Measuring Particle Properties

by Gas Adsorption
Autosorb Training Introduction
Particle Properties: What might I want to know?
 Size and Shape

 Density
Particle Properties: What might I want to know?
 Size and Shape

 Density
Particle Properties: What might I want to know?
 Size and Shape

 Density

 Porosity/Pore volume*
Particle Properties: What might I want to know?
 Size and Shape

 Density

 Porosity/Pore volume*

 Pore size*
Gas Adsorption Terminology
Nanopores: < 100 nm

 Macropores: > 50 nm

 Mesopores: 2-50 nm

 Micropores: < 2 nm
• Supermicropores: 0.7-2 nm
• Ultramicropores: < 0.7 nm
Particle Properties: What might I want to know?
 Size and Shape

 Density

 Porosity/Pore volume*

 Pore size*
Particle Properties: What might I want to know?
 Size and Shape

 Density

 Porosity/Pore volume*

 Pore size*

 Surface area*
Why Surface Area?
 Surface Area is the means through which a solid interacts with its
surroundings

 Can indicate suitability of particles for particular processes

• Consider the following interactions
o Solid-Solid: autohesiveness (cohesiveness), flow, compactibility

o Solid-Liquid: solubility, reactivity, adsorption capacity

o Solid-Gas: adsorption, catalysis, reactivity

Why Surface Area?
 Surface area is increased by division of particles (size reduction)
and the generation of porosity

 Can indicate whether a process was successful

• Consider the following processes
o Particle Creation: grinding, milling, nanoscale preparations

o Particle Destruction: melting, sintering, oswald ripening

o Pore Creation: decomposition, leaching, synthesis/templating

Methods for Pore Size Characterization

Macropores

According to: P. Klobes and K. Meyer (BAM, Germany)

Introduction to Gas Adsorption
The Measurement of Surface Area
by Physisorption
Adsorbent

Adsorbate Adsorptive
Why does this occur?
 Physisorption Gas-Solid
Interaction
• General attraction between
Potential
adsorptive and adorbent caused by
Z
van der Waals’ forces

• The interaction potential between

the gas (adsorptive) and the
surface (adsorbent) exhibits a
minimum relatively close to the
surface Gas
Density
Profile
• This leads to an accumulation, ρg
near the surface, of gas molecules
(adsorbate) Z

Z = distance of gas from surface

ρg= density of bulk gas phase
The Gas Adsorption Isotherm
 The quantity of gas adsorbed is a
function of:
• The strength of interaction
between gas and solid (intrinsic)
• Temperature (fixed)
• Pressure/concentration
(controlled variable)

 The plot of Adsorbed Amount vs.

Pressure at a specified temperature is
called an Isotherm P0: Saturation pressure of adsorptive
P/P0: Relative pressure of adsorptive
How can we use this to measure surface area?
 We can calculate the area of an
unknown surface if:
4Å
• We cover it with a known
quantity of spheres in a
monolayer 1 2 3 4 5 6 4Å
• We know the area each sphere
occupies 7 8 9 10 11 12

 Gas adsorption allows probing 13 14 15 16 17 18

of entire surface including
irregularities and pore
interiors 𝑆𝑢𝑟𝑓𝑎𝑐𝑒 𝐴𝑟𝑒𝑎 = 4Å ∗ 4Å ∗ 18 = 288 Å2
Some Caveats
 We must know both the size and the packing of the adsorbate
molecule on the surface
• E.g., both of the following surfaces are covered in 6 rows of 10 spheres but
have different areas
Some Caveats
 Not all surfaces are flat (e.g., pores!)

• Take a flat surface, cover it with spheres:

• Now curve that same surface, fewer spheres will fit:

Some Caveats
 The ideal situation is the formation of exactly one complete monolayer

1 2 3 4 5 6 7 8 9 10

 What is actually tracked or calculated by physisorption measurements is

often the formation of a statistical monolayer

3 8
5
1 2 4 6 7 9 10
Choice of Adsorptive
 To perform surface area and pore size measurements, a number of
adsorptives are available:
• Nitrogen - 77K
• Argon - 87K or 77K
• Carbon Dioxide - 273K
• Krypton - 77K or 87K
• Hydrogen, Methane, and others are used for specific applications
Nitrogen at 77K
 Most commonly used adsorptive
 Pros:
• Long history of use (traditional adsorptive for BET method)
• On non-polar surfaces, the packing of nitrogen is relatively well known
• Liquid N2 is readily available
 Cons:
• Due to its’ quadrupolar nature, surface charges can have a significant
effect on pore filling pressures and packing of molecules
• Low absolute filling pressures of pores and low temperature make
equilibrium times very long for certain materials
Argon at 77K and 87K
 IUPAC recommended adsorptive (87K) for surface area and pore size
determinations
 Pros:
• Monatomic and therefore spherical in shape (no question of orientation on
surface)
• Non-polar and inert (surface charges have no effect)
• Ar (87K) kinetics are faster than nitrogen at 77K (shorter equilibration times)
 Cons:
• If liquid argon (or a cryocooler) is not available, and the isotherm is run at 77K, a
full isotherm cannot be acquired due to being below the triple point of argon (i.e.,
Ar at 77K is limited to pores <15 nm)
Benefits of Ar over N2 350

280
Faujasite Type
N (77K) - Faujasite
2 Zeolite Zeolite
Ar (87 K) - Faujasite Zeolite

Volume [cm3 g-1] STP

Zeolites have surface charges that
210

interact with nitrogen’s quadrupole 140 N2 77K
moment
Ar 87K
70

• N2 fills pores at lower relative and absolute

pressures than Ar 0
5 10-7 5 10-6 5 10-5 5 10-4
P/P0
5 10-3 5 10-2 5 10-1 5 100

• Extremely slow kinetics below 100 mTorr 800

(P/P0=10-5) 700
CMC2-Carbon (Argon, 87.3K)

Activated Carbon
CMC2-Carbon (Nitrogen, 77.3 K)

• Difficult to interpret pore dimensions 600

Volume [cm3 g-1]

500

Quadrupole interactions are not as

400

important in carbons
300

200 N2 77K
• N2 and Ar show similar isotherms 100
Ar 87K
0 -7
10 5 10-6 5 10-5 5 10-4 5 10-3 5 10-2 5 10-1 5 100
Relative Pressure [P/P0]

Thommes, M. Textural Characterization of Zeolites and Ordered Mesoporous Materials by

Physical Adsorption in: Introduction to Zeolite Science and Practice, 2007, p. 495-523
Carbon Dioxide at 273K
 Typically used in assessment of narrow pores in microporous carbons
 Pros:
• Pores are filled at high temperature and high absolute pressures, due to high
saturation pressure, which leads to faster diffusion rates into very narrow
micropores (Pores as small as 0.4 nm can be accessed)
• Complimentary to N2 or Ar characterization
• Temperature can be easily maintained using a refrigerated circulator
(recommended) or an ice water bath
 Cons:
• Strong quadrupole moment (not recommended for solids with polar surface
groups like oxides, zeolites, MOFs, etc.)
• P/P0 at ambient pressure is only 3x10-2 (Only pores < 1 nm can be explored
easily)

See Technote 35 for experimental details

Complimentary Use of CO2: Graphene Example

Zhu, Murali, Stoller, Ganesh, Cai, Ferreira,

Pirkle, Wallace, Cychosz, Thommes, Stach,
Ruoff, Science, 2011, 332, 1537-1541

NLDFT Analysis: slit/cylinder model

Krypton at 77 K and 87K
 Typically used for analysis of materials with low surface areas
 Pros
• Total surface areas down to at least 0.05 m2 can be determined with Kr
adsorption at 77 K
o Saturation pressure is very low at 77K (assuming a supercooled liquid)
o Far fewer molecules in the void volume which means higher sensitivity to
surface area and smaller void volume error
 Cons
• Due to details of the phase diagram of confined krypton, application for pore size
analysis at 77 K is very limited (however, at 87K pore size of thin films can be
analyzed up to ~10 nm)
Use of Kr at 87K: Porous Silica Thin Film Example
300 300

Silica film 450 m thick RUN 1 (ads) Silica film 450 m thick RUN 1 (Ads)
Silica Film, 450 nm thick, RUN 2 (ads/des) Silica film 450 nm thick RUN 2 (Ads/Des)
Volume [cm3 g-1 STP 240 240

Volume [cm3 g-1 STP

180 180

120 120

60 60

0 0
0 0.2 0.4 0.6 0.8 1 10-4 5 10-3 5 10-2 5 10-1 5 100
P/P0 P/P0
0.625

0.502

Kr (87 K) pore size

Dv(logd) [cm3 g-1]

0.379

distribution from
0.256 adsorption branch

0.133

0.01
15 25 35 45 55 65 75 85 95 105 Thommes, M.; Nishiyama, N.
Pore Diameter [Å]
Stud. Surf. Sci. Catal. 2007
Recommendations
 Pore size/volume characterization of microporous carbons
• Combination of carbon dioxide (273 K) with nitrogen (77 K) or argon (87 K)

 Pore size/volume characterization of microporous materials with polar

surfaces (e.g. oxides, MOFs, zeolites)
• Argon (87 K)

 Analysis of materials with ultra-low surface area

• Krypton (77 K) adsorption for surface area only
• Krypton (87 K) adsorption for pore size analysis of thin films
 Gas Adsorption Measurements
A Basic Comparison of Vacuum-Volumetric, Flow, and
Gravimetric Methods
Gas Adsorption Basics
 The quantity of gas adsorbed is a
function of:
• The strength of interaction
between gas and solid (intrinsic)
• Temperature (fixed)
• Pressure/concentration
(controlled variable)

 The plot of Adsorbed Amount vs.

Pressure at a specified temperature is
called an Isotherm P0: Saturation pressure of adsorptive
P/P0: Relative pressure of adsorptive
Adsorption Experimental Methods
 The basic adsorption experiment requires a means to:
• Control the temperature
• Vary the concentration/pressure of adsorptive
• Measure the amount of gas adsorbed

 There are three main methods to meet these requirements:

• Vacuum-Volumetric (Manometric) - e.g., Autosorb, Nova, Quadrasorb
• Flow – e.g., Monosorb, ChemBET, ChemStar, Autosorb iQ-C
• Gravimetric – e.g., Aquadyne
Vacuum-Volumetric Methods
 Vary adsorptive pressure by
creating conditions of partial
vacuum
Vacuum

 High precision and accurate

pressure transducers monitor
pressure changes due to the
adsorption process
Vacuum-Volumetric Methods
 Based on the ideal gas law

𝑃𝑉 = 𝑛𝑅𝑇
 Amount adsorbed is expressed as

𝑛𝑎𝑑𝑠 = 𝑛𝑑𝑜𝑠𝑒𝑑 − 𝑛𝑣𝑜𝑖𝑑

𝑉 𝑃𝑉
𝑛𝑎𝑑𝑠 = ∆𝑃 −
𝑅𝑇 𝑚𝑎𝑛 𝑅𝑇 𝑐𝑒𝑙𝑙
Dynamic Flow Methods
 Vary adsorptive concentration by
diluting the adsorptive in a carrier
gas flown over the sample TCD
A B
 Adsorption initiated by immersing
adsorbent sample in coolant

 Adsorption and/or desorption

processes are monitored using a
detector capable of responding to
changes in gas composition (typically
a Thermal Conductivity Detector)
Dynamic Flow Methods
 How a Thermal Conductivity
Detector (TCD) works:
• The thermal conductivity of a gas
stream changes with changes in the
gas mixture composition

• A TCD responds to these changes in

thermal conductivity by comparing
relative thermal conductivities before
and after the sample cell

• By calibrating the TCD signal with a

known quantity of gas, the volume
adsorbed can be obtained
Gravimetric Methods
 A microbalance is used to track
the change in mass of the
sample during the adsorption
process