpolation techniques to compute the interactions between guest
molecules and framework very efficiently. Such a simplified treatment is usually
acceptable but cannot reproduce structural changes that might occur upon adsorption. The effect of framework flexibility on hydrocarbon adsorption in silicalite was
examined. At low loadings, the effect is small but seems to be increasingly larger at
high loadings [232]. In contrast to the relatively rigid zeolitic and carbon structures,
adsorption in MOFs could easily cause structural transformation due to the existence of organic linkers. For example, a hysteresis was observed in a pillared-layer
MOF, which undergoes expansion and contraction (27.9% reduction in cell volume)
during adsorption and desorption [233]. However, most simulation studies scarcely
include the flexibility of MOFs. H2 O in IRMOF-1 examined by molecular dynamics simulation with a flexible force field revealed that IRMOF-1 is stable at very low
H2 O content but unstable upon exposed to 4% H2 O [234]. Exceptionally negative
thermal expansion in IRMOFs was explored and two competing effects were identified. One is a local effect where all bond lengths increase with temperature and
a long-range effect where the thermal movement of the linker molecules leads to a
shorter average distance between corners upon heating [235].
The review is focused mainly on adsorption. To further elucidate fluid behavior
in porous media, however, dynamic diffusion should be synergistically incorporated
[236]. Similar to adsorption, a wealth of simulation studies have been reported for
diffusion in various porous materials. Diffusion of CH4 , CO2 , and N2 in silicalite
was simulated over a wide range of occupancies and compared with experimental
data [237, 238]. Comparison of the self-diffusivities of CH4 /CF4 mixture in silicalite
was conducted between simulation and NMR experiment, and good agreement was
found [239]. A dynamically corrected transition-state theory was used in simulation to quantitatively compute the self-diffusivity of adsorbed molecules in confined
systems at nonzero loading [240]. Diffusion of various gases (He, Ne, Ar, Kr, H2 ,
89
N2 , CO2 , and CH4 ) was investigated in six all-silica zeolites MFI, AFI, FAU, CHA,
DDR, and LTA [241]. The self- and transport diffusivities of light gases like H2 ,
CH4 , Ar, and Ne were simulated in CNTs and in zeolites with comparable pore
sizes. It was found that diffusion in CNTs is 13 orders of magnitude faster [242,
243]. Mass transport of O2 , N2 , and their mixture in a CNT demonstrated that a
good kinetic selectivity could be achieved for air separation by carefully adjusting
the upstream and downstream pressures [244]. Self- and transport diffusions of light
gases in MOF-2, MOF-3, MOF-5, and Cu-BTC as a function of pore loading were
found to be in the same order of magnitude as in silicalite [245]. Simulation of benzene in IRMOF-1 revealed that the diffusion and the activation energy of benzene
are considerably smaller in a flexible framework compared to a rigid one [246]. Diffusion and separation of CO2 and CH4 in silicalite, C168 schwarzite, and IRMOF1 were examined. The predictions of self-, corrected-, and transport diffusivities
from the MaxwellStefan formulation match well with the simulation results [247].
A critical appraisal of current estimation methods was presented to predict binary
mixture diffusions in a large number of porous materials, including zeolites (MFI,
AFI, TON, FAU, CHA, DDR, MOR, and LTA), CNTs, titanosilicates (ETS-4), and
MOFs (IRMOF-1 and Cu-BTC) [248].
In summary, molecular simulations have substantially enhanced the current state
of knowledge for guest molecules in nanoporous materials. Fundamental insight has
been provided to bridge the large gap between microscopic and macroscopic properties in the nanodomain. On the basis of molecular description, structureproperty
and function relations can be developed toward high-efficacy material screening.
Molecular simulations thus facilitate and accelerate the intelligent design of new
porous materials with novel topological and compositional characteristics for industrially important applications.
Acknowledgments The authors are grateful for the support from National University of
Singapore (Grants R-279-000-198-112/133 and R-279-000-243-123).
References
1. Rouquerol F, Rouquerol J, Sing K, Adsorption: By Powders and Porous Solids, Academic
Press: London, 1999
2. Henderson D, (ed.), Fundamentals of Inhomogeneous Fluids, Marcel Dekker: New York,
1992
3. Lowen H (2002) Density functional theory of inhomogeneous classical fluids: recent developments and new perspectives. J Phys Condens Matter 14:1189711905
4. Wu JZ (2006) Density Functional Theory for Chemical Engineering. AIChE J 52:11691193
5. Ye ZC, Chen HY, Liu HL, Hu Y, Jiang JW (2007) Density functional theory for copolymers
confined in a nanoslit. J Chem Phys 126:134903
6. Chen HY, Ye ZC, Cai J, Liu HL, Hu Y, Jiang JW (2007) Hybrid density functional theory
for homopolymer mixtures confined in a selective nanoslit. J Phys Chem B 111:59275933
7. Li ZD, Cao DP, Wu JZ (2005) Layering, condensation, and evaporation of short chains in
narrow slit pores. J Chem Phys 122:224701
8. Chakraborty A (ed.), Molecular Modeling and Theory in Chemical Engineering, Academic
Press: San Diego, 2001; Vol. 28
90
9. Allen MP, Tildesley DJ, Computer Simulation of Liquids, Clarendon Press: Oxford, 1987
10. Frenkel D, Smit B, Understanding Molecular Simulations: From Algorithms to Applications, 2nd ed., Academic Press: San Diego, 2002
11. Nicholson D, Parasonage NG, Computer Simulation and the Statistical Mechanics of
Adsorption, Academic Press: New York, 1982
12. Panagiotopoulos AZ (1987) Direct determination of phase coexistence properties of fluids
by Monte-Carlo simulation in a new ensemble. Mol Phys 61:813826
13. Barrer RM, Zeolites and Clay Minerals as Sorbents and Molecular Sieves, Academic Press:
London, 1978
14. Breck DW, Zeolite Molecular Sieves, Wiley: New York, 1978
15. Fuchs AH, Cheetham AK (2001) Adsorption of guest molecules in zeolitic materials: Computational aspects. J Phys Chem B 105:73757383
16. Watanabe K, Austin N, Stapleton MR (1995) Investigation of the air separation properties of zeolites type-a, type-X and type-Y by Monte Carlo simulations. Mol Simul
15:197221
17. Teraishi K, Akanuma K (1997) Zeolite acidity ranking by the frameworksorbate interaction
energy simulation. Micro Mat 11:185194
18. Heuchel M, Snurr RQ, Buss E (1997) Adsorption of CH4 CF4 mixtures in silicalite: simulation, experiment, and theory. Langmuir 13:67956804
19. Czaplewski KF, Snurr RQ (1999) Hierarchical approach for simulation of binary adsorption
in silicalite. AIChE J 45:22232236
20. Siperstein F, Myers AL, Talu O (2002) Long range corrections for computer simulations of
adsorption. Mol Phys 100:20252030
21. Maurin G, Bell R, Kuchta B, Poyet T, Llewellyn P (2005) Adsorption of non polar and
quadrupolar gases in siliceous faujasite: Molecular simulations and experiments. Adsorption
11:331336
22. Vitillo JG, Ricchiardi G, Spoto G, Zecchina A (2005) Theoretical maximal storage of hydrogen in zeolitic frameworks. Phys Chem Chem Phys 7:39483954
23. Goj A, Sholl DS, Akten ED, Kohen D (2002) Atomistic simulations of CO2 and N2
adsorption in silica zeolites: The impact of pore size and shape. J Phys Chem B 106:
83678375
24. Leyssale JM, Papadopoulos GK, Theodorou DN (2006) Sorption thermodynamics of CO2 ,
CH4 , and their mixtures in the ITQ-1 zeolite. J Phys Chem B 110:2274222753
25. Di Lella A, Desbiens N, Boutin A, Demachy I, Ungerer P, Bellat JP, Fuchs AH (2006)
Molecular simulation studies of water physisorption in zeolites. Phys Chem Chem Phys
8:53965406
26. Trzpit M, Soulard M, Patarin J, Desbiens N, Cailliez F, Boutin A, Demachy I, Fuchs
AH (2007) The effect of local defects on water adsorption in silicalite. Langmuir
23:1013110139
27. Puibasset J, Pellenq RJM (2008) Grand canonical Monte Carlo simulation study of water
adsorption in silicalite at 300 K. J Phys Chem B 112:63906397
28. Siepmann JI, Frenkel D (1992) Configurational-bias Monte Carlo: A new sampling scheme
for flexible chains. Mol Phys 75:5970
29. Frenkel D, Mooij GCAM, Smit B (1992) Novel scheme to study structural and thermal
properties of continuously deformable molecules. J Phys: Condens Matter 4:30533076
30. de Pablo JJ, Laso M, Suter UW (1992) Simulation of polyethylene above and below the
melting point. J Chem Phys 96:23952403
31. Smit B, Siepmann JI (1994) Simulating the adsorption of alkanes in zeolites. Science
264:11181120
32. Smit B, Maesen TLM (1995) Commensurate freezing of alkanes in the channels of a zeolite.
Nature 374:4244
33. Ndjaka JMB, Zwanenburg G, Smit B, Schenk M (2004) Molecular simulations of adsorption
isotherms of small alkanes in FER-, TON-, MTW- and DON-type zeolites. Micro Mesop
Mat 68:3743
91
34. Zhang D, Liu Z, Xu R (2007) Monte Carlo simulation of the adsorption of C2 C7 linear
alkanes in aluminophosphate AlPO4-11. Mol Simul 33:12471253
35. Granato MA, Vlugt TJH, Rodrigues AE (2007) Molecular simulation of propanepropylene
binary adsorption equilibrium in zeolite 13X. Ind Eng Chem Res 46:72397245
36. Granato MA, Vlugt TJH, Rodrigues AE (2007) Molecular simulation of propanepropylene
binary adsorption equilibrium in zeolite 4A. Ind Eng Chem Res 46:321328
37. Pascual P, Ungerer P, Tavitian B, Pernot P, Boutin A (2003) Development of a transferable
guesthost force field for adsorption of hydrocarbons in zeolites I. Reinvestigation of alkane
adsorption in silicalite by grand canonical Monte Carlo simulation. Phys Chem Chem Phys
5:36843693
38. Pascual P, Ungerer P, Tavitian B, Boutin A (2004) Development of a transferable guesthost
force field for adsorption of hydrocarbons in zeolites. II. Prediction of alkenes adsorption
and alkane/alkene selectivity in silicalite. J Phys Chem B 108:393398
39. Pascual P, Boutin A (2004) Adsorption of hydrocarbons in zeolites from molecular simulations. The alkaneferrierite system revisited. Phys Chem Chem Phys
6:20152017
40. Schenk M, Smit B, Maesen TLM, Vlugt TJH (2005) Molecular simulations of the adsorption
of cycloalkanes in MFI-type silica. Phys Chem Chem Phys 7:26222628
41. Schenk M, Calero S, Maesen TLM, Vlugt TJH, van Benthem LL, Verbeek MG, Schnell B,
Smit B (2003) Shape selectivity through entropy. J Cat 214:8899
42. Krishna R, van Baten JM (2007) Screening of zeolite adsorbents for separation of hexane
isomers: A molecular simulation study. Sep Purif Technol 55:246255
43. Krishna R, van Baten JM (2007) Using molecular simulations for screening of zeolites for
separation Of CO2/CH4 mixtures. Chem Eng J 133:121131
44. Yashonath S, Santikary P (1994) Diffusion of sorbates in zeolite-Y and zeolite-A- novel
dependence on sorbate size and strength of sorbatezeolite interaction. J Phys Chem
98:63686376
45. Clark LA, Snurr RQ (1999) Adsorption isotherm sensitivity to small changes in zeolite structure. Chem Phys Lett 308:155159
46. Gupta A, Clark LA, Snurr RQ (2000) Grand canonical Monte Carlo simulations of nonrigid
molecules: Siting and segregation in silicalite zeolite. Langmuir 16:39103919
47. Chempath S, Snurr RQ, Low JJ (2004) Molecular modeling of binary liquid-phase adsorption of aromatics in silicalite. AIChE J 50:463469
48. Ban S, Van Laak A, De Jongh PE, Van der Eerden J, Vlugt TJH (2007) Adsorption selectivity of benzene/propene mixtures for various zeolites. J Phys Chem C
111:1724117248
49. Zeng YP, Ju SG, Xing WH, Chen CL (2007) Computer simulation of the adsorption of
thiophene/benzene mixtures on MFI and MOR. Sep Purif Technol 55:8290
50. Zeng YP, Ju SG, Xing WH, Chen CL (2007) Computer simulation of benzene adsorbed in
all-silica Y and NaY zeolites. Ind Eng Chem Res 46:242248
51. Lachet V, Boutin A, Tavitian B, Fuchs AH (1997) Grand canonical Monte Carlo simulations
of adsorption of mixtures of xylene molecules in faujasite zeolites. Faraday Discussions
307323
52. Lachet V, Boutin A, Tavitian B, Fuchs AH (1999) Molecular simulation of p-xylene and
m-xylene adsorption in Y zeolites. Single components and binary mixtures study. Langmuir
15:86788685
53. Lachet V, Buttefey S, Boutin A, Fuchs AH (2001) Molecular simulation of adsorption equilibria of xylene isomer mixtures in faujasite zeolites. A study of the cation exchange effect
on adsorption selectivity. Phys Chem Chem Phys 3:8086
54. Lucena SMP, Snurr RQ, Cavalcante CL (2008) Studies on adsorption equilibrium of xylenes
in AEL framework. Micro Meso Materials 111:8996
55. Prasanth KP, Pillai RS, Bajaj HC, Jasra RV, Chung HD, Kim TH, Song SD (2008) Adsorption of hydrogen in nickel and rhodium exchanged zeolite X. Int J Hydrogen Energy
33:735745
92
56. Macedonia MD, Moore DD, Maginn EJ, Olken MM (2000) Adsorption studies of methane,
ethane, and argon in the zeolite mordenite: Molecular simulations and experiments. Langmuir 16:38233834
57. Beerdsen E, Smit B, Calero S (2002) The influence of non-framework sodium cations
on the adsorption of alkanes in MFI- and MOR-type zeolites. J Phys Chem B
106:1065910667
58. Beerdsen E, Dubbeldam D, Smit B, Vlugt TJH, Calero S (2003) Simulating the effect of
nonframework cations on the adsorption of alkanes in MFI-type zeolites. J Phys Chem B
107:1208812096
59. Maurin G, Llewellyn P, Poyet T, Kuchta B (2005) Influence of extra-framework cations on
the adsorption properties of X-faujasite systems: Microcalorimetry and molecular simulations. J Phys Chem B 109:125129
60. Maurin G, Bourrelly S, Llewellyn PL, Bell RG (2006) Simulation of the adsorption properties of CH4 in faujasites up to high pressure: Comparison with microcalorimetry. Micro
Meso Mat 89:96102
61. Beauvais C, Boutin A, Fuchs AH (2005) Adsorption of water and aromatics in faujasite
zeolites: a molecular simulation study. Adsorption 11:279282
62. Akten ED, Siriwardane R, Sholl DS (2003) Monte Carlo simulation of single- and binarycomponent adsorption of CO2 , N2 , and H2 in zeolite Na-4A. Energy & Fuels 17:977983
63. Liu SS, Yang XN (2006) Gibbs ensemble Monte Carlo simulation of supercritical CO2
adsorption on NaA and NaX zeolites. J Chem Phys 124:244705
64. Sebastian J, Pillai RS, Peter SA, Jasra RV (2007) Sorption of N2 , O2 , and air in Mn(II)exchanged zeolites A and X using volumetric measurements and grand canonical Monte
Carlo simulation. Ind Eng Chem Res 46:62936302
65. Pillai RS, Peter SA, Jasra RV (2007) Correlation of sorption Behavior of nitrogen, oxygen,
and argon with Ca2+ locations in zeolite A: A grand canonical Monte Carlo simulation study.
Langmuir 23:88998908
66. Jiang JW, Sandler SI (2005) Separation of CO2 and N2 by adsorption in C168 schwarzite:
A combination of quantum mechanics and molecular simulation study. J Am Chem Soc
127:1198911997
67. Maurin G, Llewellyn PL, Bell RG (2005) Adsorption mechanism of carbon dioxide in faujasites: Grand canonical Monte Carlo simulations and microcalorimetry measurements. J Phys
Chem B 109:1608416091
68. Maurin G, Belmabkhout Y, Pirngruber G, Gaberova L, Llewellyn P (2007) CO2 adsorption in LiY and NaY at high temperature: molecular simulations compared to experiments.
Adsorption 13:453460
69. Kiselev AV, Lopatkin AA, Shulga AA (1985) Molecular statistical calculation of gas adsorption by silicalite. Zeolites 5:261267
70. June RL, Bell AT, Theodorou DN (1990) Molecular dynamics study of methane and xenon
in silicalite. J Phys Chem 94:82328240
71. Pellenq RJM, Nicholson D (1994) Intermolecular potential function for the physical adsorption of rare-gases in silicalite. J Phys Chem 98:1333913349
72. Pellenq RJM, Nicholson D (1995) Grand ensemble Monte Carlo simulation of simple
molecules adsorbed in silicalite-1 zeolite. Langmuir 11:16261635
73. Pellenq RJM, Pellegatti A, Nicholson D, Minot C (1995) Adsorption of argon in silicalite a
semiempirical quantum mechanical study of the repulsive interaction. J Phys Chem
99:1017510180
74. Douguet D, Pellenq RJM, Boutin A, Fuchs AH, Nicholson D (1996) The adsorption of
argon and nitrogen in silicalite-1 zeolite: A grand canonical Monte-Carlo study. Mol Simul
17:255288
75. Nicholson D (1996) Using computer simulation to study the properties of molecules in
micropores. J Chem Soc Faraday Transaction 92:19
76. Clark LA, Gupta A, Snurr RQ (1998) Siting and segregation effects of simple molecules in
zeolites MFI, MOR, and BOG. J Phys Chem B 102:67206731
93
77. Karavias F, Myers AL (1991) Monte Carlo simulations of adsorption of nonpolar and polarmolecules in zeolite-X. Mol Simul 8:2350
78. Kiselev AV, Du PQ (1981) Molecular statistical calculation of the thermodynamic adsorption characteristics of zeolites using the atomatom approximation 2. Adsorption of nonPolar and polar inorganic molecules by zeolites of type-X and type-Y. J Chem Soc Faraday
Transactions II 77:115
79. Woods GB, Rowlinson JS (1989) Computer simulations of fluids in zeolite-X and zeolite-Y.
J Chem Soc Faraday Transactions II 85:765781
80. Pellenq RJM, Tavitian B, Espinat D, Fuchs AH (1996) Grand canonical Monte Carlo simulations of adsorption of polar and nonpolar molecules in NaY zeolite. Langmuir 12:47684783
81. Vantassel PR, Davis HT, McCormick AV (1992) Monte Carlo calculations of Xe arrangement and energetics in the Naa Alpha-Cage. Mol Phys 76:411432
82. Vantassel PR, Davis HT, McCormick AV (1993) Open system Monte-Carlo simulations of
Xe in Naa. J Chem Phys 98:89198928
83. Vantassel PR, Davis HT, McCormick AV (1994) Adsorption simulations of small molecules
and their mixtures in a zeolite Micropore. Langmuir 10:12571267
84. VanTassel PR, Davis HT, McCormick AV (1996) Adsorption of binary mixtures in a zeolite
micropore. Mol Simul 17:239254
85. Vernov AV, Steele WA, Abrams L (1993) Sorption of xenon in zeolite-Rho a thermodynamic simulation study. J Phys Chem 97:76607664
86. Cracknell RF, Gubbins KE (1993) Molecular simulation of adsorption and diffusion in vpi-5
and other aluminophosphates. Langmuir 9:824830
87. Rajappa C, Bandyopadhyay S, Subramanian Y (1997) Monte Carlo and molecular dynamics
simulation of argon clusters and n-alkanes in the confined regions of zeolites. Bulletin of
Materials Science 20:845878
88. Lachet V, Boutin A, Pellenq RJM, Nicholson D, Fuchs AH (1996) Molecular simulation
study of the structural rearrangement of methane adsorbed in aluminophosphate AlPO4-5.
J Phys Chem 100:90069013
89. Boutin A, Pellenq RJM, Nicholson D (1994) Molecular simulation of the stepped
adsorption-isotherm of methane in AlPO4-5. Chem Phys Lett 219:484490
90. Mellot C, Lignieres J (1997) Monte Carlo simulations of N2 and O2 adsorption in silicalite
and CaLSX zeolites. Mol Simul 18:349365
91. Papai I, Goursot A, Fajula F, Plee D, Weber J (1995) Modeling of N2 and O2 adsorption in
zeolites. J Phys Chem 99:1292512932
92. Goursot A, Vasilyev V, Arbuznikov A (1997) Modeling of adsorption properties of zeolites:
Correlation with the structure. J Phys Chem B 101:64206428
93. Dunne JA, Myers AL, Kofke DA (1996) Simulation of adsorption of liquid mixtures of N2 ,
and O2 in a model faujasite cavity at 77.5 K. Adsorption 2:4150
94. Hirotani A, Mizukami K, Miura R, Takaba H, Miya T, Fahmi A, Stirling A, Kubo M,
Miyamoto A (1997) Grand canonical Monte Carlo simulation of the adsorption of CO2 on
silicalite and NaZSM-5. Appl Surf Sci 120:8184
95. Zygmunt SA, Curtiss LA, Iton LE, Erhardt MK (1996) Computational studies of water
adsorption in the zeolite H-ZSM-5. J Phys Chem 100:66636671
96. Sanchez JR, Palermo A, Aldao CM (1996) Monte Carlo study of thermal desorption curves
of water from zeolite type A. Langmuir 12:3639
97. Channon YM, Catlow CRA, Gorman AM, Jackson RA (1998) Grand canonical Monte Carlo
investigation of water adsorption in heulandite-type zeolites. J Phys Chem B 102:40454048
94
98. George AR, Catlow CRA, Thomas JM (1997) A computational investigation of the sorption
of methane into zeolitic structures. Micro Mat 11:97105
99. Smirnov KS (1994) Computer simulation study of methane in silicalite. Chem Phys Lett
229:250256
100. Du ZM, Dunne LJ, Chaplin MF, Manos G (1999) Comparative study of mean-field theory
and Monte Carlo simulation of supercritical methane adsorption in zeolites. Chem Phys Lett
307:413418
101. Smirnov KS, vandeGraaf B (1996) Study of methane adsorption in MFI and MEL zeolites by
combination of the electronegativity equalization method and molecular dynamics. J Chem
Soc Faraday Transactions 92:24752480
102. Moon SD, Miyano Y (1997) Monte Carlo simulation on the adsorption properties of methane
in zeolite L. Bull Korean Chem Soc 18:291295
103. Maris T, Vlugt TJH, Smit B (1998) Simulation of alkane adsorption in the aluminophosphate
molecular sieve AlPO4-5. J Phys Chem B 102:71837189
104. Radhakrishnan R, Gubbins KE (1997) Quasi-one-dimensional phase transitions in
nanopores: Porepore correlation effects. Phys Rev Lett 79:28472850
105. Smit B (1995) Simulating the adsorption isotherms of methane, ethane, and propane in the
zeolite silicalite. J Phys Chem 99:55975603
106. Gladden LF, Hargreaves M, Alexander P (1999) Monte Carlo lattice dynamics studies of
binary adsorption in silicalite. Chem Eng J 74:5766
107. van Well WJM, Cottin X, Smit B, van Hooff JHC, van Santen RA (1998) Chain length
effects of linear alkanes in zeolite ferrierite. 2. Molecular simulations. J Phys Chem B 102:
39523958
108. van Well WJM, Janchen J, de Haan JW, van Santen RA (1999) Adsorption of linear alkanes in the alpha-cages and gamma-cages of H-ZK-5 and K-ZK-5. J Phys Chem B 103:
18411853
109. Bates SP, vanWell WJM, vanSanten RA, Smit B (1996) Energetics of n-alkanes in zeolites:
A configurational-bias Monte Carlo investigation into pore size dependence. J Am Chem
Soc 118:67536759
110. Bates SP, VanWell WJM, VanSanten RA, Smit B (1997) Configurational-bias Monte Carlo
(CB-MC) calculations of n-alkane sorption in zeolites rho and fer. Mol Simul 19:301318
111. Maginn EJ, Bell AT, Theodorou DN (1995) Sorption thermodynamics, siting, and conformation of long n-alkanes in silicalite as predicted by configurational-bias Monte-Carlo integration. J Phys Chem 99:20572079
112. Macedonia MD, Maginn EJ (1999) A biased grand canonical Monte Carlo method for simulating adsorption using all-atom and branched united atom models. Mol Phys 96:13751390
113. Goodbody SJ, Watanabe K, Macgowan D, Walton J, Quirke N (1991) Molecular simulation
of methane and butane in silicalite. J Chem Soc Faraday Transactions 87:19511958
114. Du ZM, Manos G, Vlugt TJH, Smit B (1998) Molecular simulation of adsorption of short
linear alkanes and their mixtures in silicalite. AIChE J 44:17561764
115. Vlugt TJH, Krishna R, Smit B (1999) Molecular simulations of adsorption isotherms
for linear and branched alkanes and their mixtures in silicalite. J Phys Chem B 103:
11021118
116. Smit B (1995) Grand canonical Monte-Carlo simulations of chain molecules Adsorptionisotherms of alkanes in zeolites. Mol Phys 85:153172
117. Vitale G, Mellot CF, Cheetham AK (1997) Localization of adsorbed cyclohexane in the acid
form of zeolite Y. A powder neutron diffraction and computational study. J Phys Chem B
101:98869891
118. Smit B, Loyens L, Verbist G (1997) Simulation of adsorption and diffusion of hydrocarbons
in zeolites. Faraday Discussions 93104
119. Freeman CM, Catlow CRA, Thomas JM, Brode S (1991) Computing the location and energetics of organic molecules in microporous adsorbents and catalysts a hybrid approach
applied to isomeric butenes in a model zeolite. Chem Phys Lett 186:137142
95
120. Mellot CF, Cheetham AK (1999) Energetics and structures of fluoro- and chlorofluorocarbons in zeolites: Force field development and Monte Carlo simulations. J Phys Chem B
103:38643868
121. Mizukami K, Takaba H, Oumi Y, Katagiri M, Kubo M, Stirling A, Broclawik E, Miyamoto
A, Kobayashi S, Kushiyama S, Mizuno K. Atomistic mechanism of the adsorption of CFCs
in zeolite as investigated by Monte Carlo simulation. In Progress in Zeolite and Microporous
Materials, Pts a-C, 1997; Vol. 105; pp 18111818.
122. Mellot CF, Cheetham AK, Harms S, Savitz S, Gorte RJ, Myers AL (1998) Calorimetric
and computational studies of chlorocarbon adsorption in zeolites. J Am Chem Soc 120:
57885792
123. Mellot CF, Cheetham AK, Harms S, Savitz S, Gorte RJ, Myers AL (1998) Halocarbon
adsorption in nanoporous materials: A combined calorimetric and Monte Carlo study of
trichloroethylene (TCE) in faujasite-type zeolites. Langmuir 14:67286733
124. Smirnov KS, Thibault-Starzyk F (1999) Confinement of acetonitrile molecules in mordenite.
A computer modeling study. J Phys Chem B 103:85958601
125. Snurr RQ, Bell AT, Theodorou DN (1993) Prediction of adsorption of aromatichydrocarbons in silicalite from grand canonical Monte Carlo simulations with biased insertions. J Phys Chem 97:1374213752
126. Klemm E, Wang JG, Emig G (1998) A comparative study of the sorption of benzene and
phenol in silicalite, HAl-ZSM-5 and NaAl-ZSM-5 by computer simulation. Micro Meso Mat
26:1121
127. Auerbach SM, Bull LM, Henson NJ, Metiu HI, Cheetham AK (1996) Behavior of benzene
in Na-X and Na-Y zeolites: Comparative study by H2 NMR and molecular mechanics. J
Phys Chem 100:59235930
128. Kitagawa T, Tsunekawa T, Iwayama K (1996) Monte Carlo simulations on adsorptions of
benzene and xylenes in sodium-Y zeolites. Micro Mat 7:227233
129. Lachet V, Boutin A, Tavitian B, Fuchs AH (1998) Computational study of p-xylene/mxylene mixtures adsorbed in NaY zeolite. J Phys Chem B 102:92249233
130. Kirschhock C, Fuess H (1996) m-Dinitrobenzene in zeolite NaY: Four different arrangements. Zeolites 17:381388
131. Shiriashi M, Introduction to Carbon Materials, Carbon Society of Japan: Tokyo, 1984
132. Dresselhaus MS, Dresselhaus G, Eklund PC, Science of Fullerenes and Carbon Nanotubes,
Academic Press, Inc.: San Diego, 1996
133. Heuchel M, Davies GM, Buss E, Seaton NA (1999) Adsorption of carbon dioxide and
methane and their mixtures on an activated carbon: simulation and experiment. Langmuir
15:86958705
134. Kurniawan Y, Bhatia SK, Rudolph V (2006) Simulation of binary mixture adsorption of
methane and CO2 at supercritical conditions in carbons. AIChE J 52:957967
135. Severson BL, Snurr RQ (2007) Monte Carlo simulation of n-alkane adsorption isotherms in
carbon slit pores. J Chem Phys 126:134708
136. Do DD, Do HD (2005) Evaluation of 1-Site and 5-Site Models of Methane on Its Adsorption
on Graphite and in graphitic slit pores. J Phys Chem B 109:1928819295
137. Liu JC, Monge MA (2006) MC of water adsorption in activated carbon. Langmuir
45:56495656
138. Jiang JW (2006) Pore size or geometry: Which determines the shape and inverse-shape selective adsorption of alkane isomers? J Phys Chem B 110:86708673
139. Jiang JW, Sandler SI (2003) Monte Carlo simulation of O2 and N2 mixture adsorption in
nanoporous carbon (C168 Schwarzite). Langmuir 19:59365941
140. Jiang JW, Klauda JB, Sandler SI (2003) Monte Carlo simulation of O2 and N2 adsorption in
nanoporous carbon (C168 Schwarzite). Langmuir 19:35123518
141. Jiang JW, Klauda JB, Sandler SI (2004) Hierarchical modeling O2 and N2 adsorption in
C168 schwarzite: From quantum mechanics to molecular simulation. J Phys Chem B 108:
98529860
96
142. Iijima S (1991) Helical microtubules of graphitic carbon. Nature 354:56

143. Yin YF, Mays T, McEnaney B (1999) Adsorption of nitrogen in carbon nanotube arrays.
Langmuir 15:87148718
144. Simonyan VV, Johnson JK, Kuznetsova A, Yates JT (2001) Molecular simulation of xenon
adsorption on single-walled carbon nanotubes. J Chem Phys 114:41804185
145. Zhang XR, Wang WC (2002) Methane adsorption in single-walled carbon nanotubes arrays
by molecular simulation and density functional theory. Fluid Phase Equilib 194:289295
146. Calbi MM, Gatica SM, Bojan MJ, Cole MW (2001) Phases of neon, xenon, and methane
adsorbed on nanotube bundles. J Chem Phys 115:99759981
147. Calbi MM, Cole MW (2002) Dimensional crossover and quantum effects of gases adsorbed
on nanotube bundles. Phys Rev B 66:115413
148. Gatica SM, Bojan MJ, Stan G, Cole MW (2001) Quasi-one- and two-dimensional transitions
of gases adsorbed on nanotube bundles. J Chem Phys 114:37653769
149. Jiang JW, Sandler SI (2003) Nitrogen adsorption on carbon nanotube bundles: Role of the
external surface. Phys Rev B 68:245412
150. Jiang JW, Sandler SI (2004) Nitrogen and oxygen mixture adsorption on carbon nanotube
bundles from molecular simulation. Langmuir 20:1091010918
151. Matranga C, Chen L, Smith M, Bittner E, Johnson JK, Bockrath B (2003) Trapped CO2 in
CNT Bundles. J Phys Chem B 107:1293012941
152. Huang LL, Zhang LZ, Shao Q, Lu LH, Lu XH, Jiang SY, Shen WF (2007) Simulations of
binary mixture adsorption of carbon dioxide and methane in carbon nanotubes: Temperature,
pressure, and pore size effects. J Phys Chem C 111:1191211920
153. Cao DP, Zhang XR, Chen JF, Wang WC, Yun J (2003) Optimization of single-walled
carbon nanotube arrays for methane storage at room temperature. J Phys Chem B 107:
1328613292
154. Jiang JW, Sandler SI, Schenk M, Smit B (2005) Adsorption and separation of linear and
branched alkanes on carbon nanotube bundles from configurational-bias Monte Carlo simulation. Phys Rev B 72:045447
155. Jiang JW, Sandler SI (2006) Shape versus inverse-shape selective adsorption of alkane isomers in carbon nanotubes. J Chem Phys 124:024717
156. Shi W, Johnson JK (2003) Gas adsorption on heterogeneous single-walled carbon nanotube
bundles. Phys Rev Lett 91:015504
157. Matranga C, Chen L, Bockrath B, Johnson JK (2004) Displacement of CO2 by Xe. Phys
Rev B 70:165416
158. Banerjee S, Murad S, Puri IK (2006) Hydrogen storage in carbon nanostructures: Possibilities and challenges for fundamental molecular simulations. IEEE Proc 94:18061814
159. Simonyan VV, Johnson JK (2002) Hydrogen storage in carbon nanotubes and graphitic
nanofibers. J Alloy Compd 330:659665
160. Strobel R, Jorissen L, Schliermann T, Trapp V, Schutz W, Bohmhammel K, Wolf G, Garche
J (1999) Hydrogen adsorption on carbon materials. J Power Sources 84:221224
161. van den Berg AWC, Arean CO (2008) Materials for hydrogen storage: current research
trends and perspectives. Chem Commun 668681
162. Kowalczyk P, Holyst R, Terrones M, Terrones H (2007) Hydrogen storage in nanoporous
carbon materials: myth and facts. Phys Chem Chem Phys 9:17861792
163. Darkrim F, Levesque D (2000) High adsorptive property of opened carbon nanotubes at
77 K. J Phys Chem B 104:67736776
164. Darkrim F, Aoufi A, Levesque D (2000) Quantum contribution to gas adsorption in carbon
nanotubes. Mol Simul 24:5161
165. Tanaka H, Kanoh H, Yudasaka M, Lijima S, Kaneko K (2005) Quantum effects on hydrogen
isotope adsorption on single-wall carbon nanohorns. J Am Chem Soc 127:75117516
166. Weng CI, Ju SP, Fang KC, Chang FP (2007) Atomistic study of the influences of size,
VDW distance and arrangement of carbon nanotubes on hydrogen storage. Comput Mater
Sci 40:300308
97
167. Zhou Z, Gao XP, Yan J, Song DY (2006) Doping effects of B and N on hydrogen adsorption in single-walled carbon nanotubes through density functional calculations. Carbon
44:939947
168. Yang FH, Lachawiec AJ, Yang RT (2006) Adsorption of spillover hydrogen atoms on singlewall carbon nanotubes. J Phys Chem B 110:62366244
169. Sankaran M, Viswanathan B (2006) The role of heteroatoms in carbon nanotubes for hydrogen storage. Carbon 44:28162821
170. Lan JH, Cheng DJ, Cao DP, Wang WC (2008) Silicon nanotube as a promising candidate
for hydrogen storage: From the first principle calculations to grand canonical Monte Carlo
simulations. J Phys Chem C 112:55985604
171. Hu NP, Sun XY, Hsu A (2005) Monte Carlo simulations of hydrogen adsorption in alkalidoped single-walled carbon nanotubes. J Chem Phys 123:044708
172. Gayathri V, Geetha R (2007) Hydrogen adsorption in defected carbon nanotubes. Adsorption
13:5359
173. Coluci VR, Braga SF, Baughman RH, Galvao DS (2007) Prediction of the hydrogen storage
capacity of carbon nanoscrolls. Phys Rev B 75:125404
174. Mpourmpakis G, Tylianakis E, Froudakis GE (2007) Carbon nanoscrolls: A promising material for hydrogen storage. Nano Lett 7:18931897
175. Gigras A, Bhatia SK, Kumar AVA, Myers AL (2007) Feasibility of tailoring for high isosteric
heat to improve effectiveness of hydrogen storage in carbons. Carbon 45:10431050
176. Lee SM, Lee YH (2000) Hydrogen storage in single-walled carbon nanotubes. Appl Phys
Lett 76:28772879
177. Mpourmpakis G, Froudakis GE (2007) Why boron nitride nanotubes are preferable to
carbon nanotubes for hydrogen storage? An ab initio theoretical study. Catalysis Today
120:341345
178. Ferre-Vilaplana A (2005) Ab initio computational investigation of physisorption of molecular H2. J Chem Phys 122:214724
179. Bauschlicher CW (2000) Hydrogen and fluorine binding to the sidewalls of a (10,0) carbon
nanotube. Chem Phys Lett 322:237241
180. Froudakis GE (2001) Hydrogen interaction with single-walled carbon nanotubes: A combined quantum-mechanics/molecular-mechanics study. Nano Lett 1:179182
181. Froudakis GE (2002) Hydrogen interaction with carbon nanotubes: A review of ab initio
studies. J Phys: Condens Matter 14:R453R465
182. Yaghi OM, OKeeffe M, Ockwig NW, Chae HK, Eddaoudi M, Kim J (2003) Reticular synthesis and the design of new materials. Nature 423:705714
183. Eddaoudi M, Kim J, Rosi N, Vodak D, Wachter J, OKeeffe M, Yaghi OM (2002) Systematic
design of pore size and functionality in isoreticular MOFs and their application in methane
storage. Science 295:469472
184. Snurr RQ, Hupp JT, Nguyen ST (2004) Prospects for nanoporous metal-organic materials in
advanced separations processes. AIChE J 50:10901095
185. Vishnyakov A, Ravikovitch PI, Neimark AV, Bulow M, Wang QM (2003) Nanopore structure and sorption properties of Cu-BTC metal-organic framework. Nano Lett 3:713718
186. Dubbeldam D, Frost H, Walton KS, Snurr RQ (2007) Molecular simulation of adsorption sites of light gases in the metal-organic framework IRMOF-1. Fluid Phase Equilib
261:152161
187. Duren T, Sarkisov L, Yaghi OM, Snurr RQ (2004) Design of new materials for methane
storage. Langmuir 20:26832689
188. Garberoglio G, Skoulidas AI, Johnson JK (2005) Adsorption of gases in metal organic materials: Comparison of simulations and experiments. J Phys Chem B 109:1309413103
189. Wang SY (2007) Comparative molecular simulation study of methane adsorption in metalorganic frameworks. Energy & Fuels 21:953956
190. Walton KS, Snurr RQ (2007) Applicability of the BET method for determining surface areas
of microporous metal-organic frameworks. J Am Chem Soc 129:85528556
98
191. Duren T, Snurr RQ (2004) Assessment of isoreticular metal-organic frameworks for adsorption separations: A molecular simulation study of methane/n-butane mixtures. J Phys Chem
B 108:1570315708
192. Jiang JW, Sandler SI (2006) Monte Carlo simulation for the adsorption and separation of
linear and branched alkanes in IRMOF-1. Langmuir 22:57025707
193. Yang QY, Zhong CL (2006) Electrostatic-field-induced enhancement of gas mixture separation in metal-organic frameworks: A computational study. Chemphyschem 7:14171421
194. Yang QY, Zhong CL (2006) Molecular simulation of carbon dioxide/methane/hydrogen mixture adsorption in metal-organic frameworks. J Phys Chem B 110:1777617783
195. Babarao R, Hu ZQ, Jiang JW, Chempath S, Sandler SI (2007) Storage and separation of
CO2 and CH4 in silicalite, C168 schwarzite, and IRMOF-1: A comparative study from Monte
Carlo simulation. Langmuir 23:659666
196. Ramsahye NA, Maurin G, Bourrelly S, Llewellyn PL, Devic T, Serre C, Loiseau T, Ferey G
(2007) Adsorption of CO2 in metal organic frameworks of different metal centres: Grand
Canonical Monte Carlo simulations compared to experiments. Adsorption 13:461467
197. Walton KS, Millward AR, Dubbeldam D, Frost H, Low JJ, Yaghi OM, Snurr RQ (2008)
Understanding inflections and steps in carbon dioxide adsorption isotherms in metal-organic
frameworks. J Am Chem Soc 130:406407
198. Yang QY, Zhong CL, Chen JF (2008) Computational study of CO2 storage in metal-organic
frameworks. J Phys Chem C 112:15621569
199. Babarao R, Jiang JW (2008) Molecular screening of metal-organic frameworks for CO2
storage. Langmuir 24:62706278
200. Yang QY, Zhong CL (2005) Molecular simulation of adsorption and diffusion of hydrogen
in metal-organic frameworks. J Phys Chem B 109:1186211864
201. Frost H, Duren T, Snurr RQ (2006) Effects of surface area, free volume, and heat of adsorption on hydrogen uptake in metal-organic frameworks. J Phys Chem B 110:95659570
202. Jung DH, Kim D, Lee TB, Choi SB, Yoon JH, Kim J, Choi K, Choi SH (2006) Grand
canonical Monte Carlo simulation study on the catenation effect on hydrogen adsorption
onto the interpenetrating metal-organic frameworks. J Phys Chem B 110:2298722990
203. Frost H, Snurr RQ (2007) Design requirements for metal-organic frameworks as hydrogen
storage materials. J Phys Chem C 111:1879418803
204. Mueller T, Ceder G (2005) A density functional theory study of hydrogen adsorption in
MOF-5. J Phys Chem B 109:1797417983
205. Lochan RC, Head-Gordon M (2006) Computational studies of molecular hydrogen binding
affinities: The role of dispersion forces, electrostatics, and orbital interactions. Phys Chem
Chem Phys 8:13571370
206. Negri F, Saendig N (2007) Tuning the physisorption of molecular hydrogen: Binding
to aromatic, hetero-aromatic and metal-organic framework materials. Theor Chem Acct
118:149163
207. Hubner O, Gloss A, Fichtner M, Klopper W (2004) On the interaction of dihydrogen with
aromatic systems. J Phys Chem A 108:30193023
208. Sagara T, Klassen J, Ganz E (2004) Computational study of hydrogen binding by metalorganic framework-5. J Chem Phys 121:1254312547
209. Sagara T, Klassen J, Ortony J, Ganz E (2005) Binding energies of hydrogen molecules to
isoreticular metal-organic framework materials. J Chem Phys 123: 014701
210. Blomqvist A, Araujo CM, Srepusharawoot P, Ahuja R (2007) Li-decorated metal-organic
framework 5: A route to achieving a suitable hydrogen storage medium. Proc Natl Acad Sci
USA 104:2017320176
211. Gao Y, Zeng XC (2007) Ab initio study of hydrogen adsorption on benzenoid linkers in
metal-organic framework materials. J Phys: Condens Matter 19:386220
212. Liu Y, Kabbour H, Brown CM, Neumann DA, Ahn CC (2008) Increasing the density of
adsorbed hydrogen with coordinatively unsaturated metal centers in metal-organic frameworks. Langmuir 24:47724777
99
213. Vishnyakov A, Neimark AV (2003) Specifics of freezing of Lennard-Jones fluid confined to

molecularly thin layers. J Chem Phys 118:75857598
214. Yang QY, Xue CY, Zhong CL, Chen JF (2007) Molecular simulation of separation of CO2
from flue gases in Cu-BTC metal-organic framework. AIChE J 53:28322840
215. Ramsahye NA, Maurin G, Bourrelly S, Llewellyn PL, Loiseau T, Serre C, Ferey G (2007)
On the breathing effect of a metal-organic framework upon CO2 adsorption: Monte Carlo
compared to microcalorimetry experiments. Chem Commun 32613263
216. Jhon YH, Cho M, Jeon HR, Park I, Chang R, Rowsell JLC, Kim J (2007) Simulations of
methane adsorption and diffusion within alkoxy-functionalized IRMOFs exhibiting severely
disordered crystal structures. J Phys Chem C 111:1661816625
217. Pan L, Olson DH, Ciemnolonski LR, Heddy R, Li J (2006) Separation of hydrocarbons with
a microporous metal-organic framework. Ang Chem Inter Ed 45:616619
218. Sarkisov L, Duren T, Snurr RQ (2004) Molecular modelling of adsorption in novel
nanoporous metal-organic materials. Mol Phys 102:211221
219. Zhang L, Wang Q, Wu T, Liu YC (2007) Understanding adsorption and interactions of
alkane isomer mixtures in isoreticular metal-organic frameworks. Chem Eur J 13:63876396
220. Cote AP, Benin AI, Ockwig NW, OKeeffe M, Matzger AJ, Yaghi OM (2005) Porous, crystalline, covalent organic frameworks. Science 310:11661170
221. CoteAP, El-Kaderi HM, Furukawa H, Hunt JR, Yaghi OM (2007) Reticular synthesis of
microporous and mesoporous 2D covalent organic frameworks. J Am Chem Soc 129:
1291412915
222. El-Kaderi HM, Hunt JR, Mendoza-Cortes JL, Cote AP, Taylor RE, OKeeffe M, Yaghi OM
(2007) Designed synthesis of 3D covalent organic frameworks. Science 316:268272
223. Garberoglio G (2007) Computer simulation of the adsorption of light gases in covalent
organic frameworks. Langmuir 23:1215412158
224. Babarao R, Jiang JW (2008) Exceptionally high CO2 storage in covalent-organic frameworks: Atomistic simulation study. Energy Environ Sci 1:139143
225. Park KS, Ni Z, Cote AP, Choi JY, Huang RD, Uribe-Romo FJ, Chae HK, OKeeffe M, Yaghi
OM (2006) Exceptional chemical and thermal stability of zeolitic imidazolate frameworks.
Proc Nat Acad Sci USA 103:1018610191
226. Banerjee R, Phan A, Wang B, Knobler C, Furukawa H, OKeeffe M, Yaghi OM (2008) Highthroughput synthesis of zeolitic imidazolate frameworks and application to CO2 capture.
Science 319:939943
227. Hayashi H, Cote AP, Furukawa H, OKeeffe M, Yaghi OM (2007) Zeolite a imidazolate
frameworks. Nature Mater 6:501506
228. Nicholson D, Pellenq RJM (1998) Adsorption in zeolites: intermolecular interactions and
computer simulation. Adv Colloid Interf Sci 7677:179202
229. Steele W (1993) Molecular interactions for physical adsorption. Chem Rev 93:23552378
230. Rappe AK, Casewit CJ, Colwell KS, Goddard WA, Skiff WM (1992) UFF, a full periodic
table force field for molecular mechanics and molecular dynamics simulations. J Am Chem
Soc 114:1002410035
231. Mayo SL, Olafson BD, Goddard WA (1990) Dreiding a generic force field for molecular
simulations. J Phys Chem 94:88978909
232. Vlugt TJH, Schenk M (2002) Influence of framework flexibility on the adsorption properties
of hydrocarbons in the zeolite silicalite. J Phys Chem B 106:1275712763
233. Kitaura R, Fujimoto K, Noro S, Kondo M, Kitagawa S (2002) A pillared-layer coordination
polymer network displaying hysteretic sorption: Cu-2(pzdc)(2)(dpyg) (n) (pzdc = pyrazine2,3-dicarboxylate; dpyg = 1,2-di(4-pyridyl)glycol). Ang Chem Inter Ed 41:133135
234. Greathouse JA, Allendorf MD (2006) The interaction of water with MOF-5 simulated by
molecular dynamics. J Am Chem Soc 128:1331213312
235. Dubbeldam D, Walton KS, Ellis DE, Snurr RQ (2007) Exceptional negative thermal expansion in isoreticular metal-organic frameworks. Ang Chem Inter Ed 46:44964499
100
236. Theodorou DN, Snurr RQ, Bell AT. Molecular dynamics and diffusion in microporous materials. In Comprehensive Supramolecular Chemistry; Alberti G, Bein T, Eds.; Pergamon:
Oxford, 1996; Vol. 7; pp. 507548.
237. Maginn EJ, Bell AT, Theodorou DN (1993) Transport diffusivity of methane in silicalite
from equilibrium and nonequilibrium simulations. J Phys Chem 97:41734181
238. Papadopoulos GK, Jobic H, Theodorou DN (2004) Transport diffusivity of N2 and CO2 in
silicalite: Coherent quasielastic neutron scattering measurements and molecular dynamics
simulations. J Phys Chem B 108:1274812756
239. Snurr RQ, Karger J (1997) Molecular simulations and NMR measurements of binary diffusion in zeolites. J Phys Chem B 101:64696473
240. Dubbeldam D, Beerdsen E, Vlugt TJH, Smit B (2005) Molecular simulation of loadingdependent diffusion in nanoporous materials using extended dynamically corrected transition state theory. J Chem Phys 122:224712
241. Krishna R, van Baten JM (2008) Insights into diffusion of gases in zeolites. Micro Meso
Materials 109:91108
242. Skoulidas AI, Ackerman DM, Johnson JK, Sholl DS (2002) Rapid transport of gases in
carbon nanotubes. Phys Rev Lett 89:185901
243. Ackerman DM, Skoulidas AI, Sholl DS, Johnson JK (2003) Diffusivities of Ar and Ne in
carbon nanotubes. Mol Simul 29:677684
244. Arora G, Sandler SI (2006) Air separation by single wall carbon nanotubes: Mass transport
and kinetic selectivity. J Chem Phys 124:084702
245. Skoulidas AI, Sholl DS (2005) Self-diffusion and transport diffusion of light gases in metalorganic framework materials assessed using molecular dynamics simulations. J Phys Chem
B 109:1576015768
246. Amirjalayer S, Tafipolsky M, Schmid R (2007) Molecular dynamics simulation of benzene
diffusion in MOF-5: Importance of lattice dynamics. Ang Chem Inter Ed 46:463466
247. Babarao R, Jiang JW (2008) Diffusion and Separation of CO2 and CH4 in Silicalite, C168
Schwarzite and IRMOF-1. Langmuir 24:5474
248. Krishna R, van Baten JM (2008) Onsager coefficients for binary mixture diffusion in
nanopores. Chem Eng Sci 63:31203140

BCR2

Загружено:

Сведения о документе

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

BCR2

Загружено:

Авторское право:

Доступные форматы

Chapter 4

Molecular Computations of Adsorption

Abstract Adsorption lies at the heart of many industrially important applications

R. Babarao and J. Jiang

statistical mechanics have been developed to examine the equilibrium properties of

Molecular Computations of Adsorption in Nanoporous Materials

4.2.1 Light Gases

R. Babarao and J. Jiang

was proposed to predict adsorption thermodynamics of single components and

4.2.2 Alkanes and Alkenes

Molecular Computations of Adsorption in Nanoporous Materials

R. Babarao and J. Jiang

4.2.4 Cation-Exchanged Zeolites

Molecular Computations of Adsorption in Nanoporous Materials

R. Babarao and J. Jiang

[16, 77, 78]

[109, 110, 118]

[31, 32, 105,

[103, 107, 108]

[87, 109, 110] [87, 107110,

[109, 110, 118]

[109, 110, 118]

[109, 110, 118]

[51, 52, 80,

Molecular Computations of Adsorption in Nanoporous Materials

Table 4.1 (continued)

4.3 Carbonaceous Materials

4.3.1 Activated Carbons

R. Babarao and J. Jiang

entropy effect, followed by inverse-shape selective adsorption that occurs due to

4.3.2 Carbon Nanotubes

Molecular Computations of Adsorption in Nanoporous Materials

R. Babarao and J. Jiang

account for the heterogeneity [156]. Displacement of CO2 by Xe was simulated in

Molecular Computations of Adsorption in Nanoporous Materials

R. Babarao and J. Jiang

virtually independent of chirality [178]. Another commonly used method is the

4.4 Hybrid Frameworks

4.4.1 Light Gases

Molecular Computations of Adsorption in Nanoporous Materials

R. Babarao and J. Jiang

the adsorption selectivity in IRMOF-1 is smaller [192]. Gas mixtures containing

4.4.2 CO2 Storage

Molecular Computations of Adsorption in Nanoporous Materials

R. Babarao and J. Jiang

4.4.4 New Hybrid Frameworks

Molecular Computations of Adsorption in Nanoporous Materials

Table 4.2 Simulation studies of adsorption in MOFs

[186, 188, 213]

[187, 191193, 195, 216]

R. Babarao and J. Jiang

Molecular Computations of Adsorption in Nanoporous Materials

R. Babarao and J. Jiang

Molecular Computations of Adsorption in Nanoporous Materials

R. Babarao and J. Jiang

Molecular Computations of Adsorption in Nanoporous Materials

R. Babarao and J. Jiang

Molecular Computations of Adsorption in Nanoporous Materials

R. Babarao and J. Jiang

142. Iijima S (1991) Helical microtubules of graphitic carbon. Nature 354:56

Molecular Computations of Adsorption in Nanoporous Materials

R. Babarao and J. Jiang

Molecular Computations of Adsorption in Nanoporous Materials

213. Vishnyakov A, Neimark AV (2003) Specifics of freezing of Lennard-Jones fluid confined to