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    BET Analysis Fundamentals - Sathish

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    nanosakthivel
    Surface area is created by processes that divide particles or generate porosity, such as size reduction through grinding or milling. It can be destroyed by sintering, melting, or Ostwald ripening. The Brunauer-Emmett-Teller (BET) method is commonly used to measure surface area using gas adsorption isotherms. It involves fitting a straight line to a multi-point plot based on the BET equation to determine the monolayer capacity, from which the surface area can be calculated using the cross-sectional area of the adsorbate gas, typically nitrogen. Proper measurement requires obtaining data points in the relative pressure range of 0.025 to 0.30 to ensure the BET model holds.

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    BET Analysis Fundamentals - Sathish

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    nanosakthivel
    227 views57 pages
    Surface area is created by processes that divide particles or generate porosity, such as size reduction through grinding or milling. It can be destroyed by sintering, melting, or Ostwald ripening. The Brunauer-Emmett-Teller (BET) method is commonly used to measure surface area using gas adsorption isotherms. It involves fitting a straight line to a multi-point plot based on the BET equation to determine the monolayer capacity, from which the surface area can be calculated using the cross-sectional area of the adsorbate gas, typically nitrogen. Proper measurement requires obtaining data points in the relative pressure range of 0.025 to 0.30 to ensure the BET model holds.

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    BET Analysis Fundamentals

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    Surface area is created by processes that divide particles or generate porosity, such as size reduction through grinding or milling. It can be destroyed by sintering, melting, or Ostwald ripening. The Brunauer-Emmett-Teller (BET) method is commonly used to measure surface area using gas adsorption isotherms. It involves fitting a straight line to a multi-point plot based on the BET equation to determine the monolayer capacity, from which the surface area can be calculated using the cross-sectional area of the adsorbate gas, typically nitrogen. Proper measurement requires obtaining data points in the relative pressure range of 0.025 to 0.30 to ensure the BET model holds.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    227 views57 pages

    BET Analysis Fundamentals - Sathish

    Uploaded by

    nanosakthivel
    Surface area is created by processes that divide particles or generate porosity, such as size reduction through grinding or milling. It can be destroyed by sintering, melting, or Ostwald ripening. The Brunauer-Emmett-Teller (BET) method is commonly used to measure surface area using gas adsorption isotherms. It involves fitting a straight line to a multi-point plot based on the BET equation to determine the monolayer capacity, from which the surface area can be calculated using the cross-sectional area of the adsorbate gas, typically nitrogen. Proper measurement requires obtaining data points in the relative pressure range of 0.025 to 0.30 to ensure the BET model holds.

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    of 57

    BET Analysis fundamentals

    Surface Area What is it?


    Surface Area is the means through which a solid
    interacts with its surroundings, especially liquids
    and gases.
    Surface area is created by division of particles (size
    reduction) and the generation of porosity.
    Surface area is destroyed by sintering (exceeding
    Tg), melting and Ostwald ripening.

    How to Create Area ?

    Size Reduction
    Grinding,
    milling,
    nanoscale

    preparation

    Make pores
    Partial

    decomposition

    Leach
    Gel

    then lyophilize

    How to Destroy Area ?

    Surface area is destroyed by


    melting

    sintering

    (exceeding Tg), and


    Ostwald ripening

    Adsorption Absorption

    Absorption is a phenomenon
    that occurs in a volume

    Adsorption is a phenomenon
    that occurs on a surface

    The word sorption encompasses both types of phenomena

    Adsorption processes
    Adsorption
    Physical (physisorption)
    - van der Waals interactions
    (result in attractive forces between
    adsorbent and adsorbate molecules)

    - Adsorbed molecules maintain their


    identity
    - Multilayers
    - No activation energy
    - Always reversible

    Chemical (chemisorption)

    - Chemical bonds between adsorbate


    and adsorbent formed
    - Adsorbed molecules loose their
    identity
    - Monolayers
    - Often activation energy required
    - Can be irreversible

    The gas sorption process

    Langmuir[1] described the kinetic behavior of the


    adsorption process. He postulated that at
    equilibrium, the rate of arrival of adsorptive
    (adsorption) and the rate of evaporation of
    adsorbate (desorption) were equal
    Furthermore, the heat of adsorption was taken to
    be constant and unchanging with the degree of
    coverage, .
    [1] I. Langmuir, J. Amer. Chem. Soc., 40, 1368 (1918)

    Irving Langmuir (1881-1957)


    Graduated as a metallurgical engineer from
    the School of Mines at Columbia University in
    1903
    1903-1906 M.A. and Ph.D. in 1906 from
    Gttingen.
    1935-1937 With Katherine Blodgett studied thin
    films.
    1948-1953 With Vincent Schaefer discovered
    that the introduction of dry ice and iodide into a
    sufficiently moist cloud of low temperature could
    induce precipitation.

    1932 The Nobel Prize in Chemistry "for his


    discoveries and investigations in surface
    chemistry

    Langmuirian behavior
    Confining adsorption to a monolayer, the Langmuir equation can be
    written

    V
    KP

    Vm 1 KP
    where V is the volume of gas adsorbed at pressure P, Vm is the
    monolayer capacity (i.e. =1) expressed as the volume of gas at STP
    and K is a constant for any given gas-solid pair. Rearranging in the
    form of a straight line (y=ab+x) gives

    P
    1
    P

    V KVm Vm

    Suitable Methods of Determination


    Gas adsorption allows probing of entire surface
    including irregularities and pore interiors.
    The amount adsorbed is a function of temperature,
    pressure and the strength of attraction or interaction
    potential.
    Physisorption is generally weak and reversible. The
    solid must be cooled and a method used to estimate the
    monolayer coverage from which surface area can be
    calculated.

    Adsorption Process

    Adsorbate

    Adsorptive

    Adsorbent

    The Isotherm
    The amount of gas adsorbed is a function of

    The strength of interaction between gas and solid


    (intrinsic)

    Temperature (fixed)

    Pressure (controlled variable) expressed as


    relative pressure P/Po

    Physisorption Process

    4)
    2

    Very Low Pressure Behavior

    Amount Adsorbed

    (micropore filling)

    Relative Pressure, P/Po

    Low Pressure Behavior

    Amount Adsorbed

    (monolayer)
    The knee

    Relative Pressure, P/Po

    Medium Pressure Behavior

    Amount Adsorbed

    (multilayer)

    Relative Pressure, P/Po

    High Pressure Behavior

    Amount Adsorbed

    (capillary condensation)

    Relative Pressure, P/Po

    Gas Sorption: Isotherm


    Desorption isotherm

    Va

    Adsorption isotherm

    p
    po

    p
    V a f po

    where
    p
    pressure of adsorbate
    o
    p saturated pressure of adsorptive

    Isotherm is a measure of
    the volume of gas
    adsorbed at a constant
    temperature as a function
    of gas pressure.
    Isotherms can be
    grouped into six classes.

    Types of isotherms
    according to the IUPAC classification

    I: microporous solids
    II & III: multilayer adsorption
    in non-porous solids
    IV & V: capillary condensation
    in mesoporous solids
    VI: stepped asdorption

    Volume adsorbed

    Types of Isotherms

    Limiting value (plateau) due to filled


    pores and essentially zero external
    area.
    Type I or
    pseudo-Langmuir

    Steep initial region due to


    very strong adsorption, for
    example in micropores.

    Relative Pressure (P/Po)

    Types of Isotherms

    Volume adsorbed

    Absence of hysteresis indicates


    adsorption on and desorption from a
    non-porous surface..
    Type II

    Low slope region in middle of


    isotherm indicates first few
    multilayers

    Rounded knee
    indicates approximate
    location of monolayer
    formation.
    Relative Pressure (P/Po)

    Gas Sorption: Isotherm

    Va

    Concave to the P/Po axis


    Type I
    or
    Langmuir

    Va

    P/Po

    Type II
    B

    Exhibited by microporous solids ( < 2nm )

    Exhibited by nonporous or macroporous


    solids ( > 50nm )
    Unrestricted monolayer-multilayer
    adsorption
    Point B indicates the relative pressure at
    which monolayer coverage is complete
    S. Lowell & J. E. Shields, Powder Surface Area and Porosity, 3rd Ed.
    Chapman & Hall, New York, 1991

    Types of Isotherms

    Volume adsorbed

    Example: krypton on polymethylmethacrylate

    Type III

    Lack of knee represents extremely


    weak adsorbate-adsorbent
    interaction
    BET is not applicable
    Relative Pressure (P/Po)

    Types of Isotherms

    Volume adsorbed

    Type IV

    Hysteresis indicates capillary


    condensation in meso and
    macropores.

    Closure at P/Po~0.4 indicates


    presence of small mesopores
    (hysteresis would stay open
    longer but for the tensilestrength-failure of the nitrogen
    meniscus.
    Rounded knee
    indicates approximate
    location of monolayer
    formation.

    Low slope region in middle of


    isotherm indicates first few
    multilayers

    Relative Pressure (P/Po)

    Va

    Gas Sorption: Isotherm


    Convex to the P/Po axis

    Type III

    Exhibited by nonporous solids

    Exhibited by mesoporous solids

    Type IV
    Va

    Initial part of the type IV follows


    the same path as the type II

    P/Po

    S. Lowell & J. E. Shields, Powder Surface Area and Porosity, 3rd Ed.
    Chapman & Hall, New York, 1991

    Types of Isotherms

    Volume adsorbed

    Example: water on carbon black

    Type V

    Lack of knee represents extremely


    weak adsorbate-adsorbent interaction

    BET is not applicable

    Relative Pressure (P/Po)

    Gas Sorption: Hysteresis

    Va

    Hysteresis

    P/Po

    Hysteresis indicates the presence of mesopores.


    Hysteresis gives information regarding pore shapes .
    Types I, II and III isotherms are generally reversible but type I can
    have a hysteresis. Types IV and V exhibit hysteresis.
    S. Lowell & J. E. Shields, Powder Surface Area and Porosity, 3rd Ed.
    Chapman & Hall, New York, 1991

    Gas Sorption: Isotherm


    Type V
    Va

    Highly uncommon
    Exhibited by mesoporous solids

    P/Po

    Exhibited by nonporous solids with


    an almost completely uniform surface

    Va

    Type VI

    P/Po

    S. Lowell & J. E. Shields, Powder Surface Area and Porosity, 3rd Ed.
    Chapman & Hall, New York, 1991

    Choice of Gas and Temperature

    Temperatures

    Gases
    Nitrogen
    Argon
    Krypton
    Carbon
    Others

    dioxide

    Liquid Nitrogen
    Liquid Argon
    Dry ice/acetone
    Water/ice
    Others

    Choice of Gas and Temperature

    Temperatures

    Gases
    Nitrogen
    Argon
    Krypton
    Carbon
    Others

    dioxide

    Liquid Nitrogen
    Liquid Argon
    Dry ice/acetone
    Water/ice
    Others

    Measurement Method
    Manometric
    (Classical vacuum, volumetric.)
    Requires that adsorbate be adsorbed by the
    sample, at some reduced temperature, as a
    function of pressure of pure adsorptive.

    Manometric

    P/Po values are achieved by creating conditions


    of partial vacuum

    High precision and accurate pressure


    transducers monitor pressure changes due to
    the adsorption process

    Working Equation

    PV = nRT
    nads = ndosed - nvoid
    nads = (PV/RT)man. - (PV/RT)cell

    Working Equation

    nads = (PV/RT)man. - (PV/RT)cell


    That is, the amount adsorbed is calculated as the difference between
    a) the amount of gas dosed from the manifold to the cell and b) the
    amount of gas which remains not adsorbed at the end of the
    equilibration time.

    Principles of BET Surface Area Measurement


    and Calculation
    Determine the monolayer capacity Vm from which
    the surface area of the solid can be computed.
    Adsorbate most commonly used is nitrogen
    Readily available in high purity
    Appropriate coolant, liquid nitrogen.

    Gas-solid interaction relatively strong.


    Widely accepted cross sectional area.

    Multilayer adsorption
    the BET equation (1938)
    Stephen Brunauer
    Edward Teller

    Paul Emmett

    Brunauer, Emmett & Teller

    Model of adsorption extended to multilayers.

    S. Brunauer, P.H. Emmett and E. Teller, J. Amer. Chem. Soc., 60, 309 (1938)

    V
    C ( P P0 )

    Vm (1 P P0 )(1 P P0 C ( P P0 )

    Brunauer, Emmett & Teller


    Or, in its familiar linearized form

    1
    1
    C 1 P


    V [( P0 P) 1] VmC VmC P0

    BET C constant varies from solid to solid.


    Low values represent weak gas adsorption
    typical of low surface area solids, organics
    and metals in particular.

    Measurement
    Obtain at least three data points in the relative pressure
    range
    0.025 to 0.30
    Plot 1/[VSTP(Po/P)-1] versus P/Po. It should yield a
    straight line if the BET model holds true.

    On all surfaces the BET model fails to accurately predict


    the multilayer adsorption behavior above P/Po = 0.5 (the
    onset of capillary condensation which fills pores with
    liquid adsorbate)

    X[(Po/P)-1]

    Calculation of Surface Area by


    the BET method

    negative intercepts are unacceptable


    0

    relative pressure, P/Po

    Calculation
    Fit best straight line through BET data
    set using least squares regression to
    find:

    C 1
    slope s
    Vm C
    intercept

    1
    i
    Vm C

    Calculation
    Solving for Vm

    1
    Vm
    si

    Total surface area, St, is calculated thus

    Vm Lav Am
    St
    Mv
    Adsorbate cross sectional area
    (0.162 nm2 for Nitrogen

    Lav = 6.022 x 1023


    Am = 0.162 nm2
    Mv = 22 414 mL
    nm2 to m2, x 10-18

    Multi-Point BET Plot (Interpretation)

    Never use data points too low in relative pressure (P/Po).

    Never use data points too high in (P/Po).

    Multi-Point BET Plot (Interpretation)

    Discard under-equilibrated points (at low P/Po)

    Never use less than three, preferably five data points.

    Porosity
    Pore Volume
    Total pore volume is derived from the amount
    of vapour adsorbed at a relative temperature
    close to unity (assuming pores are filled with
    liquid adsorbate).
    Vads = volume of gas adsorbed
    Vliq = volume of liquid N2 in pores
    Vm = molar vol. of liquid adsorbate (N2=34.7cm3/mol)
    Pa = ambient pressure
    T = ambient temperature

    Concept of Porosity: Open vs.


    Closed Pores
    Inter-connected
    (open)

    Closed

    Open pores are accessible


    whereas closed pores are
    inaccessible pores.

    Open pores can be interconnected, passing or dead


    end.
    Passing
    (open)

    Dead end
    (open)

    F. Rouquerol, J. Rouquerol, K. S. W. Sing, Adsorption by Powders and Porous Solids, Academic Press, 1-25, 1999

    Size of Pores (IUPAC Standard)


    Mesopores

    Micropores

    Zeolite,
    Activated
    carbon,
    Metal organic
    framework

    Macropores

    Mesoporous silica,
    Activated carbon

    2 nm

    Sintered metals
    and ceramics

    50 nm

    Porous material are classified according to the size of pores: material


    with pores less than 2 nm are called micropores, materials with pores
    between 2 and 50 nm are called mesopores, and material with pores
    greater than 50 nm are macrospores
    Sing, K. S. W. et al. Reporting Physisorption Data for Gas/Solid Systems. Pure & Appl. Chem. 57, 603-619 (1985).

    Shapes of Pores
    Cylindrical

    Slits

    Pore
    Shapes

    Conical

    Spherical or
    Ink Bottle

    Interstices

    F. Rouquerol, J. Rouquerol, K. S. W. Sing, Adsorption by Powders and Porous Solids, Academic Press, 1-25, 1999

    Techniques for Porosity Analysis

    Techniques for Porosity Analysis

    Techniques for Porosity Analysis

    Techniques for Porosity Analysis

    Techniques for Porosity Analysis

    Techniques for Porosity Analysis

    Techniques for Porosity Analysis

    Gas Sorption: Hysteresis


    Type B

    Type C

    Type D

    Type E

    Va

    Type A

    P/Po

    Cylindrical

    P/Po

    Slits

    P/Po

    Conical

    P/Po

    P/Po

    Bottle neck

    Pore Radius
    The average pore size can be estimated from the pore
    volume.
    Assuming cylindrical pore geometry (type A hysteresis)
    average pore radius (rp) can be expressed as:

    Other pore geometry models may require further


    information on the isotherm hysteresis before applying
    appropriate model.

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