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Surface Structure of Metals

How do the surfaces look like?

Technological applications of metals

supported metal catalysts
electrodes, mechanical fabrications
related to surface properties
Understanding of surface properties
know the amount of each type of surface
exposed
have detailed knowledge of the properties
of the surface plane, i.e. well-defined
surface or single crystal

most common metallic crystal structures

Bodycentered cubic (bcc)
face-centered cubic (fcc)
hexagonal close packed (hcp)
low-index surface
planes of interest & practically used
e.g. (111), (110), (100)
surface vs. bulk structures
atomic arrangement

FCC and HCP Structures

both have close packed arrangement of atoms

differ in stacking arrangement

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Close Packing of Spheres

A second layer of spheres is placed in the

indentations left by the first layer
space is trapped between the layers that
is not filled by the spheres
1st layer

2nd layer

A single layer of spheres is closest-packed with a

HEXAGONAL coordination of each sphere

TWO different types of HOLES (so-called

INTERSTITIAL sites) are left
OCTAHEDRAL (O) holes with 6 nearest sphere
neighbors
TETRAHEDRAL (T) holes with 4 nearest sphere
neighbors

Tetrahedral
hole
Octahedral
hole

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When a third layer of spheres is placed in the

indentations of the second layer there are TWO choices
The third layer lies in indentations directly in line
(eclipsed) with the 1st layer
Layer ordering may be described as ABA

The third layer lies in the alternative indentations

leaving it staggered with respect to both previous layers
Layer ordering may be described as ABC

atoms on the 1st layer

atoms on the 1st layer

(yellow spheres)

atoms on the 2nd layer

atoms on the 2nd layer

(gray spheres)

atoms on the 3rd layer (red circles)

hcp
(ABA... stacking)

3 dimensional unit cell

atom on the 3rd layer

(ABC... stacking)
atom on the 3rd layer
(ABA... stacking)

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)

hexagonal close packed

(hcp)

* Each atom has 12 nearest neighbors

(i.e. Coordination Number = 12)

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Surface Structures of fcc

metal

fcc unit cell (100)

face (blue atoms)

(100) face
(birds eye view)

EXERCISE: What is the coordination number of

the surface layer atoms of fcc (100)?

fcc (100)-(1 x 1)

obtained by cutting the fcc metal parallel to the

front surface of the fcc cubic unit cell
atomic arrangement: 4-fold symmetry

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.

Characteristics of fcc (100) planes

all surface atoms are equivalent
smooth surface at the atomic scale
various adsorption sites for the adsorbate
molecules
On-top sites (above a single metal atom)
Bridge sites (between 2 atoms)
Hollow sites (between 4 atoms)
Depending upon the site occupied, an
adsorbate species (with a single point of
attachment to the surface) is therefore likely to
be bonded to either one, two or four metal
atoms.

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Adsorption Sites on fcc 100 Surface

On top sites
Bridge sites
Hollow sites

EXERCISE: What is the coordination

number of the topmost layer atoms of fcc
(110)?
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Characteristics of fcc (110) planes

first layer surface atoms are equivalent
second layer atoms also exposed
atomically rough surface with high anisotropy
various adsorption sites for the adsorbate
molecules
On-top sites
Short bridge sites (between 2 atoms in a
single row)
Long bridge sites (between 2 atoms in
adjacent rows)
Higher coordination sites (in the troughs)

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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fcc (111) surface

Adsorption Sites on FCC surface

Ontop sites
Short bridge sites
Long bridge sites
fcc unit cell
(111) face
(blue atoms)

Higher coordination sites

(111) face
(birds eye view)

fcc(111)-(1 x 1)

obtained by cutting the fcc metal in such a way

that the surface plane intersects the x, y and
z axes at the same value
atomic arrangement: 3fold symmetry
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Adsorption Sites on fcc 111 Surface

Characteristics of fcc (111) planes

all surface atoms are equivalent and have high
CN
atomically smooth surface
various adsorption sites for the adsorbate
molecules

On top sites
Bridge Sites
Hollow sites

On-top sites
Bridge sites (between 2 atoms)
Hollow sites (between 3 atoms)

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Intersection of surfaces in irregularly

shaped samples

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Surface Structures of hcp metal

hcp 001 Surface
(0001) surface plane
e.g. Ru(0001)

Closepacked plane, and one axis (the caxis

perpendicular to these ller index notationbased on 3
axes at 120 in the planes.
Thus, the 4-index structure: hcp (0001)
3rd is redundant and sometimes left out; thus, (0001) is
reduced to (001)
resembles fcc (111)

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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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How to minimize surface energy

1. by reducing the amount of surface area
exposed
particulate metals (single-crystallites)
that of a sphere (low surface free energy;
consider a droplet of water)
2. by predominantly exposing surface planes
which have a low surface free energy
high surface atom density
surface atoms of high coordination number
decreasing stability (in vacuum):
fcc(111) > fcc(100) > fcc(110)
3. by altering the local surface atomic geometry in
a way which reduces the surface free energy
relaxation & reconstruction

Reconstruction of Surfaces
e.g. fcc (110)-(1x1)
(unreconstructed)

e.g. fcc (110)-(1x2)

(reconstructed)

- involves change in the periodicity of the surface structure

and surface symmetry relative to the bulk

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 )

Physical Adsorption (Physisorption)

weak Van der Waals
no significant redistribution of electron density in
either the molecule or at the substrate surface
Chemical Adsorption (Chemisorption)
Involves a chemical bond
involves substantial rearrangement of electron
density, formed between the adsorbate and
substrate
between extremes of virtually complete ionic or
complete covalent character

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Structure of Metals & Adsorption Geometry

What happens when a molecule becomes adsorbed
onto a surface?
Why study surface chemistry?
to identify the nature of the adsorbed species
and its local adsorption geometry (i.e. its
chemical structure and co-ordination to adjacent
substrate atoms)
to determine the overall structure of the
extended adsorbate/substrate interface (i.e.
the long range ordering of the surface)

Surface Unit Cell

Surface Unit Cell

fcc(100) surface unit cell
4fold rotational symmetry (unit cell: square symmetry")
to define the unit cell shape, size, and symmetry:
2 vectors which have a common origin are used; and
2 sides of the unit cell are defined

by convention, the 2 vectors which define the fcc(100)

unit cell are called a1 & a2;
have the same length i.e. |a1| = |a2| ;
are mutually perpendicular

Surface Unit Cell

fcc(111) surface unit cell

fcc(110) surface unit cell
2fold rotational symmetry (unit cell:
rectangular)
by convention, |a2| > |a1|

3fold symmetry (unit cell: hexagonal)

2 vectors are the same i.e. | a1| = | a2|
angle between the vectors < 90(i.e. 30) or > 90
(i.e. 120)

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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

(2 x 2) adsorbate overlayer on a fcc(100) surface

adsorbate is bonded terminally ontop site of individual
atoms of the substrate

Substrate : fcc(100)
Substrate unit cell
Adsorbate unit cell

primitive (2x2) or p(2x2)

overlayer structures

Woods Notation

Woods Notation

(2 x 2) adsorbate overlayer on a fcc(100) surface

adsorbate is bonded terminally on the 4fold hollow
site of individual atoms of the substrate

(2 x 2) adsorbate overlayer on a fcc(110) surface

adsorbate is bonded terminally on the hollow
sites of individual atoms of the substrate

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

EXERCISE: Fill in the blanks by giving the Woods notation

of the overlayer structure and the crystallographic
orientation of the substrate.

ANSWER:
Substrate : fcc(111)
Substrate unit cell
Adsorbate unit cell

Substrate : fcc(___)
__________ unit cell
__________ unit cell

(_ x _) adsorbate overlayer on a fcc(___) surface

- adsorbate is bonded terminally ______ site of individual
atoms of the substrate

Woods Notation

(2 x 2) adsorbate overlayer on a fcc(111) surface

adsorbate is bonded terminally on top site of
individual atoms of the substrate

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

- adsorbate unit cell could be:

(a) facecentered (2 x 2) or simply c(2 x 2)
(b) primitive(2 x 2)R45 or simply (2 x 2)R45
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