Surface area determination Surface area determination -- physisorption physisorption

and chemisorption and chemisorption and chemisorption and chemisorption

Motivation
Physisorption
Chemisorption Chemisorption
Outlook
Literature: Literature:
1. DIN ISO 9277: BET method
2. DIN66136: Dispersionmeasurement of metals 2. DIN 66136: Dispersion measurement of metals
3. DIN 66134: BJ H method
4. Rouquerol F, Rouquerol J , Sing K. Adsorption by Powders and Porous Solids. London:
Academic Press; 1999.
5 N i kAV Si KSW Th M S f A dP i H db k f 5. NeimarkAV, Sing KSW, ThommesM. Surface Area and Porosity. Handbook of
Heterogeneous Catalysis. Wiley-VCH VerlagGmbH & Co. KGaA; 2008.
6. Bergeret G, Gallezot P. Particle Size and Dispersion Measurements. Handbook of
HeterogeneousCatalysis. Wiley-VCHVerlagGmbH& Co. KGaA; 2008.
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
Heterogeneous Catalysis. Wiley VCH VerlagGmbH & Co. KGaA; 2008.
7. Quantachromemanuals
Surface area determination Surface area determination -- physisorption physisorption
and chemisorption and chemisorption and chemisorption and chemisorption
What doweobtain? What do we obtain?
specific surface area of a substance
specificsurfaceareaof apart of asubstance(i e of themetal particleson specific surface area of a part of a substance (i.e. of the metal particles on
a support)
Why do we need such quantities?
comparability of different charges of the same substance
comparability of catalyst activity (... not given per gram)
Idea: surface area is a measure for the number of catalytic centers (but for sure
not the number of active sites no one knows how an active site looks like)
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
Surface area determination Surface area determination -- physisorption physisorption
Weakadsorbate adsorbensinteractions first level approximation:
Adsorption energyisconstant in thefirst layer anddifferent but p gy y
nearlyconstant in thefollowingmultilayers
We measure the (in principle) whole surface area! We measure the (in principle) whole surface area!
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
Physisorption Physisorption
What What do do we we measure measure?? -- isotherms isotherms What What do do we we measure measure? ? isotherms isotherms
IUPAC isotherm
classification
Saturation behaviour for highp/p
0
concave convex
sharp kneepoint B
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
How Howdo do we we measure measure? ?
Volumetric Volumetric measurement measurement Volumetric Volumetric measurement measurement
ideal gas law:
nRT pV =
ideal gas law:
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
1. Dead volume measurement with He 1. Dead volume measurement with He
V
1
T
1
Problems: Problems:
V
2
is unknown, T
2
is not well defined:
Quantachrome:
V
2
T
2
1. V
2
at RT withHe
2. Pressurechangewithandwithout
bathyieldsvolumeof cold and y
warm zonevolumein V
2
Cold and warm zone changeover Cold and warm zone changeover
volume should be minimized!
Some adsorbens absorb also He!
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
2. Measurement with N 2. Measurement with N
22
V
1
T
1
1. Certainamount of N
2
isdosed
in V
1
2 EquilibrationwithV yields 2. EquilibrationwithV
2
yields
new(lower) p
1
=p
2
3. Steponeisrepeateduntil the
d i d desiredp
4. thelost amount isnowin V
2
,
i.e. in thecold andwarm
zonevolumeandtheresidual in
thecalculationistheadsorbed
amount of N
22
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
Analysis Analysis of of the the isotherms isotherms
the the BET BET method method the the BET BET method method
1 1 / p C p p
Brunauer, Emmett andTeller in the1930s
( ) ( )
0 0
0
1 1
/ 1
/
p
p
C n
C
C n p p n
p p
m m a
+ =

withn
a
: adsorbedamount
bx a y + = bx a y +
b a
n
m
+
=
1
1 + =
b
C
BET constant C: Monolayer capacity
b a + a
L a n a
m m s
=
nm a
m
162 . 0 = for N
2
Specificsurfacearea
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
L: Avogadro number
Analysis Analysis of of the the isotherms isotherms
the the BET BET method method the the BET BET method method
Howtodo?
Fit withtheBET equationin Fit withtheBET equationin
therangeof
p/p
0
=0.05 ... 0.3
Sometimesevenat lower
upper limit
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
BET BET equation equation, BET , BET constant constant CC,,
Langmuir Langmuir equation equation as as limit limit for for C=1 C=1 Langmuir Langmuir equation equation as as limit limit for for C 1 C 1
( ) ( )
0
1 1 / p C p p

+ =
( ) ( )
0 0
/ 1 p C n C n p p n
m m a
+

E E
e
RT
E E
L
C

=
1
Fromtheoriginal theory:
E i th d ti f th fi t l d E
1
is the adsorption energy of the first layer and
E
L
the liquefaction energy,
withE E thistransformsintotheLangmuir equation with E
1
=E
L
this transforms into the Langmuir equation
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
Isotherm Isotherm classification classification
IUPAC isotherm U C so e
classification
Saturation behaviour for highp/p
0
( filli ) (porefilling)
concave convex
sharp kneepoint B
Type I: Langmuir, saturation
Type II: C >2, sigmoid(S-shaped) yp g ( p )
non- or macroporous
Type III: C <2, weakinteractions
Type IV: C >2, mesoporous, saturation
Type V: C <2, likeIII withsaturation
TypeVI: stepwise(layer bylayer) adsorption
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
Type VI: stepwise(layer bylayer) adsorption
Adsorption and desorption hysteresis Adsorption and desorption hysteresis
H1: narrowdistributionof relativelyuniform H1: narrow distribution of relatively uniform
(cylindrical-like) pores
-delayed condensation and no network effects,
analysisof thedesorptionbranch analysis of the desorption branch
H2: complex pore structure, network effects are
i t t l i f th d ti b h important, analysis of the adsorption branch
H3: non-rigid aggregates of plate-like particles
or assemblages of slit-shaped pores
- nosaturation
H4: complex materials containing both
microporesand mesopores
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
NeimarkAV, Sing KSW, ThommesM. Surface Area and Porosity. Handbook of Heterogeneous Catalysis, Wiley; 2008.
Adsorption and desorption hysteresis, Adsorption and desorption hysteresis,
some effects some effects some effects some effects
Oftenat p/p
0
=0.42 for N
2
independent of theadsorbent
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
NeimarkAV, Sing KSW, ThommesM. Surface Area and Porosity. Handbook of Heterogeneous Catalysis, Wiley; 2008.
BET BET method method example example 11
#10904 #10904 #10904 #10904
onlytypeII andtypeIV isotherms only typeII and typeIV isotherms
the p/p0 range should give a
positive linear slope
i h li i i in the linearity region
1 /
m a
n n
must be fulfilled
for thisisfulfilled 200 100 < < C
For negative slopeor non-linearitytheBET methodisnot applicable!
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
BET BET method method example example 11
#10904 #10904 #10904 #10904
C=40 ... 55
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
BET BET method method example example 22
#9828 #9828 #9828 #9828
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
BET BET method method example example 22
#9828 #9828 #9828 #9828
C =-370 C 370
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
BET BET method method example example 22
#9828 #9828 -- Langmuir Langmuir #9828 #9828 Langmuir Langmuir
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
BET BET method method example example 11
#10904 #10904 -- Langmuir Langmuir #10904 #10904 Langmuir Langmuir
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
Reference Reference materials materials for for the the BET BET method method,,
measurement measurement errors errors measurement measurement errors errors
DIN ISO 9277:
measurement errors:
I t t ( V T ) Instrument (p, V, T, vacuum)
Scatter of different measurement
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
Surface area determination Surface area determination -- chemisorption chemisorption
Strong adsorbate adsorbensinteractions first level approximationfor metal
on a support:
Adsorption energyon themetal isconstant in thefirst layer andstrongly
exceedstheadsorptionenergieson thesupport or in multilayers
We measure (in principle) the metal surface area!
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
How Howdo do we we measure measure? ?
Pretreatment Pretreatment,, choice choice of of adsorbate adsorbate Pretreatment Pretreatment, , choice choice of of adsorbate adsorbate
Pretreatment is different from physisorption
removal of water
reduction of the metal (only!)
Quantachrome: Flow cell, reductionwithH
2
/Ar or CO, evacuation Q ,
2
,
Choice of adsorbate is crucial
only adsorption on the metal
no irreversibel subsurface absorption p
novolatile reactionproducts(carbonyles)
nobulkreaction
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
How Howdo do we we measure measure? ?
Volumetric Volumetric measurement measurement Volumetric Volumetric measurement measurement
ideal gas law:
nRT pV =
ideal gas law:
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
Chemisorption: Chemisorption:
measurement measurement measurement measurement
Twoisotherms:
1. Total amount
2. Reversible amount
( ti ft t ti (evacuationafter saturation
anda secondisotherm)
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
Chemisorption: Chemisorption:
analysis analysis analysis analysis
Linear extrapolationtop =0
yieldsthevolumeof an
adsorbed monolayer v
m
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
Chemisorption: Chemisorption:
analysis analysis analysis analysis
100 1 v
) (
100 1
22414
1 2
metal g m
wt
a
m
Ln
v
A
m
m
M

=
Specificmetal surfacearea:
wt
M
m
n v
D
m
100
22414
=
metal dispersion:
Vm volumeof an adsorbed monolayer
L Avogadro number
n chemisorption stoichiometry
m sample mass
a
m
surfaceareaoccupiedbya metal atom
wt metal loading
M atomicmassof themetal
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
Comparison Comparison of of different adsorptives different adsorptives for for Pt Pt, , Pd Pd
and and Rh Rh and and Rh Rh
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
Kunimori K, UchijimaT, Yamada M, Matsumoto H, Hattori T, Murakami Y. Appl Catal 1982;4(1):67-81.
Chemisorption Chemisorption the the heat heat of of adsorption adsorption
Triangles:
Heat of adsorption for
CO/Pt(110) is far from
being constant!
Dirk Rosenthal, Electronic Structure, Department Inorganic Chemistry, Fritz-Haber-Institut der MPG, Berlin, Germany
Stuck A, WartnabyCE, YeoYY, StucklessJ T, AlSarraf N, King DA. An improved single crystal adsorption
calorimeter. Surf Sci 1996;349(2):229-40.