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A

7
The Adsorption arrd Absorption of Hydrogen
by Metals
BY R. BURCH

The reversible interaction of hydrogen with metals is an essential part of many


catalysed reactions, is used to determine specific surface areas, and offers the prospect
of using metal hydrides for hydrogen storage. A number of comprehensive reviews
dealing with various aspects of H in metals have appeared and reference is made to
these at appropriate points in the text. It is not our intention, therefore, to attempt
an in-depth survey of the interaction of H with metals. Instead, we shall trace the
progress of a H atom from its initial state in a gaseous molecule through a variety of
intermediate adsorbed states to its final absorbed state.
Problems of current interest to which we draw attention in this review are (1) the
nature of adsorbed hydrogen, (2) the possibility of weak adsorption in excess of a
monolayer and its influence on surface area determinations, (3) the adsorption/
absorption transition and the mechanism of absorption, and (4)the selectivity of H for
special sites in alloys and the structural modifications in alloys caused by H. Finally,
we shall comment briefly on the extent to which existing theoretical models can
account for some of these features.

1 Adsorption of Hydrogen
Many different forms of adsorbed hydrogen have been observed or postulated.
These include molecular hydrogen, positively and negatively charged H atoms,
weakly and strongly bound states, etc. We consider first the adsorption of H on
Pt( 111) surfaces in the knowledge that similar adsorption occurs on other Pt surfaces,
and in the expectation that Pt is representative of face-centred-cubic metals in general.

Pt(ll1) Single Crystal Surfaces.-Somorjai and co-workers investigated the adsorp-


tion of hydrogen on Pt(ll1) at elevated temperatures and reported that hydrogen
adsorbed readily only on to stepped Pt(ll1) surfaces. This is not correct. Hydrogen
adsorption on any clean Pt surface is rapid 2-4 even at low temperatures (initial
sticking coefficient z 0.1). The discrepancy arises because the comparatively small
heat of adsorption of hydrogen on Pt means that in experiments in V ~ C U Oabove
room temperature the equilibrium amount of adsorbed H is very smalL5
Thermal desorption spectra (TDS) of hydrogen preadsorbed at 78 K show three
peaks (PI, P2, and P 3 ) with T,,, at 140, 230, and 310 Preadsorption at 150 K
gives two peaks in the desorption spectrum. Typical spectra are shown in Figures

B. Lang, R. W. Joyner, and G. A. Sornorjai, Surface Sci., 1972, 30,454.


K. E. Lu and R. R. Rye, Surface Sci., 1974, 45, 671.
K. Christmann, G. Ertl, and T. Pignet, Surface Sci., 1976, 54, 365.
R. W. McCabe and L. D. Schmidt, Surface Sci., 1977, 65, 189.
K. Christmann and G . Ertl, Surface Sci., 1976, 60, 365.
1
2 Chemical Physics of Solids and their Surfaces
l(a) and l(b). The total surface coverage is about a monolayer (0 = 1). Christmann
et aL3 have calculated heats of desorption ( E d ) from TDS and from adsorption
isotherms and obtained values of 30 and 40 kJ mol- ' for the p2 and /j3 states, respect-
ively. In contrast, from spectra having almost identical T,,, McCabe and Schmidt
calculate values of 53 and 75 kJ mol- ' for p2 and p 3 , and 33 kJ mol- for pl. However,
they report a strong composition dependence of Ed over the range 0.03 < 0 < 0.25,
so that Ed Y , 42 kJ mol-' at 0 = 0.25. The discrepancies at low coverage (0 < 0.25)
may be due to diflerences between the surfaces examined (the high value of Ed at
0 = 0.03 may reflect preferential adsorption at surface defects), or because of errors
in the calculation of Ed. King has pointed out a possible error when deriving Ed
from TDS if weakly bound intermediate states exist. Schwartz et al.' also describe
how errors can arise if the wrong order of reaction is assumed. By utilizing the entire
desorption spectrum of H/Ti they show that the order of the desorption reaction is
1.5, yielding a value for Ed of 88 kJ mol-'. Analysis using only T,,, and assuming a
second-order reaction gave Ed = 210 kJ mol-'.

n 1CCll

+
2
c
U
A 200 400

I
200 400

T/ K
Figure 1 Thermal desorption spectra for H on metals: ( a ) HIPt(l11) after adsorption at 80 K ;
(b) H/Pt(lll) after adsorption at 150 K ; ( c ) Hlstepped Pt(ll1); ( d ) Histepped Pt(l11) after
argon ion bombardment; ( e ) H/Pt black; ( f ) H/Pd wire

McCabe and Schmidt note that the /j3 state for H/Pt( 1 I 1) could equally well be
described by second-order kinetics or by first-order kinetics with a variable Ed.
However, H,/D, exchange experiments 2 , 3 confirm that p 2 and /j3 are both atomic
states. Adsorbed atomic hydrogen could still desorb as molecular hydrogen with
first-order kinetics if only a single surface site is involved in the desorption. This
seems to be the case for H on Pd at high surface coverages (see later), but is unlikely
to be important for the P3-state which only desorbs when 0 < 0.5.

D. A. King, Surface Sci., 1977, 64, 43.


J. A. Schwartz, R. S. Polizzotti, and J. J. Burton, Surface Sci., 1977, 67, 10.
The Adsorption and Absorption of Hydrogen by Metals 3
Work function data '* at 150 K show that after a small positive maximum (2 meV),
attributed to preferential adsorption of Ha- at surface steps, the work function
decreases continuously with H coverage (H") t o - 230 meV. Neither a change in
polarity nor even a discontinuity in the dipole moment is observed when the p2 state
begins to fill after completion of the p3 state. The sign of the work function change is
opposite to that found with Ni or Pd.9 However, in all three cases the dipole
moment is small, indicating essentially covalent bonding.
The distribution of H atoms on Pt(l1 I ) has been considered. Christmann et aL3
reject the possibility that the p2 and p3 states correspond to different geometric
locations. Toya l o had previously proposed two types of adsorbed H, an 'r-adatom'
situated above a single metal atom and located outside the electronic surface of the
metal, and an 's-adatom' situated at a surface interstitial site. However, this is not
consistent with the observed smooth decrease in work function up to 8 = 1.0.
Christmann et al.3 suggest instead that repulsive interactions between H atoms pro-
duce an ordered structure in which H desorbs from the p3 state by the recombination
of two H atoms when neighbouring sites are empty, while H desorbs from the p2 state
when neighbouring sites are occupied.
It is difficult t o determine whether H atoms are adsorbed above or between metal
atoms. Flores et a1.l' have presented a model for H/Pt(l 1 1) which is consistent with
the data described above, and also with n.m.r., i.r., and neutron inelastic scattering
data, all of which point to H bound to more than one Pt atom. In this model the
H-H repulsions originate from the interaction of the screening potentials around the
hydrogens. Their model (Figure 2) is interesting with regard to absorption (see later)

Figure 2 Proposed structure for H/Pt( 1 1 1) after ref. 11. Large circles, Pt atoms. 0 and 0 ,
H atoms. Up to 6 = 0.5, only the 0 sires are occupied (p2 state). At 6 = 1 .O, 0 and 0 are
equivalent (PI state)

because it shows that as 8 -+ 1.0 both forms of hydrogen ( / j 2 and p3) become equi-
valent. Only when hydrogen is being adsorbed or desorbed are /j2 and p3 distinguish-
able. A very similar structure for Ni( 1 11) has been proposed on the basis of LEED
results.'

K. Christmann, 0. Schober, G . Ertl, and M. Neumann, J. Chem. Phys., 1974,60,4528.


H. Conrad, G. Ertl, and E. E. Latta, Surface Sci., 1974, 41,435.
lo T. Toya, Supplement of Progress in Theoretical Physics, 1962, 23, 250.
F. Flores, N. H. March, and C. J. Wright, Phys. Letters, 1977, 64A, 231.
IZ M. A. van Hove, G . Ertl, K. Christmann, R. J. Behm, and W. H . Weinberg, Sofid State Comm.,
1978, 28, 373.
4 Chemical Physics of Solids and their Surfaces
The Influence of Surface Imperfections. Bernasek and Somorjai l 3 suggested that the
rate of the H2/D2 exchange reaction was lo4 times faster at surface steps than at
terrace atoms, and, therefore, that surface steps are necessary for the facile dissociation
of hydrogen molecules. This is incorrect.2, 3 , 5 * l 4 At low coverages the sticking
coefficient is four times higher for a stepped surface than for a flat surface, but above
0 = 0.25 the two surfaces are similar.5 On a stepped surface there is a clearer distinc-
tion between the B2 and p3 states as shown by the fact that the p3 state is almost
saturated before adsorption into the p2 state commences. [Compare Figures 1(b) and
I(c).] However, the positions of the desorption maxima are hardly altered. Similarly,
when a Pt( 11 1) surface is distorted by argon ion bombardment a small shoulder is
observed on the high-temperature side of the f13 peak, but otherwise the desorption
spectra remain unaltered [Figure 1 (d)].
With respect to the absorption of H the important conclusions from single crystal
data for Pt are first, that as 8 -+ 1 all the adsorbed H atoms become equivalent and
have the same binding energies, and second, that surface imperfections enhance
strong adsorption at low surface coverages, but have little effect as 0 approaches a
monolayer.

Polycrystalline Platinum.-Three desorption peaks are observed with Pt powders


(170, 250, and 360 K) and films l 6 (120, 200, 330 K) [compare Pt(l1 l)]. Calculated
heats of desorption for Pt films are 34, 50, and 88 kJ mol-l. Similar values are
found with Pt wire l 7 (71 kJ mol-’ at 0 = 0.37 decreasing to 46 kJ mol-’ at 8 =
0.46). Surface potential measurements on Pt films are consistent with work function
data for single crystals. In both cases the most strongly bound H, located at surface
imperfections, has a partial negative charge, while H on terrace sites has a partial
positive charge. Dus and Tompkins l 8 also report a weakly bound (5 kJ mol-’)
molecular species, H,, which only adsorbs at high pressures.
Additional States of Hydrogen. Temperature programmed desorption (TPD) of H
from Pt blacks between 77 and 670 K revealed four peaks (a,p, y, 6) with T,,, of
170, 250, 360, and 570 K. A further peak ( E , T,,,, z 470 K) has been reported’”
[see Figure I(e)], and a very stable form of hydrogen 2 o (Q) is retained by Pt black even
after outgassing at 630 K. Dixon et ~ 1 detected
. ~ five
~ states of hydrogen adsorbed on
alumina-supported Pt. The u, p, and y states of Tsuchiya et a1.I’ apparently corres-
pond to the PI, p2, and p3 states found on single crystal Pt.4 However, this may be
misleading because unlike the p2 and p3 hydrogens, p and y hydrogens are not inter-
changeable. Thus, H and D do not equilibrate if, for example, H is adsorbed into the
fi state and D into the y state. At the same time the total amount of /3 + y + 6
hydrogen is apparently constant, which led Tsuchiya et al. t o propose that all three
states used the same surface sites. It was suggested that a, p, y, and 6 hydrogen
corresponded respectively to linearly bonded H, molecules, bridge-bonded H,
molecules, linearly bonded H atoms, and bridge-bonded H atoms, with all four types
of hydrogen adsorbed on the external surface of the Pt.
l3 S. L. Bernasek and G. A. Somorjai, J . Chem. Phys., 1975,62, 3149.
‘4 I. E. Wachs and R. J. Madix, Surface Sci., 1976, 58, 590.
S. Tsuchiya, T. Amenomiya, and R. J. Cvetanovic, J . Catalysis, 1970, 19, 245.
l6 J. J. Stephen, V. Ponec, and W. M . H. Sachtler, J . Catalysi~,1975, 37, 81.
l7 P. R. Norton and P. J. Richards, Surface Sci.,1974, 41, 293.
R. Dus and F. C . Tompkins, J.C.S. Faraday I , 1975, 71, 930.
l9 D. Moger, M. Hegedus, G. Besenyei, and F. Nagy, Reaction Kinetics Catalysis Letters, 1976,5,73.
*O Z. Paal and S. J. Thomson, J . Catalysis, 1973, 30, 96.
21 L. T. Dixon, R. Barth, R. J. Kokes, and J. W. Gryder, J. Catalysis, 1975, 37, 376.
The Adsorption and Absorption of Hydrogen by Metals 5
This model is not consistent with recent experimental results. Single crystal data
show that all hydrogen adsorbed above 150 K is atomic, and that the p2 and p3 states
are on geometrically equivalent sites. It is also difficult to see how y and 6 hydrogens
can both be on the Pt surface and yet not be in equilibrium. It seems more probable
that the y and 6 hydrogens are ‘incorporated’ in different ways into the Pt, so that H
transfer to and from these adsorption sites is a slow activated process.
Further evidence that the 6, E , and R H are not surface states comes from the kinetics
of their formation and removal, Moger et ~ 1 observe . ~ that ~ the y state fills long
before the E or 6 states are occupied. At room temperature E and 6 states are not
formed from the y state even after 80 h.19 Moreover, y, E , or 6 hydrogen can only
interact with oxygen at temperatures close to those at which desorption would occur.
Szabo et observed that after covering the surface of Pt black with gold the TPD
spectrum was almost identical to that for clean Pt, but the electrolytic charging curve
was quite different. They conclude that most of the hydrogen is dissolved in the Pt
rather than adsorbed on the surface. They also report that on Pt black only 13 % of
the adsorbed H is on the external surface.
Stephen et aE.I6 have also reported the slow formation of a type of hydrogen which
subsequently desorbed at 330 K. The magnitude of the desorption peak was depen-
dent on the time of adsorption at 78 K. About I % of a monolayer of extra hydrogen
is adsorbed in 10 minutes.
Further evidence for ‘occluded hydrogen’ comes from the work of Paal and
Thomson 2 o and Wells.24 Paal and Thomson found that tritium was retained by Pt
black at 630 K long after the initial exposure to gaseous tritium was terminated. They
propose two forms of occluded hydrogen (QI and QII), the first of which exchanges
with gaseous hydrogen, hydrogenates ethylene, hexene, and cyclohexene, and is
oxidized by oxygen, and the second of which only exchanges with hydrogen. Wells
observed with Pt powders that after evacuation at 373 K about 10% of a monolayer
of H was readily available for H2/D2exchange or butene hydrogenation, and that a
further 40% of a monolayer became available over a period of several days. Wells
postulates a cavity model to explain his results. Another possibility is that his readily
accessible hydrogen is located along dislocations or low-angle grain boundaries. The
very strongly bound hydrogen reported by Paal and Thomson (RII) could then be
located on the internal surfaces of voids within the Pt crystallites. However, it is also
possible that this hydrocarbon-inaccessible hydrogen is present in a combined form
(hydroxyl ?) which can exchange with tritium atoms but cannot desorb as hydrogen
molecules.
We can summarize the data for polycrystalline Pt as follows. There are seven or
eight types of adsorbed hydrogen, half of which refer to hydrogen adsorbed on the
external surface of the Pt, and the remainder refer to hydrogen incorporated in
different forms at dislocations, grain boundaries, or inclusions. In view of the extent to
which H can be incorporated into Pt black it is perhaps surprising that good agreement
is often obtained between surface areas of Pt powders measured by krypton adsorption
and by hydrogen chemisorption. It is possible that the ‘correct’ amount of adsorbed
hydrogen corresponds to a partial coverage of the external surface combined with a
contribution from occluded hydrogen. Particularly in cases where there is any doubt
about the cleanliness of a Pt surface, H chemisorption is unlikely to be a reliable
method for the determination of metal surface areas. Even with Pt single crystals it is
22 D. Moger, G . Besenyei, and F. Nagy, Reaction Kinetics Cutalysis Letters, 1975, 3, 231.
23 S. Szabo, D. Moger, M . Hegedus, and F. Nagy, Reactiorz Kinetics Catalysis Letters, 1977, 6, 89.
24 P. B. Wells, J. Cafalysis, 1978, 52, 498.
6 Chemicul Physics of Solids and their Surfaces
interesting that enhanced dissolution seems to occur, possibly in the vicinity of surface
steps.'

2 Adsorption and Absorption of Hydrogen by Palladium


Palladium is typical of a number of' metals which unlike Pt are capable of not only
adsorbing but also absorbing large quantities of hydrogen. A collection of excellent
articles on various aspects of the absorption of hydrogen by metals has been published
recently,25 to which the reader is referred for more detailed accounts of recent work.

Adsorption of Hydrogen.---Pd Singlc Crj..ctals. Conrad et ~ 1 1 investigated


. ~ the adsorp-
tion of hydrogen on Pd(l10) and Pd(ll1) surfaces and found many similarities with
Pt. Above room temperature there is a single desorption peak at about 350-360 K
for both surfaces. The heat of desorption is 96 kJ mol-' for Pd(ll0) and 88 kJ mol-'
for Pd( 1 1 l), and is constant up to 0 3 0.5. On a stepped surface the heat of desorption
at low coverages increases to 97 kJ niol- [compare Pt( 1 1 l)]. Conrad et a/. have also
observed a large flat peak at about 670 K due to the desorption of absorbed hydrogen.
This peak appears after the desorption of strongly chemisorbed hydrogen because the
rate of desorption of dissolved H is determined by the rate of diffusion from the bulk
to the surface.
LEED data for Pd(l11) indicate 2 6 a 'true' 1 x 1 structure. The H atoms are
thought to be between rather than above Pd atoms. This is supported by semi-
empirical calculation^,^^ by the fact that the photoelectron spectrum of H/Pd(l 1 1)
can best be interpreted by assuming that the H penetrates the metal surface," and
by analogy with Pt(l1 l), Ni(ll1) 1 2 9 2 9 and Ni(100).30 Adsorption onto Pd( 11 1)
probably occurs first by adsorption into strongly bound states where repulsions
between H atoms are negligible. Further adsorption into additional sites will be
accompanied by a progressive decrease in the heat of adsorption due to repulsive
interactions. At 0 = 1.0 all the hydrogen atoms will be equally weakly adsorbed
and in equilibrium with dissolved hydrogen (see later).
Polycr,t~stal/int~Pd. Aldag and Schmidt 3 1 in flash-desorption experiments (heating
rate 100-500Ks-') have observed three very ill-defined peaks (p,, lj2, and p 3 ; T,
350-650 K) after exposure of Pd wires to hydrogen at 200 or 300 K. The binding
energies are calculated to be 92, 105, and 146 kJ mol-', respectively, and the three
peaks are assumed to correspond to adsorption on different crystal planes. Adsorption
at 100 K results in a new low-temperature peak (a) at 250 K which is due to absorbed
H . Couper and John 3 2 have recently observed a low temperature a peak and a p peak
after adsorption of H at 90 K [Figure l(f)], but only a single p peak after preadsorption
at 400 K. This is probably because at low temperatures H will only penetrate a few
layers below the surface before diffusion becomes extremely slow, whereas at higher
temperatures H will diffuse deep into the bulk Pd. The temperature at which the
absorbed H desorbs will depend on the heating rate and the depth of penetration of

25 Hydrogen in Metals, ed. G . Alefeld and J. Volkl, 'Topics in Applied Physics', Vols. 28 and 29,
Springer Verlag, Berlin, 1978.
26 K. Christniann, G. Ertl, and 0. Schober, Surface Sci., 1973, 40, 61.
27 G . Doyen and G. Ertl, J . Chent. Phys., 1978, 68, 5417.
28 H. Conrad, G. Ertl, J. Kuppers, and E . E. Latta, J.C.S. Faraday Discuss., 1974, 58, 116.
29 G. Casalone, M. G . Cattania, M . Simonetta, and M. Tescari, Surface Sci., 1978, 72, 739.
30 S. Anderson, Chem. Phys. Letters., 1978, 55, 185.
31 A. W. Aldag and L. D. Schmidt, J. Caralysis, 1971, 22,260.
32 A. Couper and C. S . John, J.C.S. Furaduy I , 1978,14, 326.
The Adsorption arid Absorption of Hydrogen by Metals 7
the H. T P D by itself does not appear to be a reliable method for distinguishing
between absorbed and adsorbed H.
The surface potential data of Dus 33 and Dus and Lisowski 34 indicate three types
of adsorbed H on Pd films a t 78 K. These are a n electronegative atomic form ( p - ) , an
electropositive atomic form (p+), and an electropositive molecular hydrogen (u). p-
is found at low coverage but as Pd hydride forms, the p’ appears and the p- state
declines. The a state is observed as a n adsorbed state on top of the p’ state at high
pressures. Above 195 K, where the hydride is thermodynamically unstable, only the
/I-state is found. Ratajczykowa 3 5 has used i.r. reflectance spectroscopy to study
the surface of Pd films after exposure t o H. He finds that chemisorbed H does not
absorb in the i.r. However, after the formation of the hydride two peaks were observed
whose intensity increases with H gas pressure. It would appear that the i.r.-active H
corresponds t o the 8’ state detected by Dus. Since it is only found in both cases after
Pd hydride is formed, it does not appear to be involved in the absorption process.
It is interesting, therefore, that adsorption into the p- state does not terminate at a
surface coverage of a monolayer. In fact, at 78 K, H sorption continues up t o the
equivalent of NN 10 monolayers before the surface potential reverses sign. Since
dissolved H will not have much affect on the potential of the surface, these results
suggest that the surface is only saturated after about 9 ‘monolayers’ of H have been
absorbed. Apparently absorption begins some time before completion of an adsorbed
monolayer.

Mechanism of Absorption.-Lynch and Flanagan 3 6 , 3 7 and Bucur and co-workers 3 8 , 3 9


have investigated the adsorption to absorption transition on Pd. Lynch and Flanagan
have argued that since the rate of diffusion of hydrogen into Pd is not affected by
surface reactions the adsorbed hydrogen which is in rapid equilibrium with absorbed
H cannot have a heat of adsorption which exceeds -68 kJ mol-‘. This is the sum
of the heat of absorption and the activation energy for diffusion. They conclude that
no absorption can occur until a monolayer of strongly adsorbed H is first formed.
After completion of a strongly chemisorbed monolayer further excess adsorption
into a weakly bound state (Ed from 45 to 36 kJ mol-’) occurs as a precursor to
absorption. At 273 K up to 34% of a monolayer can apparently be adsorbed in
excess of the strongly chemisorbed layer. The strongly bound H was thought to
occupy sites directly above Pd atoms (Toya’s I--state), and the precursor state H was
located at surface interstitial sites.
Auer and Grabke 40 have studied the kinetics of H absorption and conclude that
the rate-determining step is the dissociation of a H, molecule. However, only a
single surface site is involved in the rate-determining step so they postulate a mech-
anism as follows
H,(ads) + [H,(ads) . . . H,(in lattice)]* + 2H(dissolved)
The transition state (it)is a H, molecule normal to the metal surface in which one H
atom is adsorbed on the external surface of the metal and the second atom is in a
33
R. Dus, Surface Sci., 1973, 42, 324; J . Catalysis, 1976, 42, 334.
34
R. Dus and W. Lisowski, Surface Sci., 1976, 59, 141.
35
I. Ratajczykowa, Surface Sci., 1975, 48, 549.
36
J . F. Lynch and T. B. Flanagan, J . Phys. Chem., 1973, 77, 2628.
37
J. F. Lynch and T. B. Flanagan, J.C.S. Faraday I , 1974, 70, 814.
38
R. V. Bucur, V. Mecea, and T. B. Flanagan, Surface Sci., 1976, 54, 477.
39
R. V. Bucur, Surface Sci., 1977, 62, 519.
40
W. Auer and H. J. Grabke, Ber. Biinsengesellschaft phys. Chem., 1974, 78, 58.
8 Chemical Physics of Solids and their Surfaces
subsurface interstitial position. They estimate the enthalpy difference between Ha
and H, to be about 8 kJ mol-'. Even allowing for the fact that a H atom in the first
layer below the surface would be more stable than a H atom deep in the bulk, this
work also points to a weakly bound adsorbed state being in equilibrium with absorbed
hydrogen.
In contrast, Konvalinka and Scholten 4 1 propose a breakthrough mechanism for H
desorption in which a H molecule desorbs by the combination of any surface H atom
with a subsurface H atom in an interstitial site directly below the first. Furthermore,
molecular-beam experiments 4 2 also show that equilibrium is achieved between all
adsorbed H atoms and H atoms dissolved just below the surface. There is apparently
no distinction between different surface states.
Whether the precursor state to absorption is a special surface site or any normal
surface site depends on whether or not adsorbed H atoms remain in distinguishable
energy states as the surface coverage increases. Recent calculations for H/Pt(l 1 1)"
suggest that this is not the case. The idea that H absorption occurs via special sites
derives from the assumption that no absorption can occur before a strongly chemi-
sorbed monolayer is filled. This may not be correct. Heat of adsorption data (E,) on
polycrystalline Pd show a continuous decrease with surface coverage. Therefore,
since absorption becomes possible in principle when Ea is less than 68 kJ mol-',
absorption is to be expected after filling about 70% of a monolayer. Eley and Pear-
son 43 find at 100 K that E, z AH(absorption) at 0 = 0.75. However, this may be a
special case because Couper and John 3 2 also observe that absorption can occur at
comparatively low surface coverages at 104 K because of adatom immobility.
Although very little absorbed H ( A H e = -20 kJ mol-') would be in equilibrium
with adsorbed H when AHSs = -68 kJ mol-', a simple calculation shows 44 that
the additional configurational entropy of absorbed H as compared with adsorbed H
means that significant absorption will occur when A H Z , z - 55 kJ mol-'. This
corresponds to a surface coverage of z 80-90 %. It would appear that up to 8 ;=: 0.8
the sorption of H by Pd follows a similar pattern to H/Pt (see earlier). At higher gas
pressures, adsorption (0 increasing to 1.0) and absorption (into the a phase of Pd)
occur simultaneously, with the precursor states for absorption being the same sites
as for adsorption. At 8 = 1.0 all adsorbed H atoms (except those trapped at surface
imperfections, etc.) are equivalent and have Ed = 35-40 kJ mol-'. The precursor
state to absorption is then an adsorbed H atom occupying a normal surface site pro-
viding that all the nearest neighbours of the same type which surround this site are
also occupied by H atoms. If all these sites are not occupied the precursor H atom
will be lowered in energy and will not diffuse into the bulk. The interrelationship
between the different types of H is shown in Figure 3.

The Nature of Weak Chemisorption on Pd.-Several workers have investigated


adsorption and absorption of H on Pd in order to determine the surface areas of both
unsupported 3 7 * 4 5 and supported 4 1 , 4 6 powders. Lynch and Flanagan 3 6 have
presented adsorption isotherms for weak chemisorption on Pd. At 273 K the iso-
therm shows no tendency to saturate and the excess sorption is >0.34 monolayers.

41 J. A. Konvalinka and J. J. F. Scholten, J. Catalysis, 1977, 48, 374.


42 T. Engel and H. Kuipers, to be published.
43 D. D. Eley and E. J. Pearson, J.C.S. Faraday I, 1978, 74, 223.
44 R. Burch, unpublished results.
45
P. A. Sermon, J. Catalysis, 1912, 24, 460, 467.
46 M. Boudart and H. S. Hwang, J. Catalysis, 1975, 39, 44.
The Adsorption and Absorption of Hydrogen by Metals 9

(b)
(a)

(c)
x
1
m
L
QI
c
W

. -m
+
c
aJ
+
a
0

Figure 3 Relationship between diflerent types of H sorbed on Pd: E strongly chemisorbedH;


a,
weakly chemisorbed H; 0 , intermediate state H; e, absorbed H.
(a) Pd(l11) surface; (6) Adsorption to absorption transition: is precursor to absorption;
(c) Rough potential energy diagram for adsorbed and absorbed H

(Tanaka et ~ 1 . ~have
’ suggested a similar type of excess adsorption on LaNi, powders,
although their adsorption isotherms seem unusual in that the extent of adsorption
increases with increasing temperature.) The excess adsorption on Pd is determined by
assuming that a complete monolayer remains after evacuation. This may not be
correct. Couper and John 3 2 found that a Pd wire retains only 50% of a monolayer
after evacuation for 200 s at 298 K. Dus and Lisowski 34 have shown by surface
potential measurements that 60% of the H adsorbed on Pd films at 348 K is removed
by evacuation, and total desorption occurs at 372 K. With Pd powders Sermon 4 5
found that the coverage at zero pressure decreased almost linearly with temperature.
The coverage at 273 K agreed with the surface area determined by Kr adsorption
(assuming 1.2 x lOI9 Pd atoms m-2), but the H surface area at 363 K was 15% less
than at 273 K. Boudart and Hwang 46 investigated silica-supported Pd and also
found that the coverage at 373 K was only 84% of the coverage at 273 K.
The difference between Pd films and powders is notable. Some of the H retained
by the powders may be situated at surface imperfections. However, it is also possible
that some of the hydrogen is incorporated within the defect structure of the powders,
in much the same way as suggested earlier for Pt blacks. Indeed, Aben 4 8 and Frieske
and Wicke 49 have noted that very high temperatures (> 700 K) are required to
desorb all the H from Pd blacks. As with Pt blacks the agreement between surface
areas derived from H chemisorption and Kr adsorption may be fortuitous. In any
case it is apparent that evacuation at T 3 300 K causes the desorption of some H from
the adsorbed monolayer. Consequently, at these temperatures the excess adsorption
may actually correspond to readsorption into the original monolayer.
47 S . Tanaka, J. D. Clewley, and T. B. Flanagan, J . Catalysis, 1978, 51, 9.
48 P. C . Aben, J . Catalysis, 1968, 10, 224.
49 H. Frieske and E. Wicke, Ber. Biinsengrsellsctiaft phys. Chern., 1973, 77, 48.
10 Clzemical Physics of Solids and their Surface5
The reason why a large excess of H apparently adsorbs on Pd black at 273 K maq
be as follows. When the sorption data are plotted as p* against the H/M atomic
ratio (Figure 4) sigmoid-shaped curves are obtained both at 273 and at 298 K. The
first part of the curve probably corresponds to readsorption into a monolayer, the
middle part to simultaneous completion of the adsorbed monolayer and absorption
into the c( phase of Pd, and the final part to formation of the /?-phase hydride. This
presupposes that in small, highly distorted Pd particles the /I-phase hydride begins to
nucleate at lower pressures than in the case of bulk Pd. This is a reasonable assump-
tion because a lowering of the absorption plateau pressure in Pd powders has been
~ b s e r v e d . ~Only
’ a small proportion of the (smallest?) Pd particles would need to
form the hydride phase to account for the excess sorption.

298 K

20 40

Figure 4 Sorption isotherms for PdiH : arrowed lines, absorption by bulk Pd at 298 and 273 K.
1. sorption on Pd black at 298 K after evacuation (refs. 36, 37); 2. sorptiori oti Pd black ai
273 K after evacuatiori (refs. 36, 37). Broken line, sorptiori 011 Pd black at 273 K withoui
evacuation (ref. 45)

Recent data of Konvalinka and Scholten 4 1 may also be interpreted as support for
easy hydride formation in small Pd particles. When they expose a Pd sponge to
pulses of H at 233 K they observe a ‘kink’ in a plot of H uptake versus number of
pulses, which they assume to be the point at which a monolayer of H is formed.
Since the total uptake of H is equivalent to 5.75 monolayers they suggest that there is
also rapid absorption into the o! phase of Pd/H. However, the maximum solubility of’
H in the c1 phase of their sample would only be equivalent to about 1 m ~ n o l a y e r . ~ ~
The remaining excess H may be accommodated at structural imperfections, although
the enhanced solubility is considerably more than would be expected.’ 1-53 It is
more likely that some P-phase hydride is being formed, possibly only in the surface
layers of the sponge. Eley and Pearson 4 3 have also postulated the formation of a

J. D. Clewley, T. Curran, T. B. Flanagan, and W. A. Oates, J.C.S. Faruduy I, 1973, 69,449.


51 J. F. Lynch, J. D. Clewley, and T. B. Flanagan, Phil. Mug., 1973, 28, 1415.
52
M. L. H. Wise, J. P. G . Farr, I. R. Harris, and J. R. Hirst, ‘L’Hydrogene dans les Metaux’,
Tome 1, Editions Science et Industrie, Paris, 1972, p. 1.
” J. F. Lynch, J. D. Clewley, T. Curran, and T. B. Flanagan, J . Less-Common Metals, 1977,55, 153.
The Adsorption and Absorption of Hydrogen by Metals 11
surface hydride phase on Pd wire. If partial hydride formation can occur with low
surface area sponge or wire it is even more probable with high surface area powders.
One final important fact which comes from Sermon's data45 is that at 300K a
monolayer coverage is only completed at a hydrogen pressure of 400 Nm-2. Data
for bulk Pd 5 0 9 5 4 shows that at this temperature and pressure hydrogen will have been
absorbed up to PdH,.,,,. Here again absorption and adsorption (0 < 1.0) seem to
occur simultaneously.
The problem of whether the precursor state for absorption of H by Pd is a special
site, or a normal site, cannot yet be resolved. However, there does not seem to be any
unequivocal evidence for adsorption in excess of a monolayer at normal temperatures
and pressures, so that the viewpoint that all adsorbed H atoms are equally available
for absorption may be ~ o r r e c t .9~4 '2

3 Hydrogen Absorption Leading to Hydride Formation


Current research in metal hydrides has been stimulated by the possibility of storing
hydrogen as a solid hydride. Rare-earth * 5 6 and titanium * 5 8 intermetallic alloys
have been most investigated for this purpose, but there is also a continuing interest
in the Pd/H system because its comparative simplicity makes it popular as a model
system.

Site Selectivity of Hydrogen in Metals and Alloys.-Entropy Data for Pd/H. The
partial molar entropy (S,) of H in Pd and its alloys is of great interest because of the
information which can be obtained concerning the nature and distribution of H atoms
in the metal lattice. At low temperatures hydrogen atoms are randomly distributed
over the octahedral sites in the lattice, of which there is 1 per Pd atom. However, at
high temperatures it is possible that both tetrahedral and octahedral sites are partially
occupied. 59-61
To summarize the arguments on which this proposal is based it is convenient to
separate the experimental entropy S, into individual entropy terms as follows 5 9 y 6 0

S" = s, + s, + s3 + S,
where S, is a vibrational term, S2 is an electronic term, S3 is a degeneracy term, and
S, is a communal entropy term. S, consists of two parts, S,(H) due to the vibrational
motion of the H atoms, and S,(Pd) due.to modification of the vibrational spectrum of
Pd resulting from the lattice expansion and lattice strain caused by the introduction of
H. S,(H) is calculated from the vibrational frequency of the H, and S,(Pd) from the
acoustic spectrum of the hydride. Magerl et ~ 1 calculate
. ~ S,(H)
~ and S1(Pd) at 400 K
to be 24.5 and 19.9 J K - ' mol-', respectively. Boureau and Kleppa 6 o obtain similar
values at 555 K, 26.8, and 16.7 J K - ' mol-l, respectively. However, Boureau and
Kleppa also point out that low-temperature specific-heat data would give a value of
about zero for S,(Pd).

54 R. Burch and N. B. Francis, J.C.S. Furuduy I, 1973, 69, 1978.


s5 J . H . N. van Vucht, F. A. Kuijpers, and H. C. A. Bruning, Philips Research Reports, 1970,25, 133.
56 H. H. van Mal, K. H. J. Buschow, and A. R. Miedema, J. Less-Common Metals, 1974,35,65.
57 J. J. Reilly and R. H. Wiswall, Znorg. Chem., 1974, 13, 218.
58 For a recent review see R. H. Wiswall in ref. 25, Vol. 2, p. 201.
59 G. Boureau, 0. J. Kleppa, and P. Dantzer, J. Chem. Phys., 1976, 64, 5247.
6o G. Boureau and 0.J. Kleppa, J. Chem. Phys., 1976, 65, 3915.
61 C. Labes and R. B. McLellan, Acta Metallurgicu, 1978, 26, 893.
62 A. Magerl, N. Stump, H. Wipf, and G. Alefeld, J. Phys. Chem. Sofids, 1977, 38, 683.
12 Chemical Physics of Solids and their Surfaces
S,, the electronic term, has been calculated from the electronic specific heat of'
Pd 6 3 to be - 10 J K - ' mol-'. Boureau et point out that the temperature
dependence of the electronic specific heat means that this value overestimates S , by a
factor of 2 or 3. They calculate S2 to be -6.7 J K - ' mol-', but use an average value
of -8.3 J K - ' mol-'.
By assuming that S , and S , are zero Magerl et ~ 1obtain
. ~close~ agreement between
the experimental entropy (34.2 J K - ' mol-') and their calculated value (36.3 J K - '
mol-'). They conclude that H only occupies octahedral sites in Pd. They note,
however, that calculated values are lower than experimental values at high tempera-
tures, which they attribute to the temperature dependence of the vibrational frequency
of the H. Boureau and Kleppa suggest that the discrepancy at high temperatures
may be due t o lattice degeneracy arising from the simultaneous occupancy of tetra-
hedral and octahedral sites. There are 2 tetrahedral sites per Pd atom which makes
S , = 2 R In 3 = 18.3 J K - ' mol-'. They also introduce the concept of a communal
entropy term (S,) which derives from the assumption that dissolved H atoms in a
metal at high temperatures will have liquid-like properties. They estimate S, to be
16.6 J K - ' mol-'. Boureau and Kleppa point out that equally good agreement
between experimental and calculated entropies can be obtained by setting S,(Pd) =
16.7 and S , = 0, or by setting S,(Pd) = 0 and S4 = 16.6. It would seem more
realistic, bearing in mind the neutron-scattering data of Rowe et u I . , ~ to ~ choose
the first alternative; there seems no necessity to introduce the communal entropy
term. The interesting feature introduced by Boureau and Kleppa is that H may
occupy both octahedral and tetrahedral sites at high temperatures, and that information
on this point comes from entropy data.
Elitropy Datafor Pd AIfoys. Information on the distribution of H atoms in alloys
can also be obtained from entropy data. The relevant entropy term is the relative
partial molar excess entropy, ASxs, defined by

where S, is the partial molar entropy of dissolved H (and is essentially constant for a
series of similar alloys), Sg2 is the standard entropy of gaseous H, and S, is the
configurational entropy given by
X - n
S , = 2R In ~

where iz is the H/M atomic ratio and X i s the number of interstitial sites available to
H atoms. Gallagher and Oates 6 5 pointed out that there is a correlation between
AS""and A H e for H in metals. Flanagan and Lynch 6 6 used this correlation to show
that the change in ASxs with alloy composition for Pd alloys was disproportionately
large. This could be explained by assuming that X < 1. The H was thought to have a
preference for sites in which its nearest neighbours were Pd atoms. An earlier example
of this type of site preference had been reported for Pd,Fe alloys.67 The ordered
alloy, in which there are some sites surrounded by 6 Pd atoms, absorbs about 5 times
as much H as the disordered alloy which has only mixed Pd and Fe sites.
63
W. A. Oates and T. B. Flanagan, Solid State Comm., 1971, 9, 1841.
64 J. M. Rowe, J. J. Rush, H. G. Smith, M . Mosteller, and H. E. Flotow, Phys. Rev. Letters, 1974,
33, 1297.
65 P. T. Gallagher and W. A. Oates, Trans. Met. SOC.AIME, 1969, 245, 179.
titi T. B. Flanagan and J . F. Lynch, Met. Trans., 1975, 6A, 243.
67
T. B. Flanagan, S . Majchrzak, and B. Baranowski, Phil. Mag., 1972, 25, 257.
The Adsorption and Absorption of Hydrogen by Metals 13
The selective occupation of interstitial sites implies that the atoms in an alloy
retain some individuality. This is a feature which has long been recognized as import-
ant in surface reactions on alloys, but it is a much more recent observation in respect
of bulk properties. Certainly in the case of hydrogen dissolution in a wide range of
alloys of Pd with transition 6 8 - 7 0 or non-transition metal 7 1 - 7 5 partners the H seems
to be capable of differentiating between the metal atoms.
Oates and Ramanathan 7 6 have taken the concept of selective site occupancy one
stage further in an analysis of data for PdAg/H systems. From entropy data at low H
contents they derive values for the fraction of octahedral sites (X)which should be
available to H to give a constant ASxs. For 10, 20, 30, and 40% Ag alloys the calcu-
lated values of X are 1.O, 0.32,0.20, and 0.21, respectively. They further suggest that
the value of X determines the limiting solubility of H in the hydride phase of these
alloys. This contrasts with the model proposed by Brodowsky 7 7 in which this
limiting solubility is attributed to an enthalpy change associated with the filling of the
d-band of Pd with electrons from H or Ag atoms (see later). A comparison of solu-
bility data for PdAg and PdCu alloys gives support to a model based on an enthalpy
effect. The dissolution of H in PdCu 7 3 and PdAg 71 alloys gives almost identically
shaped isotherms at high H contents (Figure 5), but, in contrast to PdAg, ASxs only

w
l
l
0
l
II
0.2
80 90 100

0.4 0.6

Figure 5 Absorption isotherms for ( a ) PdCu/H (ref,73), and (6) PdAg/H (ref. 71). (Numbers
refer to % Pd in alloy)

changes very slowly with Cu content in PdCu alloys. The entropy data for PdAg
probably originate because H enters only Pd-rich sites initially, but as further H is
added other sites only marginally higher in energy become available. As a result X
is not constant, but increases continuously with H content.

h8 M. LaPrade, K. Allard, J. Lynch, and T. B. Flanagan, J.C.S. Faraday I, 1974, 70, 1615.
69 J. D. Clewley, J. F . Lynch, and T. B. Flanagan, J.C.S. Faraday I, 1977, 73,494.
70 T. B. Flanagan, G . Gross, and J. D. Clewley, Second International Congress on Hydrogen in
Metals, Paris, 1977, paper 1C3.
71 H. Brodowsky and E. Poeschel, Z. Phys. Chern., 1965, N.F.144, 143.
72 K. D. Allard, A. Maeland, J. W. Simons, and T. B. Flanagan, J. Phys. Chem., 1968, 72, 136.
73 R. Burch and R. G. Buss, J.C.S. Faraday I , 1975, 71,913,922.
74 D. Fisher, D. M. Chisdes, and T. B. Flanagan, J . Solid State Chem., 1977,20, 149.
75 K. D. Allard, J. F. Lynch, and T. B. Flanagan, Z. Phys. Chem., 1974, N.F.93, 15.
'6 W. A. Oates and R. Ramanathan, Second International Congress on Hydrogen in Metals, Paris,
1977, paper 2Al.
77 H. Brodowsky, Z. Phys. Chem., 1965, N.F.144, 129.
14 Chemical Physics of Solids and their Surfaces
The concept of selective site occupancy is useful, and will be seen to have a fairly
general applicability. Indeed, the way in which the critltalpy of dissolved H is affected
by the environment of the absorption site needs to be investigated further.

Rare-earth and Titanium Intermetallic Alloy Hydrogen Systems.-Structure of the


Deutwides. Neutron diffraction 7 8 3 7 9 shows that D selectively occupies octahedrnl
positions in a distorted body-centred-cubic structure [Figure 6(a)]. The preferred
sites have Ti,Fe, co-ordination reflecting the affinity of I> atoms for Ti. However, the
very short D-Fe distances (0.148 and 0.172 nm) as compared with D-Ti distances
of 0.214 and 0.246 nm shows that the D is not averse to Fe atoms. In contrast,
neutron diffraction data for TiCu/DBOshow that D atoms are situated at Ti, tetra-
hedral sites [Figure 6(b)]. N o neutron data are available for the analogous TiCo and
TiNi/H systems. Entropy data 81 suggest that only 1 site per metal atom is available
to H in TiCo and TiNi, which again suggests a selective site occupancy. It is not
possible from entropy data alone to distinguish between a TiFeH or a TiCuH type
structure, but the corresponding enthalpy data 8 1 may offer some support for a
TiCuH type structure. The enthalpy of H in TiFe (-28 kJ mol-’) is close to the
average value of the enthalpy of H in Ti and Fe (-30 kJ mol-I). In contrast, for
both TiCo and TiNi the enthalpy is ~ 3 kJ0 mol-’ more negative than the average
value for the corresponding metals. This could indicate that the H in TiCo and TiNi
is in Ti-type sites.
Similar site selectivity has been suggested by Rudman et aZ.82-84 for H in Ti,AI
and Ti,Sn alloys, based on calculations of configurational entropies.
LaNi,D, has the structure ” shown in Figure 6(c). It is formed by an expansion
and distortion of the CaCu,-type structure of LaNi,. The D atoms are a reasonable

Figure 6 Structures of intermrtallic alloy deuterides. ( a ) TiFeD 0, Ti; 0, Fe; 0 , D;


( 6 ) TiCuD 0, Ti ; 0,Cu; 0 , D; (c) LaNiDs 0, L a ; 0 , N i ; 0 , D (100% occupied)
0, D (50 % occupied)

78 P. Thompson, M. A. Pick, F. Reidinger, L. M . Corliss, J. M. Hastings, and J. J. Reilly, J . Phys. F:


Metal Physics, 1978, 8, L75.
79 P. Fischer, W. Halg, L, Schlapbach, F. Stucki, and A. F. Andresen, Mat. Res. Bull., 1978,13,931.
A. Santoro, A. Maeland, and J. J. Rush, Actu Cryst., 1978, B34, 3059.
81 R. Burch and N. B. Mason, J.C.S. Faraduy I , 1979, 75, 561, 578.
82 P. S Rudrnan, J. J. Reilly, and R. H. Wiswall, Ber. Bunsengesellschuftphys. Chem., 1977, 81, 76.
83 P. S. Rudman, J. J. Reilly, and R. H. Wiswall, Ber. Bunsengesellschaft phys. Chem., 1978,82,611.
84 P. S. Rudman, J. J. Reilly, and R. H. Wiswall, J . Less-Common Metals, 1978, 58, 231.
85 P. Fischer, A. Furrer, G . Busch, and L. Schlapbach, Helv. Physica Actu, 1977, 50,421.
The Adsorption and Absorption of Hydrogen by Metals 15
distance from La atoms (0.256 and 0.291 nm) but the Ni-D distances (0.145 and
0.174 nm) are very short. There is an interesting similarity here with the Fe-D
distances in TiFeD. It would be interesting to know whether Ni behaves differently
in TiNi and LaNi,. In either case it is apparent that just as in the case of Pd alloys
the H can distinguish the different metals in the alloy and chooses the most stable site
accordingly.

Structural Reorganisation of the Hydrided Alloys.-The distortion of the lattice when H


dissolves can allow structural changes to occur at low temperatures. Hemplemann
and Wicke 8 6 have observed that when TiFe is hydrided and dehydrided several times
there is an irreversible change in the magnetic moment, which they attribute to the
formation of iron clusters about 3.4 nm in diameter dispersed throughout the bulk,
However, Schlapbach et ~ 1 . ~8 8” using surface spectroscopic techniques on fresh and
on ion-sputtered TiFe samples conclude that segregation of Ti and Fe occurs only in
the surface layers (5-15 nm deep). The surface consists of a Ti-rich layer containing
some Ti oxide, below which is an Fe-rich layer, and finally a core of TiFe. They
conclude that the magnetic changes observed by Hemplemann and Wicke are confined
to the surface layers. Support for this comes from the neutron diffraction data of
Fischer et al.79 which show no change in the order parameter (i.e., the distribution
of Ti and Fe atoms in the bulk) after hydriding and dehydriding.
Some segregation of La and Ni occurs in LaNi, in the presence of oxygen and ap-
pears to be important in restoring and retaining an active surface. Siegmann et aZ.89
have shown using photoemission and magnetic measurements that in the presence of
oxygen or water, La diffuses to the surface where it forms a stable oxide. This pro-
duces a self-cleaning mechanism for the surface, and the dissociation of hydrogen
molecules can proceed unhindered at the Ni atoms. They estimate that about 1 % of
the Ni, corresponding to a surface layer 10 nm thick, is segregated after 10 absorption-
desorption cycles. The excellent absorption kinetics of LaNi, derive from the combi-
nation of an active Ni surface and the fact that bulk diffusion of H is rapid.85i90
A further type of structural reorganization caused by H has been observed 8 1 ’ 9 1 ’ 9 2
in TiNi and TiCu. When the hydrided alloys are heated in H some desorption occurs
as expected. However, at e6 5 0 K the alloys begin to reabsorb hydrogen. This
continues up to 2 850 K , at which point desorption recommences and continues until
all the H has desorbed. Yamanaka et suggested that there was a complete phase
separation into TiH, and Ni (or Cu). This seems unlikely and it has been proposed
instead 9 1 that there is some ordering of Ti atoms to produce a small Ti cluster. The
cluster must be sufficiently small, however, not to have bulk Ti properties; a size of 2
to 20 nm has been suggested. (Calculations on the electronic properties of small
metal-atom clusters 9 3 also put an upper limit of about 10 nm on the size of a cluster
before bulk properties are obtained.) With TiNi and TiCu the site preference of H is
sufficient to bring about major structural changes. TiFe and TiCo do not appear to
undergo this type of rearrangement.

86 R. Hemplemann and E. Wicke, Ber. Buttsengesellschaft phys. Chem., 1977, 81,425.


’’ L. Schlapbach, A. Seiler, and F. Stucki, Mat. Res. Bull., 1978, 13, 692.
L. Schlapbach, A. Seiler, and F. Stucki, Mat. Res. Bull., 1978, 13, 1031.
89 H. C . Siegmann, L. Schlapbach, and C. R. Brundle, Phys. Rev. Letters, 1978,40,972.
90 S. Tanaka, J. D. Clewley, and T. B. Flanagan, J. Less-Common Metals, 1977, 56, 137.
9’ R. Burch and N. B. Mason, Hydrogen in Metals Conference, Munster, 1979, to be published.
92 K. Yamanaka, H. Laito, and M . Someno, Nippon Kagakir Kaishi, 1975, 8, 1267.
93 P. Kadura and L. Kunne, Phys. Stat. Sol., 1978, B88,537.
16 Chemical Physics of Solids and their Surfaces

4 The Binding of Adsorbed and Absorbed Hydrogen


Adsorption.-The interaction between hydrogen and a metal surface is remarkably
complex. Any conclusions based on currently available data, therefore, are at risk of
being overtaken by subsequent events. However, there seems to be a consensus on
one point at least. This is that as the surface coverage approaches a monolayer there
is an essentially homogeneous distribution of H atoms in geometrically equivalent
surface sites. This appears to be a general phenomenon and has been suggested for
H on W,94-96 Fe,g7 Ni,8 and pt."5,11.17 The different binding energies observed
in thermal desorption spectra are thought to arise from interactions between adsorbed
H atoms. Very simply this means that a H atom on a site surrounded by occupied
sites is at a higher energy, and will desorb at a lower temperature, than a H atom on a
site which is surrounded by vacant sites (see Figure 3). Repulsive interactions prob-
ably also account for the continuous decrease in the heat of adsorption with coverage.
These repulsive interactions cannot be due to direct H-H interactions - the H-H
distance even on Ni is much larger than the diameter of a H atom (0.249 and 0.15 nm)
- but arises instead from an indirect interaction via the conduction electrons of the
meta1."~98*99The magnitude of the interaction has been calculated to be
z 15-25 kJ mol- which is more than sufficient to account for the observed decrease
in the heat of adsorption with coverage.95 Assuming that there are comparable
repulsive interactions between H atoms on a Pd surface, we conclude, as discussed
earlier, that all the H atoms on Pd are in equilibrium with absorbed hydrogen.
Weinberg and Merrill l o o have presented a very simple and attractive model of
H/Pt( 1 11) which, by taking account of the spatial distribution of the d-orbitals,
draws attention to the differences between various metal planes. This model has been
used to describe the adsorption of H on Pd."' It is obviously important to take note
of orbital geometry (similar considerations have been used to identify the most
favourable sites for absorption ' 0 2 ) , but the fairly small differences in heats of adsorp-
tion on different planes may indicate only a small dependence on the geometry of the
orbitals, Moreover, it has also been shown 2 7 p that the interaction between H and
Ni is mainly between the 1s orbital of H and the s-band of Ni, whereas with Pd and
Pt the d-band interacts with the H 1s orbital. The simple orbital model would not
distinguish between Ni, Pd, and Pt.
The delocalization of the surface interactions has been emphasized recently by
Christmann et aI.lo4 who introduce the concept of 'atomic bands', analogous to
surface electronic states, to describe H adsorbed on Ni( 111).

Absorption.-Electronic Interactions. In the rigid band model for H in metals it is


assumed that H is ionized and that the protons enter the lattice where they are screened
by the conduction electrons of the metal, and the electrons fill up holes in the d-band.

94 T. E. Madey, J. J. Czyzewski, and J. T. Yates, Surface Sci., 1975, 49, 465.


9s A. Couper and C . S. John, J.C.S. Faraday I, 1977, 73, 950.
96 R . Jaeger and D. Menzel, Surface Sci., 1977, 63, 950.
97 F. Bozso, G. Ertl, M. Grunze, and M. Weiss, Applications Surface Sci.,1977, 1, 103.
98 T. B. Grimley and M. Torrini, J. Phys., 1973, C6, 868.
99 E. Einstein and J. R. Schrieffer, Phys. Rev., 1973, B7, 3629.
loo W. H. Weinberg and R. P. Merrill, Surface Sci., 1972, 33, 493.
Iol E. Wicke and H. Brodowsky, in ref. 25, Vol. 2, p. 73.
Io2 J. Hauck and H. J. Schenk, J. Less-Common Metals, 1977 51,251.
lo3 J. E. Demuth, Surface Sci., 1977 65, 369.
Io4 K. Christmann, R. J. Behm, G . Ertl, M. A. van Hove, and W. H. Weinberg, to be published.
The Adsorption and Absorption of Hydrogen by Metals 17
The limitations of this model have been known for some time and Switendick ' 0 5 has
shown by energy band calculations that when H is added to Pd both the shape and the
position of the bands are altered. This has been confirmed by photoemission measure-
ments which show a H-induced band about 5 eV below the Fermi level. It is
interesting that similar results are found for H adsorbed on Ni, Pd, and Pt.103i107
More recent calculations have confirmed '08-' the general features of Switendick's
model. Nevertheless, many data for H in Pd alloys are consistent with a model in
which progressive filling of holes in the d-band is a dominant consideration. The
concept of a sliding band 1 1 1 9 1 1 2 would still seem to have some relevance to these
systems.
Elastic Interactions. When H dissolves in a metal it expands the lattice and introduces
an elastic strain. The release of part of this strain energy is believed to be the driving
force for the nucleation of a hydride phase. This nucleation process has been examined
using statistical models 7 7 by assuming that there is a pairwise attractive interaction
between H atoms on adjacent lattice sites. Alefeld ' I 3 has pointed out, however, that
macroscopic elasticity theory would predict that short-range interactions are repulsive,
and that long-range interactions are responsible for the phase transformations. There
is still some debate as to whether short-range or long-range forces are dominant, and
both viewpoints have been reiterated recently."" '14
There is also discussion 1 1 5 3 1 1 6 as to whether it is necessary to make a correction
to experimental (constant pressure) data before comparisons can be made with statis-
tical models which, strictly speaking, refer to conditions of constant volume.
Wagner had pointed out that under conditions of constant volume the pairwise
attractive interaction between H atoms virtually disappeared. However, there now
seems to be some doubt concerning Wagner's analysis.'"
The absorption of H by alloys poses even more complicated and less well under-
stood problems. None of the theoretical models currently available can account
satisfactorily for the fact that H can distinguish between interstitial sites surrounded
by different types of metal atoms, although Switendick has commented ' l o on the
need to allow for substantial local effects in calculations of the band structure of
alloy hydrides.
lo'
A. C . Switendick, Ber. Bunsengesellschaft phys. Chem., 1972, 76, 535.
lo6 D. E. Eastman, J. K. Cashion, and A. C. Switendick, Phys. Rev. Letters. 1971, 27, 35.
lo' H. Conrad, G. Ertl, J. Kuppers, and E. E. Latta, Sirrface Sci., 1976, 58, 583.
lo' D. A. Papaconstantopoulos, B. M. Klein, E. N. Economou, and L. L. Boyer, Phys. Rev., 1978,
B17, 141.
log C. D. Gelatt, H. Ehrenreich, and J. A. Weiss, Phys. Rev., 1978, B17, 1940.
110 A. C. Switendick, in ref. 25, Vol. 1, p. 101.
'I1
J. S. Dugdale and A. M. Guenault, Phil. Mag., 1966, 13, 503.
'I2 H. Montgomery, G . P. Pells, and E. M. Wray, Proc. Roy. SOC.,1967, A301, 261.
'I3 G. Alefeld, Phys. Stat. Sol., 1969, 32, 67.
H. Wagner, in ref. 25, vol. 1, p. 5.
l5
W. A. Oates and T. B. Flanagan, Scripta Met., 1978, 12, 759.
C. H. P. Lupis, Scripta Met., 1978, 12, 763.
'I7
C. Wagner, Acta Met., 1971, 19, 843.
'I8
C. H. P. Lupis, Acta Met.. 1977, 25, 751.