Академический Документы
Профессиональный Документы
Культура Документы
2
AA1 2012
AA2 2014
AA3 Dmitrij Rappoport Nathan R. M. Crawford 2008
AB1
1
2
3
4
5
Title
Prediction of Adsorption Properties of Cyclic Hydrocarbons in MOFs Using DFT-
Derived Force Fields
probing the adsorption for CO2 in Metal Organic Frameworks materials MIL-
53(Al, Cr) and MIL-47(V) by Density Functional Theory
Metal organic framework as potential shock absorbers: the case of highly flexible
MIL-53(Al)
Comparative Study of Hydrogen Sulfide Adsorption in the MIL-53(Al, Cr, Fe), MIL-
47(V), MIL-100(Cr) Metal-Organic Frameworks at Room Temperature
Detailed study of the topic using osmotic potential model and stress model. They predicted
a temp-vapor phase diagram for different pore structures.
They predicted the mechanical properties of 5 MOFs using QM calculations and showed that
the framework flexibility and existance of structural transition are clearly visible in their
local elastic properties. These properties are anisotropic. In case of MIL-53, stifness
coefficients are dependent on metal centers and so is the flexibility.
They provided a plausible stress based mechanism for the breathing structural transition of
MIL-53 upon guest adsorption. Also the model shed some light onto the existence of lp/np
phase mixtures at pressures close to the breathing pressure.
This paper explains transition of large pore to narrow pore to large pore on temperature
change and CO2 adsorption using molecular dynamics
Paper studies the effect of external pressure on MIL-53-Cr structure and produces a
hyterical loop by increasing then decreasing the pressure. Also, the same effect is studied
by putting some molecules of CO2 in the structure
After single component diffusion for both species, effect of CO2 concentration on CH4
diffusion is studied in this paper for both the given MOFs. Structure transition is considered
and logically neglected for MIL-53 material
2-O absence in MIL-47 compared to MIL-53 materials leads to no preferntial adsorption
sites in MIL-47 material for CO2 adsorption. Also differences between MIL-53-Cr and MIL-53-
Al are subtle
MoFs can be used as mechanical shock absorber. MIL-53-Al goes into irreversible LP to NP
structural transition compared to MIL-53-Cr and MIL-47 which go to reversible structural
transitions
Study of C1-C4 alkanes adsorption of MIL-53-Fe structure showing its very narrow pore,
intermediate, narrow and large pore forms and their effect on isotherms. Also comparison
with other MIL-53 materials (Cr/Al) having only two pore forms are also shown in the paper
Explanation of flexibility of MOFs (IRMOF-1, MIL-47, MIL-53, MIL-88 etc.) along each
parameter (a,b,c,alpha,beta,gamma) using mechanical examples
large pore to narrow pore to large pore structure transition in MIL-53-Cr is explained with
reasons
Difference between different surface areas e.g. BET, langmuir, NASA etc. Discription of
surface area measurement method dependent on poresize distribution of MOF
A study of n-alkens on MIL-53(Al,Cr) shows clear influence of alkyl chain length on the shape
of the adsorption curves. Transition pressures for substeps are dependent on the metal. Also
temperature dependence of hexane adsorption capacity is studied in details including
flexibility of the material
XRD patterns for MIL-53-as/lt/ht structures with detailed discussion about the structures,
effect of temperature on that, sorption properties and magnetism measurements
Different behavior of MIL-53 materials with different metals for hydrogen adsorption. MIL-
100 and MIL-101 are irreversible pore structure transitions while MIL-53 is reversible
Xylene isomers adsorption and selectivity is compared in CPO-27-Ni and HKUST-1. Also it is
concluded that first one is intrinsically ortho selective which is further increased by
electrostatic interactions. However 2nd one is intrinsically para selective which is
overcompensated by electrostatic forces making it overall ortho selective material
In conclusion, a novel MOF has been successfully synthesized from a strategically designed
ligand bearing two ether linkages as its flexible nodes which shows high degree of flexibility
and presented selective adsorption of p-xylene over its isomers
Adsorption of styrene is selective over ethylbenzene and others in MIL-47 and MIL-53 but
both have different mechanism MIL-47 is mainly entropic based while MIL-53 is enthalpy
based
MIL-53 has a pronounced preference for ortho-isomers, for xylene molecular packing plays
an important role. The preference found is determined by interaction of methyl group with
pore walls. Read for the details
The computationally most efficient basic approaches to account for London dispersion
effects in DFT calculations have been reviewed. DFT-D method in the most recent forms is
truly competitive with other methods.
Authors have compared MOF-5 and MOF-monoclinic for the adsorption and separation of C8
isomers. The elution orfer of xylene isomers and EB on MOF-5 was controlled by equilibrium
constants while for MOF-monoclinic pore shape was more important
An anioinc MOF constructed with a new hexanuclear nickel(II) unit and a trigonal planar
ligand. Although being 2-fold interpenetrated, this MOF shows the capability to adsorb H2,
Co2, and light hydrocarbons, and most important is that it exhibits high separation
selectivity of C2H2, C2H4, and C2H6 over CH4
Normal mode calculations using periodic dft calculations from partial hessian vibrational
analysis and comparison with full hessian vibration analysis. Also mobile block hessian is
also used for efficient calculations. Calculations are done to calculate entropy for
physiosorbed and chemisorbed hydrocarbons in some zeolites
Authors reviewed general design principles of iMOFs i.e. both cationic and anionic MOFs and
explained their applications in various fields. The inherent polarizable ions present in such
MOFs gives an added advantage in incorporation of ionic species by ion exchange processes
which would thereby help to fabricate specific funcitonality which would otherwise is not
possible in neutral MOFs
Various techniques for introducing accesible metal centers have been briefly given. In
summery, they introduced noncatenated -OH functionalized MOF and exchanged the
hydroxyl protons for lithium and magnesium cations via solution methods.
Authors examined sod-ZMOF exchanged with alkali (Li, Na, K, Rb and Cs) cations and gas
(CO2, N2, CH4) adsorption and admission using DFT calculations at PBE and DFT-D3 levels.
They found that large cations prefer to occupy sites close to 6MR gate and directly affect
admission of gas into framework while small cations do not.
Experimental and simulation isotherms for xylene isomers in MIL-47, vapor breakthrough
experiments also. Also IAST calculations for binary mixtures
Use of GCMC to calculate adsorption isotherms, surface area, heat of adsorption and siting
of adsorbate molecules can be predicted well for MOFs.
Synthesized different functionalized MOFs of Co(bdp) to obtain frameworks which can open
up at lower pressure or higher pressure than the original ones.
Xylene isomers interact differently with phenylene ring making linker rotation speed
different for each of them leading toward a selectivity under a certain temperature
Activation energy and Arrhenius constant changes for free and loaded MIL-53 structure for
rotation of linker but it is same for both oX and pX loadings
Single component isotherms of xylene isomers in MIL-53-Al; Henry coefficient in Langmuir
isotherms, dG, dS, Q calculations using experiments and adsorption orientation using
simulations
OFAST calculations