ARTICLES

PUBLISHED ONLINE: 2 MARCH 2014 | DOI: 10.1038/NCHEM.1873

Discovery of a Ni-Ga catalyst for carbon dioxide

reduction to methanol
Felix Studt1, Irek Sharafutdinov2, Frank Abild-Pedersen1, Christian F. Elkjær2, Jens S. Hummelshøj1,
Søren Dahl2, Ib Chorkendorff2 and Jens K. Nørskov1,3 *

The use of methanol as a fuel and chemical feedstock could become very important in the development of a more
sustainable society if methanol could be efficiently obtained from the direct reduction of CO2 using solar-generated
hydrogen. If hydrogen production is to be decentralized, small-scale CO2 reduction devices are required that operate at low
pressures. Here, we report the discovery of a Ni-Ga catalyst that reduces CO2 to methanol at ambient pressure. The
catalyst was identified through a descriptor-based analysis of the process and the use of computational methods to
identify Ni-Ga intermetallic compounds as stable candidates with good activity. We synthesized and tested a series of
catalysts and found that Ni5Ga3 is particularly active and selective. Comparison with conventional Cu/ZnO/Al2O3 catalysts
revealed the same or better methanol synthesis activity, as well as considerably lower production of CO. We suggest that
this is a first step towards the development of small-scale low-pressure devices for CO2 reduction to methanol.

N
ature reduces CO2 photochemically to store energy, and show experimentally that it has the unique property that it
devising an artificial process to replicate this remains one of reduces CO2 to methanol without producing large amounts of CO
the grand challenges in modern chemistry1–4. One possibility, via the rWGS reaction.
which is currently the subject of very active research, is a photo-elec-
trochemical process, but finding an electrocatalyst that is selective Results
and has a low overpotential is challenging5–11. An alternative A large literature exists about the methanol synthesis reaction over
approach would be to first generate molecular hydrogen via a supported copper catalysts18–28. Here, we consider the direct CO2
photo-electrochemical process or an electrochemical process using reduction to methanol. Grabow and Mavrikakis have considered
electrical power from photovoltaic cells or wind turbines12,13. If many different reaction paths and suggested the following to be
the hydrogen were then used in a heterogeneously catalysed most likely29,30:
process to reduce CO2 to methanol, a sustainable source of liquid
fuel would be established. H2 (g) + 2* ↔ 2H* (1)
Today, methanol is produced in large facilities from CO, CO2 and
H2 (derived from fossil resources) in a high-pressure (50–100 bar) CO2 (g) + H* ↔ HCOO* (2)
process using a Cu/ZnO/Al2O3 catalyst14. If hydrogen production is
to be distributed and produced in small-scale devices, it would be HCOO* + H* ↔ HCOOH* + * (3)
attractive if the subsequent conversion of H2 into a liquid fuel
could also be performed in simpler, low-pressure decentralized HCOOH* + H* ↔ H2 COOH* + * (4)
units. This is not, however, simply a case of reengineering the technol-
ogy currently optimized for high-pressure conversion of syngas into H2 COOH* + * ↔ H2 CO* + OH* (5)
methanol, because a low-pressure CO2 reduction process may
require a different catalyst. Another challenge arises with the use of H2 CO* + H* ↔ H3 CO* + * (6)
CO-free CO2 , which will lead to CO as a by-product of methanol
via the reverse water–gas shift (rWGS) reaction. The production of H3 CO* + H* ↔ CH3 OH(g) + 2* (7)
CO not only reduces the yield of methanol—it also has a negative
effect when methanol is used in fuel cells because CO poisons the OH* + H* ↔ H2 O(g) + 2* (8)
Pt catalyst used. Using the industrial Cu/ZnO/Al2O3 catalyst
(which is optimized for different reaction conditions including a The symbol * represents a surface site or an adsorbed species.
CO-rich feed) in low-pressure methanol synthesis leads to significant A simple mean-field kinetic model is used to elucidate trends in
CO production, so new catalysts are needed to advance this field. reactivity. The model treats all reaction steps as being potentially
In the present Article, we report the discovery of a new, non- rate-determining and solves the rate of methanol production
precious metal catalyst working at low pressure with similar or under steady-state conditions, similar to those described for other
higher methanol yield than the current Cu/ZnO/Al2O3 methanol reactions31,32. There are a total of eight activation energies for the
synthesis catalyst15–17. We use a computational descriptor-based forward elementary steps. Together with the eight elementary reac-
approach to guide us towards a new class of Ni-Ga catalysts and tion energies, these define the complete energy-space of the

1
SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, USA,
2
Centre for Individual Nanoparticle Functionality (CINF), Department of Physics, Building 307 Technical University of Denmark, DK-2800 Lyngby, Denmark,
3
SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, Stanford, California 94305, USA.
* e-mail: norskov@stanford.edu

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ARTICLES
1 a
Cu + Zn
Ni3Ga
Ni5Ga3
0 Ni5Ga3 Cu
log (TOF/TOFCu)
NiGa
–1 NiGa Pd
Ni
Ni3Ga
–2
–2 –1 0 1
Cu
ΔEO – ΔEO (eV)
Figure 1 | Theoretical activity volcano for CO2 hydrogenation to methanol.
Turnover frequency (TOF) is plotted as a function of DEO , relative to
Cu(211). DEO for the stepped 211 surfaces of copper, nickel and palladium is
depicted as open black circles, and Cu þ Zn is depicted in orange. DEO for
Ni-Ga intermetallic compounds is depicted in red. Closed circles indicate
nickel-rich sites, open circles gallium-rich sites and half-open circles mixed
sites. Reaction conditions are 500 K, 1 bar, and a CO2:H2 ratio of 1:3.
reaction. These energies have been calculated with density func-
tional theory (DFT) using the RPBE exchange-correlation energy
functional33 for a selected set of metals (see Supplementary Tables
1 and 2 for a table of all the energies). In each case we chose a
stepped face-centred cubic fcc(211) surface to represent the active
site30,34. We have shown that van der Waals (vdW) interactions
can be important for the energetics of CO2 reduction for Cu(211)
using the BEEF–vdW functional35,36. In the following we include
such effects by assuming that the extra effect of van der Waals inter-
actions is the same as on copper for all the other metals considered.
Given the non-specific nature of the dispersion interactions, and the
fact that the catalytically interesting metals are close in bonding to
copper, this is a very reasonable approximation.
We will now describe the approach we have taken to reduce the
number of energy parameters in the methanol synthesis from 16 to
only 1. In doing so we lose some accuracy, but it is important
to build such a model for at least two reasons. First, it allows us to
understand the trends in catalytic activity among the metals.
Second, it is a very efficient way of identifying new catalyst
leads37,38. We find that scaling relations exist between the oxygen
adsorption energy, DEO , and the adsorption energies and tran-
sition-state energies of all the hydrogenated forms of CO2 when
we compare different metal surfaces (see Supplementary Figs. 1
and 2 for the complete set of scaling relations). The result is a com-
plete mapping of all the relevant energies in the methanol kinetics
onto only one parameter, DEO. To a first approximation this par-
ameter characterizes the catalytic properties uniquely.
Solving the steady-state microkinetic model with the input of
these scaling relations yields the calculated rate of CO2 hydrogen-
ation as a function of DEO at ambient pressure and 500 K, as
shown in Fig. 1. Values of DEO for the elemental metals copper, pal-
ladium and nickel are included in this volcano plot. The optimum in
reaction rate is a result of competition between having a too weak
interaction with oxygen (resulting in too unstable intermediates
and high reaction barriers) and a too strong coupling to oxygen
(giving rise to surface poisoning by formate, and possibly other
species bound through oxygen).
At atmospheric pressure, elemental copper is closest to the top,
while nickel and palladium bind oxygen too strongly and weakly,
2 NATURE CHEMISTRY | ADVANCE ONLINE PUBLICATION | www.nature.com/naturechemistry
© 2014 Macmillan Publishers Limited. All rights reserved.
NATURE CHEMISTRY DOI: 10.1038/NCHEM.1873
Ni5Ga3 NiGa
10 nm 10 nm
b
In situ XRD
after reduction/alloying
2
α-Ni3Ga
Intensity (a.u.)
δ-Ni5Ga3
β-NiGa
Cu/ZnO/Al2O3
40 50 60 70 80 90
2θ (deg)
Figure 2 | Characterization of the catalysts studied. a, TEM images of
Ni5Ga3 and NiGa. b, In situ XRD patterns of Ni3Ga, Ni5Ga3 and NiGa
intermetallic compounds as well as Cu/ZnO/Al2O3.
respectively. In the figure we have also included zinc doping in a
copper step to model the active site of the ZnO promoted commer-
cial catalyst. This has been shown theoretically and experimentally
to be a good description30, and the model captures the near-
optimal activity of such a site. Our one-descriptor model therefore
provides a good starting point for discovering other potential cata-
lysts. We note that even though the zinc promoted copper steps have
close to optimal activity, the density of such sites is small in a doped
system30, and a more homogeneous catalyst with the same activity
per site but more active sites would be advantageous.
In Fig. 1 we have included predictions of the simple models for
the mixed-metal system Ni-Ga. We chose Ni-Ga because this com-
prises a series of stable intermetallic compounds with large ordering
energies (for example, Ni-Ga is calculated to have a heat of for-
mation of 20.64 eV/formula unit (two atoms)). This increases the
chance that the surfaces exhibit a truncated bulk structure,
making modelling simpler.
Several of the Ni-Ga intermetallic compounds show active
sites with oxygen adsorption energies close to the optimum. We
synthesized a series of Ni-Ga catalysts with different Ni:Ga ratios sup-
ported on silica using incipient wetness co-impregnation followed by
high-temperature reduction in H2. The Ni-Ga catalysts were charac-
terized using X-ray diffraction (XRD) together with transmission
electron microscopy (TEM) (Fig. 2). As can be seen from the XRD
diffraction patterns, all three different Ni-Ga intermetallic com-
pounds, Ni3Ga, NiGa and Ni5Ga3 , could be prepared rather phase-
pure, which can be attributed to the high formation energy of the
different phases and the very sharp lines in the Ni-Ga phase
diagram39. The TEM images presented in Fig. 2a reveal an average
particle size of 5.1 nm for the Ni5Ga3 and 6.2 nm for the NiGa.
NATURE CHEMISTRY DOI: 10.1038/NCHEM.1873 ARTICLES
a important consideration for the present group of catalysts. A CO2
MeOH
0.25 reduction process that mainly produces methanol and water is
mol [active metal]*h

highly desirable, because the CO will need to be recycled or

mol[MeOH]/

0.20
CuZnO burned. The conventional Cu-Zn catalyst has a high rate of
0.15 Ni5Ga3 rWGS. The data in Fig. 3 show that this is not the case for the
0.10 Ni-Ga catalysts.
NiGa
0.05
Ni3Ga Discussion
The experimental data raise two interesting questions: (1) what is
160 180 200 220 240 260
the relationship between the activity volcano in Fig. 1 and the
Temperature (°C)
ranking of the activity data in Fig. 3; (2) why is the rWGS activity
b of the Ni-Ga catalysts lower than for the copper-based catalyst.
100
CuZnO NiGa
Part of the answer to the first question is related to the obser-
Selectivity Ni5Ga3
vation made earlier that there are two factors affecting the rate,
MeOH + DME

80
selectivity (%)

the activity and number of active sites. The copper particles will
60
be most active at the relatively few places where they are promoted
40 Ni3Ga by zinc, whereas the active sites on the intermetallic compounds do
20
not need the presence of a promoter. The difference in activity
between Cu-Zn and the intermetallic compounds is therefore prob-
0 ably masked by differences in the number of active sites. When it
160 180 200 220 240 260
comes to the ranking of the different Ni-Ga catalysts, the main dis-
Temperature (°C)
crepancy between the volcano in Fig. 1 and the experimental data in
c Fig. 3 is the Ni3Ga mixed sites catalyst, which is predicted to be very
CO/MeOH active, but found not to be so. The reason for this, we suggest, is that
100
CO/MeOH ratio

the nickel sites become poisoned by adsorbed CO and eventually

CuZnO
10
1 very well.
160 180 200 220
Temperature (°C)
Figure 3 | The measured activity and selectivity towards methanol
synthesis as a function of temperature for the studied catalysts. a, Yield of
methanol of a series of NixGay catalysts compared with Cu/ZnO/Al2O3 as a
function of temperature at atmospheric pressure. Gas composition: 75% H2
and 25% CO2. Gas hourly space velocity ¼ 6,000 h21. b, CO-free selectivity
towards methanol and dimethyl ether in per cent. c, Comparison of the CO
to MeOH ratio of Cu/ZnO/Al2O3 with Ni5Ga3.
We tested the Ni-Ga catalysts with CO2 hydrogenation at a
pressure of 1 bar in a tubular fixed-bed reactor. For comparison, a
conventional Cu/ZnO/Al2O3 catalyst was synthesized following
the procedure described in ref. 40. This procedure has been
shown to produce catalysts that are at least as good as the commer-
(through dissociation) by carbon (see the following and the
Supplementary Fig. 3) and subsequent phase separation. In fact, if
Ni5Ga3
we distinguish between nickel-rich sites and gallium-rich sites (as
done in Fig. 1 by using different symbols), it can be seen that the
gallium-rich sites follow the ordering observed experimentally
240 260 The difference in rWGS and methanol synthesis activity can be
understood with the same picture. The gallium-rich sites facilitate
methanol synthesis and the nickel-rich sites do rWGS (and metha-
nation) until they become self-poisoned by CO and carbon. It is
different for Cu-Zn, where both rWGS and methanol synthesis
proceed at the same surface site. Because CO does not bind
strongly enough to copper, no poisoning effect will be observed,
which translates into a higher rWGS activity and hence lower
methanol selectivity. A more detailed analysis supporting this
argument can be found in the Supplementary Section ‘Reverse
water-gas-shift volcano’. We note that the high activity of the
0.20
After regeneration
in H2 at 350 °C
0.15
Product (g[product]/g[cat]*h)

cial catalysts for short-term testing17. The XRD pattern of the CO

Cu/ZnO/Al2O3 catalyst is also shown in Fig. 2b. The measured *
Brunauer-Emmet-Teller surface area of this catalyst (92 m2 g21) is 0.10
*
comparable to that reported in ref. 40. MeOH
Figure 3 shows the measured activity and selectivity towards Ni5Ga3
methanol synthesis as a function of temperature for the different 200 °C
SiO2 supported Ni-Ga catalysts. The amount of active metal (Ni þ 1 atm
Ga or Cu), in moles, was the same for all catalysts under investi- CO2:H2 1:3
gation. The corresponding values of the active surface area, esti- DME
5 × 10–4
mated from XRD and TEM analysis, can be found in
CH4
Supplementary Table 3. Ni5Ga3/SiO2 stands out as being particu- 0
larly active towards methanol synthesis. In fact, at temperatures 0 20 40 60 80
above 220 8C, the yield of methanol is considerably higher than Time on stream (h)
with Cu/ZnO/Al2O3. The selectivity, including all products except
CO, is very high for Cu-Zn, Ni5Ga3 and NiGa. Only Ni3Ga produces Figure 4 | Deactivation of Ni5Ga3 with time on stream. The reaction was
significant amounts of methane. Notably, the CO-to-methanol ratio carried out at 200 8C, atmospheric pressure and with a CO2 to H2 ratio of
of Ni5Ga3 is significantly lower than that of Cu/ZnO/Al2O3 (Fig. 3c). 1:3. Regeneration of the catalyst in H2 at 350 8C is shown. Asterisks mark
The selectivity towards CO compared to methanol, that is, temperature crashes for several hours that have not been accounted for in
the rate of the rWGS versus the rate of methanol synthesis is an the total time on stream.

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ARTICLES
Ni-Ga catalysts at high temperatures is related to the low rWGS
activity. The amount of water in the gas is smaller, shifting the equi-
librium concentration of methanol up, hence substantially reducing
the backwards reaction.
We performed stability tests for the best catalyst, Ni5Ga3/SiO2 ,
under reaction conditions. Figure 4 shows the production of metha-
nol, CO, dimethyl ether and methane of Ni5Ga3/SiO2 as a function
of time on stream, at 200 8C and atmospheric pressure. After initial
deactivation of the catalyst, the activity with respect to all products
remains quite constant, with CO and methane activity dropping
most, supporting the notion developed above that there are two
different sites, one for rWGS and methanation (nickel-rich site)
and one for methanol formation (gallium-rich site). Ni5Ga3 was
tested for a period of over 60 h, after which we tried to regenerate
the catalyst through reduction with hydrogen at 350 8C for 2 h.
As can be seen in Fig. 4, the catalyst could be successfully regener-
ated to its original activity. Reduction with hydrogen yields an
amount of methane equivalent to poisoning of 10% of the catalyst
surface area (see Supplementary Table 3 for details), again
confirming our analysis above.
Concluding remarks
The Ni-Ga catalysts are not optimized but already show interesting
activity, selectivity and stability for ambient-pressure CO2 reduction.
Importantly, they are superior to the existing Cu/ZnO/Al2O3 catalyst
with respect to their ability to reduce the rWGS activity in favour of
methanol production. A process producing mainly methanol and
water would provide an excellent fuel for a fuel cell41,42 and could
be interesting in connection with a decentralized use of solar- or
wind-generated hydrogen. There are many challenges to be overcome
to make such a process viable. A process to efficiently separate CO2
from air may be the largest43–46, followed by process design and, of
course, optimization and test, including stability and resistance to poi-
soning of the catalysts. The Ni-Ga catalysts provide a good starting
point for a new catalyst system based on non-precious metals
showing new and interesting effects of suppressing the rWGS.
Methods
Density functional theory (DFT) calculations for the intermediates and transition
states were carried out on the (211) surfaces of copper, silver, palladium, platinum
and rhodium using the Dacapo code (http://wiki.fysik.dtu.dk/dacapo). The
computational set-up and model surfaces used are identical to those described in
ref. 47. Determination of NiGa and Ni3Ga intermetallic compound stability was
performed as described in ref. 47. DEC and DEO were retrieved from ref. 47, as
found in CatApp48. Further information about calculations regarding Ni5Ga3 as
well as CO adsorption can be found in the Supplementary Fig. 4. Gas-phase values
obtained for CO2 and HCOOH were corrected as described in refs 35 and 49.
Contributions from van der Waals interactions were included as estimated by
comparison to calculations performed with the BEEF–vdW functional described
elsewhere.35 Steady-state solutions to the microkinetic model were found as
described in ref. 32.
Ni-Ga catalysts were prepared using incipient wetness impregnation of a mixed
aqueous solution of nickel and gallium nitrates (Sigma Aldrich) on silica (Saint-
Gobain NorPro). The samples were directly reduced in H2 for 2 h at 700 8C. The
conventional Cu/ZnO/Al2O3 catalyst was prepared following the procedure
described in ref. 40.
Activity measurements were carried out at a total flow rate of 100 Nml min21 in
a tubular fixed-bed reactor with a CO2 to H2 ratio of 3:1 at atmospheric pressures.
Catalyst loading was 0.472 g for Ni3Ga, 0.476 g for NiGa, 0.474 g for Ni5Ga3 and
0.167 g for Cu/ZnO/Al2O3 , ensuring that the total amount of nickel and
gallium in moles matched the amount of copper in Cu/ZnO/Al2O3. The metal
loading of the Ni-Ga and Cu/ZnO/Al2O3 catalysts was 17 wt% and 48 wt%,
respectively. The outlet stream was sampled every 15 min using a gas chromatograph
(Agilent 7890A).
TEM measurements were performed using a FEI Technai TEM operating at
200 kV. XRD patterns were recorded with a PANalytical X’Pert PRO diffractometer
equipped with an Anton Paar XRK in situ cell and a gas flow control system.
Received 12 November 2013; accepted 14 January 2014;
published online 2 March 2014
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NATURE CHEMISTRY DOI: 10.1038/NCHEM.1873
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Acknowledgements
F.S., F.A-P., J.S.H. and J.K.N. acknowledge support from the US Department of Energy.
This work was partly supported by The Danish National Research Foundation’s Centre for
Individual Nanoparticle Functionality (DNRF54) and partly by the Catalysis for
Sustainable Energy initiative, which is funded by the Danish Ministry of Science,
Technology, and Innovation. The authors also thank J. R. Rostrup-Nielsen for
helpful discussions.
Author contributions
F.S., F.A-P., J.S.H. and J.K.N. contributed to the computational work in this article. I.S.,
C.F.E., S.D. and I.C. contributed to the experimental work.
Additional information
Supplementary information is available in the online version of the paper. Reprints and
permissions information is available online at www.nature.com/reprints. Correspondence and
requests for materials should be addressed to J.K.N.
Competing financial interests
The authors declare no competing financial interests.
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