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11. M. N. Timofeeva, O. A. Kholdeeva, S. H. Jhung,
We report that the addition of alkali ions (sodium or potassium) to gold on KLTL-zeolite and
J. S. Chang, Appl. Catal. A Gen. 345, 195–200 mesoporous MCM-41 silica stabilizes mononuclear gold in Au-O(OH)x-(Na or K) ensembles.
(2008). This single-site gold species is active for the low-temperature (<200°C) water-gas shift (WGS)
12. Z. Bohström, I. Rico-Lattes, K. Holmberg, Green Chem. 12, reaction. Unexpectedly, gold is thus similar to platinum in creating –O linkages with more
1861–1869 (2010).

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13. Y. Deng, Z. Ma, K. Wang, J. Chen, Green Chem. 1, 275–276
than eight alkali ions and establishing an active site on various [Link] intrinsic activity of
(1999). the single-site gold species is the same on irreducible supports as on reducible ceria, iron
14. K. M. Draths, J. W. Frost, J. Am. Chem. Soc. 116, 399–400 oxide, and titania supports, apparently all sharing a common, similarly structured gold active
(1994). site. This finding paves the way for using earth-abundant supports to disperse and stabilize
15. H.-K. Fun, S. Chantrapromma, L.-H. Ong, Molecules 19,
10137–10149 (2014).
precious metal atoms with alkali additives for the WGS and potentially other fuel-processing
16. B. Barletta et al., Ozone Sci. Eng. 20, 91–98 (1998). reactions.

T
17. Y. Matsumi et al., J. Geophys. Res. 107, 10.1029/
2001JD000510 (2002). he water-gas shift (WGS) reaction (CO + is not advantageous for the stability of the active
18. Y. Matsumi, M. Kawasaki, Chem. Rev. 103, 4767–4782
(2003).
H2O → CO2 + H2) is an important reaction (atomically dispersed) Au sites.
19. P. Michaud, R. J. Cvetanovic, J. Phys. Chem. 76, 1375–1385 for hydrogen upgrading during fuel gas Other approaches—for example, AuCl3 vapor
(1972). processing. Emerging applications in fuel produced by sublimation and introduced into
20. T. H. Varkony, S. Pass, Y. Mazur, J. Chem. Soc. Chem. Commun. cells require active, nonpyrophoric, and cost- various zeolites (14, 15)—may be used to produce
1975, 457–458 (1975).
21. M. D. Hoops, B. S. Ault, J. Mol. Struct. 929, 22–31
effective catalysts. Along with a new group of active Au(I)-Cl species for ambient-temperature
(2009). platinum catalysts with atomically dispersed Pt NO reduction to N2O by CO. Mohamed and
22. I. Ignatyev, M. Montejo, P. G. R. Ortega, J. J. L. González, sites to maximize activity and catalytic efficiency Ichikawa (16) have shown that the Au(I) species
Phys. Chem. Chem. Phys. 13, 18507–18515 (2011). (1–3), the lower apparent activation energy Ea for are the main active sites for the WGS reaction
23. S. J. Blanksby, G. B. Ellison, Acc. Chem. Res. 36, 255–263
(2003).
the WGS reaction (~45 kJ/mol) for gold (Au) at temperatures as low as 50°C. Because these
24. E. Reisz, W. Schmidt, H. P. Schuchmann, C. von Sonntag, versus ~75 kJ/mol for platinum (3–5) can be sites are not chloride-free (Au-Cl bonds exist) and
Environ. Sci. Technol. 37, 1941–1948 (2003). exploited for low-temperature WGS and other have weak chemical binding to the zeolites, the
25. B. J. Finlayson-Pitts, J. N. Pitts Jr., Science 276, 1045–1052 reactions (6, 7). Low-temperature activity is im- Au(I) sites are easily reduced to inactive Au(0)
(1997).
26. M. S. Chen, M. C. White, Science 318, 783–787 (2007).
portant to avoid multiple-treatment units in prac- and form Au NPs upon increasing the temper-
27. T. Newhouse, P. S. Baran, Angew. Chem. Int. Ed. 50, tical low-temperature proton-exchange membrane ature to only 100°C (16). Similarly, low stability
3362–3374 (2011). (PEM) fuel cell systems, whereby the deleterious of gold on zeolites was found by Gates and co-
28. H. M. L. Davies, T. Hansen, M. R. Churchill, J. Am. Chem. Soc. CO should be totally removed for stable, long- workers (17, 18). Careful anchoring of mono-
122, 3063–3070 (2000).
29. K. Chen, A. Eschenmoser, P. S. Baran, Angew. Chem. Int. Ed.
term operation. The active Au species in the WGS nuclear Au(III) complexes from organometallic
48, 9705–9708 (2009) and references therein. catalysts are atomic species anchored through –O precursors produced chloride-free single-atom
30. H. Varkony, S. Pass, Y. Mazur, J. Chem. Soc. Chem. Commun. ligands to different supports such as ceria (3, 8, 9), Au(III)-O-NaY catalytic centers that were ac-
1974, 437–438 (1974). iron oxide (10–12), lanthana (13), and titania (4), tive for CO oxidation but unstable at 25°C and
31. S. I. Chan et al., J. Catal. 293, 186–194 (2012).
and the number of the active Au sites can be 760 torr, losing ~75% of their initial activity after
ACKN OW LEDG MEN TS increased through a variety of catalyst prepa- 15 min on stream (17). Finally, attempts to ion
We are grateful for financial support from the Ministry of Science ration protocols. Gold nanoparticles (Au NPs) exchange gold in zeolites have been unsuccessful.
and Technology, Taiwan. K.C.H. conceived the idea, designed that can form during catalyst preparation are Thus, gold ions in zeolites tend to be unstable
the experiments, and wrote the manuscript. A.S. conducted the spectator species in these chemistries (3, 4, 10), toward aggregation in realistic reaction gas en-
experiments. Metrical parameters for the x-ray structures of
2b and 2g are available free of charge from the Cambridge
in that most of the Au atoms are not activated vironments at temperatures above the ambi-
Crystallographic Data Centre under accession numbers CCDC by the support. Thus, the approach of “cage en- ent, an issue already understood for other inert
1025098 and CCDC 1025099, respectively. A patent application capsulation” of Au NPs in mesoporous supports supports such as silica or alumina, minimally in-
is pending. teracting with gold (19). Hence, it is difficult to
determine if the gold catalysts operate through
1
Department of Chemical and Biological Engineering, Tufts
similarly structured Au-O(OH)x- species on inert
SUPPLEMENTARY MATERIALS supports as in the Au-CeOx, Au-FeOx, and Au-TiOx
University, MA 02155, USA. 2Department of Chemical and
[Link]/content/346/6216/1495/suppl/DC1 Biological Engineering, University of Wisconsin–Madison, WI systems (20).
Materials and Methods 53706, USA. 3Department of Chemical Engineering,
Supplementary Text
To study the nature of the active gold sites on
Louisiana State University, Baton Rouge, LA 70803, USA.
Figs. S1 to S6 4
Materials Science and Technology Division, Oak Ridge
inert supports, it is important to maximize the
Tables S1 to S15 National Laboratory, Oak Ridge, TN 37831, USA. 5X-ray number of the atomically dispersed gold sites
References (32–44) Science Division, Argonne National Laboratory, 9700 South and fully eliminate the formation of Au NPs.
1
H and 13C NMR Data Cass Avenue, Argonne, IL 60439, USA. 6School of Chemical
1
H and 13C NMR Spectra
Titania is inferior to ceria and iron oxide in that
and Biomolecular Engineering, University of Sydney, NSW
2006, Australia.
Au NP growth occurs rapidly on its surfaces (21),
6 August 2014; accepted 11 November 2014 *Corresponding author. E-mail: [Link]-stephanopoulos@ but with special ultraviolet (UV)–assisted prepa-
10.1126/science.1259684 [Link] ration methods, mononuclear Au-O(OH)x- species

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 RE S EAR CH | R E P O R T S

Table 1. Composition and reaction activity of supported gold catalysts.

Alkali:gold WGS reaction Ea for WGS Surface –OH

Sample wt % atomic ratio rate at 150°C reaction (mmol/gcat, Average gold
Au/support (10−7 mol H2/gcat s)* (kJ/mol) 50°–350°C)† size (nm)‡
Na K
0.25 Au/KLTL – 1.0§ 1.0 46.5 34 T 5 > 10
0.25 Au-K/KLTL – 11.0§ 8.2 49.0 174 T 10 Atomically dispersed
0.25 Au/ 0.0 – 0.0 Inactive below 300°C 20 T 5 > 10
[Si]MCM41
0.25 Au-Na/ 10.0 – 7.9 43.6 164 T 10 Atomically dispersed
[Si]MCM41
*The kinetics were measured in a simulated reformate gas mixture of 11% CO, 26% H2O, 7% CO2, 26% H2-He (100- to 500-mg sample, steady-state CO conversion
<15%). †The total amount of –OH species was titrated by CO TPR (10% CO-He, 30 ml/min, 100 mg, 5°C/min, from 50° to 350°C). ‡Gold nanoparticles
larger than 1 nm were determined by HRTEM. The atomically dispersed gold species were imaged by STEM and also fitted by EXAFS. §Value is for the added
potassium; it does not include the ion-exchanged potassium in the as-received zeolite KLTL.

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can be stabilized on titania up to 1.2 weight % Fig. 1. Aberration-corrected
(wt %), and the cations remain stably anchored high-angle annular dark-
and active for the WGS reaction from ~ 80° to field–STEM images of the
250°C (4). Alkali ion addition was investigated 0.25Au-Na/[Si]MCM41 cat-
in this work as a means to boost further the alyst. The circles are drawn
number of stable mononuclear Au-O(OH)x- around isolated gold atoms.
species. This was reported as a successful The size distribution (inset)
approach to prepare single-site active Pt-O(OH)x- is based on >150 observed
(Na or K)y species on silica and alumina, which gold species counted
were activated at low temperatures (~100°C) from the high-magnification
for the WGS reaction and were stable to tem- images (recorded at 8 to
peratures exceeding 300°C and for many hours 10M× original magnification).
(1). Washing of the surfaces could not remove
the alkali ions stably associated with the Pt
ion through -O linkages. Zugic et al. showed
that the Pt-O(OH)x-(Na or K)y species could be
prepared, stabilized, and similarly activated
for the WGS reaction on inert (800°C-annealed)
carbon nanotube surfaces (2). However, the
extension of the platinum findings to gold is
neither obvious nor anticipated. A few reports
exist on alkali (and alkaline earth) addition
to gold to structurally stabilize small Au NPs
(1 to 3 nm) on alumina for ambient-temperature
CO oxidation (22). Miller et al. (19) adopted a
NaOH wash to remove the adsorbed Cl ions
from the Au/Al2 O 3 catalysts and estimated Notably, the KLTL-zeolites used here have an plays a crucial role in the WGS reaction, pro-
by extended x-ray absorption fine structure abundance of potassium ions (16.8 wt %), but viding facile dissociation of water molecules to
(EXAFS) that the gold was 100% dispersed on gold addition from a typical precursor (e.g., supply –OH species to the vicinal gold sites where
these washed samples under mild reduction HAuCl4) by incipient wetness impregnation (IWI) CO is adsorbed (24), but the active sites were not
(up to 200°C) or oxidation (up to 225°C), but or deposition precipitation fails to prepare an resolved. These may still involve just the Au-(OH)x
their stability under reaction conditions was active catalyst. However, using IWI of KAu(CN)2 species attached to the support through –O lig-
not reported. on the KLTL-zeolites followed by solid-state im- ands. We present evidence here for the latter by
We show how to use alkali addition to activate pregnation of KOH (Au:K = 1:10) did form an surrounding the gold atom with a large number
and stabilize atomic Au for the WGS reaction active Au-K/KLTL catalyst after careful heating (8 to 10) of Na or K ions through –O ligands. The
even on inert zeolite (KLTL) and mesoporous [details of the preparation methods are described choice of the supporting surface (zeolite, silica,
[Si]MCM-41 silica materials. The WGS activity in the supplementary materials (23)]. In another alumina, etc.) is then unimportant for the
was measured to be comparable to that of Au preparation, a gold sol formed from HAuCl4 with chemistry.
on reducible oxide supports, and good stabil- NaOH (Au:Na = 1:10) at pH ~14 was used to pre- The lack of sensitivity of Ea for the WGS re-
ity was found up to 200°C (Table 1). The Ea pare an active Au-Na/[Si]MCM41 catalyst (table action on the type of support is a strong first
values measured for the reaction over alkali- S1). For other supports, including a hydrothermally indication of a structurally similar gold active
stabilized gold on the inert supports are all 45 T treated alumina in NaOH, see preparation details site present on all supports. Corroborating this
5 kJ/mol, similar to those on the Au-CeOx, Au- in the supplementary materials and in fig. S1 and finding, kinetics measurements found that the
FeOx, and Au-TiOx systems (20), indicating that tables S1 and S2. reaction order for H2O is 0.7 to 0.8 for all the
the gold active sites are of similar structure on The preparation protocols show that the re- catalysts (with or without alkali) used in this
all support types. It is not straightforward to quirement for an active catalyst is that the alkali work (fig. S2), demonstrating that the role of
produce the active alkali-stabilized gold cen- ions are linked to the atomic gold through –O water is common on all the gold catalysts. The
ters on the inert supports, as the alkali ions ligands and not merely be present on the sup- alkali addition modifies the support properties
must interact with the gold, not the support. port. It has been widely reported that the support at higher temperatures; for example, after a

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R ES E A RC H | R E PO R TS

thermal treatment to 600°C, Amenomiya and co-

workers found that alkalized alumina was acti-
vated for the WGS reaction above 400°C with Ea
of ~ 80 kJ/mol (25, 26).
CO temperature-programmed reaction (TPR)
tests were conducted to titrate the WGS-active
hydroxyls on the alkali-stabilized gold sites (up to
350°C) (Table 1, table S2, and fig. S3). The pres-
ence of alkali markedly increased the amount
of these hydroxyls, and correspondingly the over-
all WGS activity of the catalyst within the same
temperature window. These hydroxyls are regen-
erable, as shown by consecutive CO-TPR cycles
with intermittent rehydration of the catalyst at
25°C (fig. S3). In the absence of gold, the addition
of K+ only provides trace amounts of dry [O]
through the surface transformation of –OK to
K2O (27). With the gold present, as in Au-K/

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KLTL, gold associated with the potassium shows a
large amount of CO2 formation from active –OH
species corresponding to a Au:K atomic ratio of
1:8. This was accompanied by the production of
a large amount of H2 (1/2 of CO2) from the –OH
species (fig. S3). Notably, from the samples with
fully dispersed gold (0.25Au-K/KLTL and 0.25Au-
Fig. 2. Bader charge of Au in AuOx(OH)yNa9 cluster sites. For reference, the Bader charges of Au
Na/[Si]MCM41) and earlier reports (4), we found
in bulk Au2O (+0.41) and Au2O3 (+1.11) are given by the dashed horizontal lines. Au, Na, O, and H
that the total activity is proportional to the num-
atoms are shown with yellow, purple, red, and white spheres, respectively. The clusters shown are
ber of the surface –OH species, whereas the ac-
examples of promising structural candidates for the WGS active site. The circled data correspond to
tivity per gold atom (turnover frequency) is the
clusters that have Au oxidation states between that of Au2O and Au2O3.
same for all gold catalysts irrespective of the sup-
port (fig. S4). The Au-K/KLTL sample also shows
good stability in 100 hour-long operation in a
reformate-type gas mixture (fig. S5).
Electron microscopy studies revealed that al-
kali ion addition markedly increased the disper-
sion of gold on all the inert supports that we
investigated in this work (Table 1, Fig. 1, and figs.
S6 to S9). For example, 72% of the gold counted
in the images was present as isolated atoms away
from each other on the surface of the 0.25Au-Na/
[Si]MCM41 sample (Fig. 1 and fig. S6). A minority
of subnanometer gold clusters present on the
same sample did not have the packed gold atom
structure of Au NPs. These species appear to com-
prise a few atoms of gold anchored close to each
other but nonaggregated. The presence of the
surrounding alkali atoms could not be deter-
mined by imaging because of the low contrast
of these light elements. EXAFS analysis under
in situ conditions for the working catalysts fur-
ther confirmed that the gold species were atom-
ically dispersed and associated with alkali ions
before and after reaction (table S3 and fig. S10).
For both the KLTL-zeolite and [Si]MCM41-
supported samples, the Nax-Oy linkages to gold
effectively reduced the Au-Au coordination
number from 11 or 12 to the 3 or 4 range, which
Fig. 3. TOF plot for the WGS reaction over samples with atomically dispersed gold in a reformate-
means that 100% dispersion of Au had been
type gas mixture of 11% CO, 26% H2O, 7% CO2, and 26% H2-He. The data for the 1.16Au/TiO2
achieved (19). Although microscopic analysis
(G5, UV) sample are from (4), for the 0.50Au/CeO2 (La doped CeO2, DP) sample from (8), and for the
(transmission electron microscopy or scanning
0.12Au/Fe2O3 (DP) sample from (35). The experimental error for the reaction rate measurements is less
transmission electron microscopy) provides a
than 10%. The R2 for the linear fit is 0.9927.
number-weighted particle distribution, the volume-
weighted distribution provided by EXAFS can
be heavily skewed by a few large particles (23). near-edge structure spectra (fig. S11) and x-ray tain metallic Au NPs exclusively. The extra K+
Along with the EXAFS results showing an photoelectron spectroscopy data (fig. S12) show ions stabilizing the Au-Ox site in the Au-K/KLTL
enrichment of the Au-O shell for the alkali- the cationic nature of the gold species, whereas sample are different from the ion-exchanged
containing samples, in situ x-ray absorption the alkali-free, catalytically inactive samples con- K-O-Al sites in the as-received KLTL zeolite,

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 RE S EAR CH | R E P O R T S

but are associated with –O (28), –OH, and The O/OH groups in the clusters play vital 16. M. M. Mohamed, M. Ichikawa, J. Colloid Interface Sci. 232,
H2O in their vicinity (29), as indicated by the K2p roles in H2O dissociation. First, O/OH stabilize 381–388 (2000).
17. J. C. Fierro-Gonzalez, B. C. Gates, J. Phys. Chem. B 108,
x-ray photoelectron spectra (fig. S12). These re- H2O binding through hydrogen bonding (33). As
16999–17002 (2004).
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between gold and potassium through oxygen clusters than on Au(111). Second, the hydrogen Ed. 51, 5842–5846 (2012).
bonding. atom released during H2O dissociation prefers to 19. J. T. Miller et al., J. Catal. 240, 222–234 (2006).
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(2014).
tive site [Au-O(OH)x- species] for the WGS ing to a much more exothermic water disso- 21. G. M. Veith, A. R. Lupini, S. J. Pennycook, N. J. Dudney,
reaction that is stabilized by several alkali ions ciation event than on clean Au(111) or Cu(111) ChemCatChem 2, 281–286 (2010).
via -O- linkages. To gain further insights, we surfaces. The more exothermic activation should 22. A. C. Gluhoi, X. Tang, P. Marginean, B. E. Nieuwenhuys, Top.
used density functional theory (DFT) calcula- increase activity for H2O dissociation. Although Catal. 39, 101–110 (2006).
23. Supporting materials are available on Science Online.
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24. J. A. Rodriguez, S. D. Senanayake, D. Stacchiola, P. Liu,
molecular dynamics (30), by using the VASP code sible. The colocation of adsorbed CO and the –OH J. Hrbek, Acc. Chem. Res. 47, 773–782 (2014).
(31) (details of the computational methods are groups bound on the threefold “Na3” sites that 25. B. W. Krupay, Y. Amenomiya, J. Catal. 67, 362–370
described in the supplementary materials). To surround the gold atom offers the possibility for (1981).
create candidate structures for the Au-O(OH)x-Nay facilitating COOH formation, a critical interme- 26. Y. Amenomiya, G. Pleizier, J. Catal. 76, 345–353 (1982).
27. W. H. J. Stork, G. T. Pott, J. Phys. Chem. 78, 2496–2506
system, we began by inspecting a series of diate in the WGS reaction (34). An analog of this
(1974).
AuNax clusters (x = 1 to 10, without oxygen). Out structure was recently proposed for single gold 28. R. Sawyer, H. W. Nesbitt, R. A. Secco, J. Non-Cryst. Solids 358,

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of these, the AuNa9 precursor was selected for atoms stabilized over uncapped oxygen and sur- 290–302 (2012).
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30. S. Nosé, J. Chem. Phys. 81, 511 (1984).
in a single shell around Au; beyond 9, additional oxide (35) is similar to that of Au in the alkali-
31. G. Kresse, J. Furthmüller, Phys. Rev. B 54, 11169–11186
Na atoms must be accommodated in a second stabilized structure reported here, as shown in (1996).
shell around the gold atom; see supplementary Fig. 3. 32. G. Henkelman, A. Arnaldsson, H. Jonsson, Comput. Mater. Sci.
materials for details) and because its Na:Au In Fig. 3, we scaled the steady-state reaction 36, 354–360 (2006).
ratio closely matches the experimental facts/ rates by the amount of gold loading for the atom- 33. L. R. Merte et al., Nat. Commun. 5, 4193 (2014).
34. A. A. Gokhale, J. A. Dumesic, M. Mavrikakis, J. Am. Chem. Soc.
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detected experimentally and to account for the for other gold catalysts reported to comprise only 35. Y. Zhai, thesis, Tufts University (2011).
involvement of oxygen in the active site, electron- atomic gold on other supports—e.g., after leaching
withdrawing groups (O/OH) were then added of gold particles—and cast them in terms of a AC KNOWLED GME NTS
to the AuNa9 cluster, and the Bader charge turnover frequency (TOF) in an Arrhenius plot. The financial support by the U.S. Department of Energy,
Office of Basic Energy Sciences (DOE-BES) under grant
was calculated (32). For reference, the calcu- In addition to the similar Ea values, the close-
DE-FG02-05ER15730 is gratefully acknowledged. M.Y.
lated Bader charges of Au in bulk gold oxides ness of the TOFs over gold catalysts prepared thanks H. Luo (Massachusetts Institute of Technology) for
Au2O and Au2O3 (used as references for Au(I) on different supports and from different precur- some of the surface area and pore structure analysis,
and Au(III), respectively) are +0.41 and +1.11, sors, and subjected to different treatment methods, C. Wang (Tufts University) for acquiring the XRD data,
and B. Reinhart [Argonne National Laboratory (ANL)]
respectively. In a systematic study of cluster is noteworthy. With these findings, we conclude
for assisting with the in situ XAS experiments. Microscopy
sites of the general composition AuOx(OH)yNa9, that, being structurally similar as on CeO2, Fe2O3 research was sponsored in part by a user project supported
several clusters in which the charge of the Au and TiO2, single-site cationic Au-O(OH)x- spe- by the Center for Nanophase Materials Sciences (CNMS),
atom is similar to that of Au in bulk Au2O and cies, stabilized by a number of alkali ions in the which is sponsored at Oak Ridge National Laboratory
(ORNL) by the Scientific User Facilities Division,
Au2O3 were identified (the circled models in Fig. form of AuOy(OH)z(Na or K)x clusters, may be
DOE-BES, and by the U.S. DOE Office of Energy Efficiency
2). To evaluate if any of these structures that formed in appreciable amounts on inert supports. and Renewable Energy, Vehicle Technologies Office,
feature an oxidized Au atom would be active for These species are highly active for the WGS re- Propulsion Materials Program. The XAS research is
WGS, the thermochemical properties relevant action, the single gold atom maximizing the sponsored by the Advanced Photon Source at ANL under
contract DE-AC02-06CH11357. Work at the University of
to the key steps of WGS (including CO and H2O catalyst efficiency.
Wisconsin–Madison was supported by DOE-BES, Office of
adsorption, OH binding, and H2O activation) were Chemical Sciences. Computational work was performed in part
calculated on these candidate AuOx(OH)yNa9 RE FERENCES AND NOTES with supercomputing resources from the following institutions:
structures and compared with those on ex- 1. Y. Zhai et al., Science 329, 1633–1636 (2010). Environmental Molecular Sciences Laboratory (EMSL), a
2. B. Zugic, S. Zhang, D. C. Bell, F. F. Tao, M. Flytzani-Stephanopoulos, national scientific user facility at Pacific Northwest National
tended Cu(111) and Cu(211) surfaces. As Cu is
J. Am. Chem. Soc. 136, 3238–3245 (2014). Laboratory (PNNL); the Center for Nanoscale Materials
one of the best low-temperature WGS catalysts, 3. Q. Fu, H. Saltsburg, M. Flytzani-Stephanopoulos, Science 301, (CNM) at ANL; the CNMS at ORNL; and the National Energy
these are the properties that are most relevant to 935–938 (2003). Research Scientific Computing Center (NERSC). EMSL is
mimic. 4. M. Yang, L. F. Allard, M. Flytzani-Stephanopoulos, J. Am. Chem. sponsored by the Department of Energy’s Office of
Soc. 135, 3768–3771 (2013). Biological and Environmental Research located at PNNL.
Based on both the Bader charge and the
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thermochemical analysis (see table S4), AuO7 - 6. M. Flytzani-Stephanopoulos, B. C. Gates, Annu. Rev. Chem. Energy, Office of Science, under contracts DE-AC02-06CH11357
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(2011). authors declare no conflict of interest.
ters on this list are shown in Fig. 2, and the last
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two are shown in fig. S13) were identified as Appl. Catal. B 56, 57–68 (2005).
promising candidates for the active WGS re- 9. R. Si, M. Flytzani-Stephanopoulos, Angew. Chem. Int. Ed. 47, SUPPLEMENTARY MATERIALS
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ligands. (1994). 10.1126/science.1260526

SCIENCE [Link] 19 DECEMBER 2014 • VOL 346 ISSUE 6216 1501

 Catalytically active Au-O(OH)x- species stabilized by alkali ions
on zeolites and mesoporous oxides
Ming Yang, Sha Li, Yuan Wang, Jeffrey A. Herron, Ye Xu,
Lawrence F. Allard, Sungsik Lee, Jun Huang, Manos Mavrikakis
and Maria Flytzani-Stephanopoulos (November 27, 2014)
Science 346 (6216), 1498-1501. [doi: 10.1126/science.1260526]
originally published online November 27, 2014
Editor's Summary

Downloaded from [Link] on November 4, 2016

Dispersing catalytic gold as widely as possible

In order to maximize the activity of precious metals in catalysis, it is important to place the metal
on some support with a high surface area (such as a zeolite) and to maintain the metal as small clusters
or even atoms to expose as much metal as possible. The latter goal is more readily achieved with oxides
of reducible metals such as cerium or titanium than with the aluminum and silicon oxides that make up
most zeolites and mesoporous oxides. Yang et al. show that sodium and potassium can stabilize gold
along with hydroxyl and oxo groups to create highly active catalysts for the water-gas shift reaction at
low temperatures, a reaction that can be useful in applications such as fuel cells.

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