We adapt the computational hydrogen electrode approach to explicitly account for photo-generated charges and use it to computationally screen for viable catalyst/co-catalyst combinations for photo-catalytic water splitting. The hole energy necessary to thermodynamically drive the reaction is employed as descriptor for the screening process. Using this protocol and hybrid-level density-functional theory, we show that water oxidation on bare TiO2 surfaces is thermodynamically more complex than previously thought. This motivates a screening for suitable co-catalysts for this half-reaction, which we carry out for Au particles down to the non-scalable size regime. We find that almost all small Au clusters studied are better suited for water photo-oxidation than an extended Au(111) surface or bare TiO2 facets.

1.
A.
Fujishima
and
K.
Honda
,
Nature (London)
238
,
37
(
1972
).
2.
A.
Fujishima
,
X.
Zhang
, and
D. A.
Tryk
,
Surf. Sci. Rep.
63
,
515
(
2008
).
3.
M. A.
Henderson
,
Surf. Sci. Rep.
66
,
185
(
2011
).
4.
K.
Maeda
and
K.
Domen
,
J. Phys. Chem. Lett.
1
,
2655
(
2010
).
5.
S.
Kim
and
W.
Choi
,
J. Phys. Chem. B
106
,
13311
(
2002
).
6.
S.
Sakthivel
,
M.
Shankar
,
M.
Palanichamy
,
B.
Arabindoo
,
D.
Bahnemann
, and
V.
Murugesan
,
Water Res.
38
,
3001
(
2004
).
7.
V.
Subramanian
,
E. E.
Wolf
, and
P. V.
Kamat
,
J. Am. Chem. Soc.
126
,
4943
(
2004
).
8.
A.
Iwase
,
H.
Kato
, and
A.
Kudo
,
Catal. Lett.
108
,
7
(
2006
).
9.
M. D.
Hernández-Alonso
,
F.
Fresno
,
S.
Suárez
, and
J. M.
Coronado
,
Energy Environ. Sci.
2
,
1231
(
2009
).
10.
U.
Heiz
and
U.
Landman
,
Nanocatalysis, Nanoscience and Technology
(
Springer
,
Berlin
,
2007
).
11.
J. K.
Nørskov
,
T.
Bligaard
,
J.
Rossmeisl
, and
C. H.
Christensen
,
Nat. Chem.
1
,
37
(
2009
).
12.
J. K.
Nørskov
,
J.
Rossmeisl
,
A.
Logadottir
,
L.
Lindqvist
,
J. R.
Kitchin
,
T.
Bligaard
, and
H.
Jonsson
,
J. Phys. Chem. B
108
,
17886
(
2004
).
13.
Á.
Valdés
,
Z.-W.
Qu
,
G.-J.
Kroes
,
J.
Rossmeisl
, and
J. K.
Nørskov
,
J. Phys. Chem. C
112
,
9872
(
2008
).
14.
J.
Cheng
and
M.
Sprik
,
Phys. Rev. B
82
,
081406
(R) (
2010
).
15.
M.
Grätzel
,
Nature (London)
414
,
338
(
2001
).
16.
W.
Kang
and
M. S.
Hybertsen
,
Phys. Rev. B
82
,
085203
(
2010
).
17.
P.
Zawadzki
,
A. B.
Laursen
,
K. W.
Jacobsen
,
S.
Dahl
, and
J.
Rossmeisl
,
Energy Environ. Sci.
5
,
9866
(
2012
).
18.
M.
Valden
,
X.
Lai
, and
D.
Goodman
,
Science
281
,
1647
(
1998
).
19.
H.
Häkkinen
,
S.
Abbet
,
A.
Sanchez
,
U.
Heiz
, and
U.
Landman
,
Angew. Chem., Int. Ed.
42
,
1297
(
2003
).
20.
B.
Yoon
,
H.
Häkkinen
,
U.
Landman
,
A. S.
Wörz
,
J.-M.
Antonietti
,
S.
Abbet
,
K.
Judai
, and
U.
Heiz
,
Science
307
,
403
(
2005
).
21.
M. E.
Vaida
,
T. M.
Bernhardt
,
C.
Barth
,
F.
Esch
,
U.
Heiz
, and
U.
Landman
,
Phys. Status Solidi B
247
,
1001
(
2010
).
22.
M. J.
Berr
,
F. F.
Schweinberger
,
M.
Döblinger
,
K. E.
Sanwald
,
C.
Wolff
,
J.
Breimeier
,
A. S.
Crampton
,
C. J.
Ridge
,
M.
Tschurl
,
U.
Heiz
,
F.
Jäckel
, and
J.
Feldmann
,
Nano Lett.
12
,
5903
(
2012
).
23.
V.
Blum
,
R.
Gehrke
,
F.
Hanke
,
P.
Havu
,
V.
Havu
,
X.
Ren
,
K.
Reuter
, and
M.
Scheffler
,
Comput. Phys. Commun.
180
,
2175
(
2009
).
24.
J. P.
Doye
and
D. J.
Wales
,
New J. Chem.
22
,
733
(
1998
).
25.
K.
Michaelian
,
N.
Rendon
, and
I.
Garzón
,
Phys. Rev. B
60
,
2000
(
1999
).
26.
H.
Häkkinen
and
U.
Landman
,
Phys. Rev. B
62
,
R2287
(
2000
).
27.
B.
Assadollahzadeh
and
P.
Schwerdtfeger
,
J. Chem. Phys
131
,
064306
(
2009
).
28.
K.
Bao
,
S.
Goedecker
,
K.
Koga
,
F.
Lançon
, and
A.
Neelov
,
Phys. Rev. B
79
,
041405
(R) (
2009
).
29.
J. P.
Perdew
,
K.
Burke
, and
M.
Ernzerhof
,
Phys. Rev. Lett.
77
,
3865
(
1996
).
30.
B.
Hammer
,
L. B.
Hansen
, and
J. K.
Nørskov
,
Phys. Rev. B
59
,
7413
(
1999
).
31.
C.
Adamo
and
V.
Barone
,
J. Chem. Phys.
110
,
6158
(
1999
).
32.
M. J.
Frisch
,
G. W.
Trucks
,
H. B.
Schlegel
 et al, GAUSSIAN 09, Revision A.1, Gaussian, Inc., Wallingford, CT,
2009
.
33.
R. A.
Kendall
,
T. H.
Dunning
 Jr.
, and
R. J.
Harrison
,
J. Chem. Phys.
96
,
6796
(
1992
).
34.
K. A.
Peterson
and
C.
Puzzarini
,
Theor. Chem. Acc.
114
,
283
(
2005
).
35.
J. P.
Perdew
and
K.
Schmidt
,
AIP Conf. Proc.
577
,
1
(
2001
).
36.
J. P.
Perdew
and
Y.
Wang
,
Phys. Rev. B
45
,
13244
(
1992
).
37.
J. P.
Perdew
,
A.
Ruzsinszky
,
G. I.
Csonka
,
O. A.
Vydrov
,
G. E.
Scuseria
,
L. A.
Constantin
,
X.
Zhou
, and
K.
Burke
,
Phys. Rev. Lett.
100
,
136406
(
2008
).
38.
A. D.
Becke
,
Phys. Rev. A
38
,
3098
(
1988
).
39.
C.
Lee
,
W.
Yang
, and
R. G.
Parr
,
Phys. Rev. B
37
,
785
(
1988
).
40.
A.
Tkatchenko
and
M.
Scheffler
,
Phys. Rev. Lett.
102
,
073005
(
2009
).
41.
Y.
Zhao
and
D. G.
Truhlar
,
Theor. Chem. Acc.
120
,
215
(
2008
).
42.
A. D.
Becke
,
J. Chem. Phys.
98
,
5648
(
1993
).
43.
A. V.
Krukau
,
O. A.
Vydrov
,
A. F.
Izmaylov
, and
G. E.
Scuseria
,
J. Chem. Phys.
125
,
224106
(
2006
).
You do not currently have access to this content.