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2nd layer
Tetrahedral
hole
Octahedral
hole
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fcc
hcp
bcc structure
not a close packed
structure
quite similar to fcc
(i.e. cubic nature of
its unit cell)
C. N. = 8
face-centered cubic
(fcc)
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(100) face
(birds eye view)
fcc (100)-(1 x 1)
ANS. ANSWER: CN = 8
RATIONALE: Each surface atom has four
nearest neighbours in the 1st layer, and
another four in the layer immediately below ;
a total of 8.
This contrasts with the CN of metal atoms in
the bulk of the solid which is 12 for a fcc
metal.
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On top sites
Bridge sites
Hollow sites
ANSWER: CN = 7
RATIONALE: Each surface atom has two
nearest neighbours in the 1st layer, and
another four in the layer immediately below,
and one directly below it in the third layer ;
this gives a total of 7
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(111) face
(birds eye view)
fcc(111)-(1 x 1)
On top sites
Bridge Sites
Hollow sites
On-top sites
Bridge sites (between 2 atoms)
Hollow sites (between 3 atoms)
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Energetics of Surfaces
all surfaces are energetically unfavorable in
that they have a positive free energy of
formation
formation of new surfaces by cleavage of a
solid and bond-breaking between atoms on
either side of the cleavage plane in order to
split the solid and create the surfaces
Bondbreaking requires work to be done on
the system, so the surface free energy (surface
tension) contribution to the total free energy of
a system must therefore be positive.
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Reconstruction of Surfaces
e.g. fcc (110)-(1x1)
(unreconstructed)
Summary
surface structures of single-crystals
most frequently studied surface planes of the fcc
((100), (110), (111)) and hcp systems
basic understanding of surface structure and
crystallography helpful in the study of surface
chemistry of some important fcc (e.g. Pt, Rh,
Pd, Au, etc.) and hcp metals (e.g. Ru)
Some metallic single-crystal undergo
reconstruction to minimize surface energy
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ADSORPTION OF
MOLECULES ON SURFACES
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Terminologies:
Substrate
- solid surface onto which adsorption can occur;
- e.g. Pt disc, Au(111) electrode
Adsorbate
atomic or molecular species which are adsorbed (or are
capable of being adsorbed) onto the substrate.
inorganic and organic species
Adsorption
process in which a molecule becomes attached onto a
surface of another phase
to be distinguished from absorption - uptake into the
bulk of a solid or liquid phase
Molecular Adsorption
Five basic steps:
1. Diffusion of reactants to the active surface
2. Adsorption of one or more reactants onto
the surface
3. Surface reaction
4. Desorption of products from the surface
5. Diffusion of products away from the surface
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Modes of Adsorption
- Terminologies:
Coverage
measure of the extent of adsorption of a
species onto a surface
denoted by (theta)
Exposure
measure of the amount of gas which a surface
has seen
product of pressure and time of exposure (unit:
Langmuir; where 1 L = 10-6 Torr s )
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Woods Notation
simplest and most frequently used method for
describing a surface structure
only works, however, if 2 unit cells are of the
same symmetry or closely-related symmetries
(more specifically, the angle between b1 & b2
(adsorbate vectors) must be the same as that
between a1 & a2 (substrate vectors))
involves specifying the lengths of the 2 overlayer
vectors, b1 & b2 , in terms of a1 & a2 respectively
written in the format: ( |b1|/|a1| x |b2|/|a2| ) i.e. a
(2 x 2) structure has |b1| = 2|a1| and |b2| = 2|a2|
Woods Notation
Substrate : fcc(100)
Substrate unit cell
Adsorbate unit cell
Woods Notation
Woods Notation
Substrate : fcc(100)
Substrate unit cell
Adsorbate unit cell
Substrate : fcc(110)
Substrate unit cell
Adsorbate unit cell
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Woods Notation
Woods Notation
ANSWER:
Substrate : fcc(111)
Substrate unit cell
Adsorbate unit cell
Substrate : fcc(___)
__________ unit cell
__________ unit cell
Woods Notation
Summary
atomic / molecular adsorption on substrate
surface unit cell of adsorbate (inorganic or
organic) species relative to the substrate (e.g.
single-crystal)
Woods notation for describing surface
structures of overlayers
Substrate : fcc(100)
c(2 x 2)
(2 x 2)R45
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