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Letter
Nickel-Gallium-Catalyzed Electrochemical Reduction of
CO2 to Highly Reduced Products at Low Overpotentials
Daniel A. Torelli, Sonja A Francis, J. Chance Crompton, Alnald Javier, Jonathan
R Thompson, Bruce S. Brunschwig, Manuel P. Soriaga, and Nathan S. Lewis
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.5b02888 • Publication Date (Web): 17 Feb 2016
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4 Nickel-Gallium-Catalyzed Electrochemical Reduction of CO2 to
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Highly Reduced Products at Low Overpotentials
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8 Daniel A. Torelli¶†‡, Sonja A. Francis¶†‡£, J. Chance Crompton†‡, Alnald Javier‡, Jonathan R.
9 Thompsonǁ, Bruce S. Brunschwig*§, Manuel P. Soriaga*‡, and Nathan S. Lewis*†‡§
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11 †Division of Chemistry and Chemical Engineering, ‡Joint Center for Artificial Photosynthesis,
£Resnick Sustainability Institute, ǁ Division of Engineering and Applied Sciences, and §Beckman
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13 Institute Molecular Materials Research Center, California Institute of Technology, Pasadena,
14 California 91125, United States
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16 ¶These authors contributed equally
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Abstract: We report the electrocatalytic reduction of CO2 to the highly reduced C2 products, ethylene and ethane, as
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well as to the fully reduced C1 product methane, on three different phases of nickel-gallium (NiGa, Ni3Ga, and
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23 Ni5Ga3) films prepared by drop-casting. In aqueous bicarbonate electrolytes at neutral pH, the onset potential for
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25 methane, ethylene, and ethane production on all three phases was found to be -0.48 V vs. the reversible hydrogen
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27 electrode (RHE), among the lowest onset potentials reported to date for the production of C2 products from CO2.
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29 Similar product distributions and onset potentials were observed for all three nickel-gallium stoichiometries tested.
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31 The onset potential for the reduction of CO2 to C2 products at low current densities catalyzed by nickel-gallium was
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33 > 250 mV more positive than polycrystalline copper, and approximately equal to single crystals of copper, which
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35 have some of the lowest overpotentials to date for the reduction of CO2 to C2 products and methane. The nickel-
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37 gallium films also reduced CO to ethylene, ethane, and methane, consistent with a CO2 reduction mechanism that
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39 first involves the reduction of CO2 to CO. Isotopic labeling experiments with 13
CO2 confirmed that the detected
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41 products were produced exclusively by the reduction of CO2.
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45 Keywords: CO2 reduction, electrocatalysis, nickel gallium, NiGa, ethane, methane, low overpotential, C2
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47 production
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50 Introduction
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53 Pioneering work in the 1980s showed that Cu is the only pure metal capable of catalyzing the electrochemical
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55 reduction of CO2 to highly reduced products (any product requiring the transfer of > 6 electrons, with needed
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57 protons, to one molecule of CO2) in an aqueous solution at near-neutral pH in high yields.1-3 Under 1 atm of CO2,
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3 polycrystalline Cu produces a mixture of gaseous and liquid hydrocarbons (CH4, C2H4, C2H5OH, and C3H7OH) at
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5 >70% Faradaic efficiency. However, potentials more negative than -1 V vs. the reversible hydrogen electrode
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7 (RHE) are required to reduce CO2 to these products at cathodic current densities > 1 mA cm-2. Detailed
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9 investigations indicate that as many as 14 different highly reduced products, at a variety of yields, can be produced
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11 by Cu under aqueous, neutral pH conditions.4
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14 The electrocatalytic activity of Cu has inspired efforts to improve the selectivity, and to lower the overpotentials
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16 required to produce these more reduced products.5-13 Although these efforts have resulted in an improvement in
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18 selectivity for both CH48 and various C2 products,5,7,10-12 overpotentials of > 500 mV are required to reach current
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20 densities > 1 mA cm-2 towards these products. The discovery of new families of electrocatalysts that do not contain
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copper, but produce highly reduced products from CO2 could be advantageous because CO2 reduction at non-copper
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surfaces might proceed via lower-energy pathways than those accessible on copper-containing surfaces. Therefore,
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such a discovery would offer not only alternatives to copper for the electrocatalytic reduction of CO2, but also the
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possibility that different constraints than those which govern the highly studied copper surface would govern the
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performance of the new catalysts. Such a system could provide a route to low-overpotential, tunable, and selective
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31 catalysts. Alloys and intermetallics are an attractive set of materials for this purpose as they not only provide
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33 multiple binding sites for reaction intermediates, but also provide materials with variable composition that may
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35 exhibit altered reactivity relative to their bulk counterparts.
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38 Theoretical14 and experimental13,15-24 investigations have recently focused on the development of new or improved
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40 electrocatalysts for CO2 (or CO) reduction based on the use of metal alloys. Much of the experimental work has
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42 focused on improving the selectivity and/or overpotential of Cu by forming alloys of Cu with other metals.15,17-24
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44 Non-copper-containing alloys such as AuPd16 or PdPt25 have been used to study the effects of composition on
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46 reactivity. Other non-copper-containing catalysts such as the III-V semiconductors GaP, GaAs, and InP have been
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48 reported to produce CH3OH,26-28 although the products, yields, and reproducibility of these reports have not been
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50 well established.29,30 Modified carbon supports such as metal-doped nitrogenated carbon,31 or nitrogen-doped
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52 nanodiamond32, as well as modified gold electrodes with self-assembled monolayers33 have also been shown to
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54 provide copper-free materials that can produce highly reduced products at a range of efficiencies and overpotentials.
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3 Ni-based alloys and intermetallics are a particularly promising route to explore alternatives to Cu-based materials,
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5 because Ni is the only other single metal reported to reduce CO2 to C2 products at potentials more negative than -1
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7 V vs. RHE, although Ag has also been shown to make small amounts of CH3CH2OH at -1.35 V vs. RHE.3,34
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9 Furthermore, Ni has been shown to have the second highest yields of CH4, albeit only at 0.5% Faradaic efficiency at
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11 highly reducing potentials, i.e. more negative than -1 V vs RHE.34 The synthesis of Ni-based intermetallics or alloys
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13 should offer the opportunity to modify the reactivity of Ni, possibly improving the activity of Ni for CO2 reduction.
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16 The work described herein follows, and was inspired by, theoretical and experimental literature on CO2
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18 hydrogenation. Specifically, SiO2-supported nanoparticles of Ni5Ga3, Ni3Ga, and NiGa are highly active for
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20 thermochemical, gas-phase CO2 hydrogenation to CH3OH at temperatures above ambient.35 These materials are
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stable intermetallic compounds with large ordering energies, and have calculated oxygen-adsorption energies close
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to the optimum benchmark methanol-producing catalyst (Cu/ZnO/Al2O3). A volcano curve has been developed to
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describe the theoretically predicted activity for some metals, including Ni and Ni intermetallics, for the
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thermochemical reduction of CO2. The volcano curve indicated that the oxygen-adsorption energy is a relevant
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parameter for predicting the catalytic activity. Experimental data were in accord with this suggestion, and the
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31 highest yields of ~ 0.25 mol h-1 were obtained for the production of CH3OH from the Ni5Ga3 phase. Based on these
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33 findings and conclusions, we have evaluated these NixGay materials for their electrocatalytic CO2 reduction activity.
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36 Experimental Section
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38 NiGa, Ni5Ga3, and Ni3Ga films were synthesized by a temperature-programmed reduction method adapted from
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40 Studt et. al.35 (See Supporting Information, SI). After annealing, scanning-electron microscopy (SEM) showed that
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42 the synthesized films consisted of aggregates of particles in the size range of 1-5 µm (Figure S1). X-ray diffraction
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44 (XRD) indicated that the materials were crystalline and of the desired phase (Figure 1), with all peaks assignable
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46 and consistent with the proposed composition (Table S1). X-ray photoelectron spectroscopy (XPS) showed that the
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48 films had Ni:Ga ratios of approximately 1:1, 3:1, and 5:3 for NiGa, Ni3Ga, and Ni5Ga3 respectively (Figure S2 and
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50 Table S2), with some surface Ni and Ga oxides resulting from exposure of the films to air during transfer to the
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52 ultra-high vacuum instrumentation.36
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54 The electrocatalytic activity of the films for CO2 reduction was evaluated in a modified two-compartment
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56 electrochemical cell, Figure S3. The cell was sealed to facilitate bulk electrolysis, and gas chromatography (GC)
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3 and nuclear magnetic resonance (NMR) spectroscopy were used to analyze the gaseous and liquid products,
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5 respectively, (see SI). Electrochemical surface area measurements were carried out similar to literature reports, and
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7 all electrodes were found to be only slightly roughened, Figure S4.37
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26 Figure 1. XRD data for the 3 different phases of nickel-gallium. The asterisk denotes signals from the quartz
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29 Results and Discussion
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31 Analysis of the electrolysis products using the synthesized NixGay phases as the catalysts indicated the formation
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33 of highly reduced products such as CH4, C2H4, C2H6, representing reductions that require the transfer of 8, 12, or 14
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35 electrons per molecule of product, respectively. Figure 2 and Figure S5 show the product distribution and rate of
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37 production of hydrocarbon products as a function of the electrode potential. The partial cathodic current density for
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39 CH4 production exceeded 140 µA cm-2 at -1.18 V vs. RHE, with Faradaic efficiencies > 2 % at potentials more
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41 negative than -0.48 V vs. RHE for NixGay films of varying stoichiometries. Partial cathodic current densities for the
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43 production of C2H6 reached 100 µA cm-2 at -1.18 V vs. RHE, while Faradaic efficiencies were 1.3% at -0.48 V for
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45 C2H6. The sum of the partial cathodic current densities towards all three hydrocarbons reached > 200 µA cm-2
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47 at -1.18 V. The balance of the current yielded H2 along with trace amounts of CO and CH3OH.
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35 Figure 2. Potential-dependent Faradaic efficiencies (solid lines) and current densities (dotted line) for CO2 reduction
36 in CO2-saturated 0.1M NaHCO3 (aq) to methane (triangles), ethane (exes) and ethylene (squares). (a) Hydrocarbon
37 production for the Ni5Ga3 phase of NixGay and (b) for Cu where data were taken from ref.4 in 0.1 M KHCO3.
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39 No electrocatalysts, other than Cu and to some extent Ni, have been reported to produce gaseous C2 products in
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41 any detectable yields from the electrochemical reduction of CO2 in an aqueous electrolyte solution.3,38,39 Other Cu-
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43 free materials, such as organic self-assembled monolayers,33 or nonmetallic electrocatalysts,32 have produced liquid
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45 C2 products at low overpotentials, while Ag40 and carbon nanotube confined metallic nanoparticles41 have been
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47 shown to produce liquid C2 products at large overpotentials. The production of gaseous C2 products allows for
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49 simpler product separation and collection. Moreover, the onset potential of -0.48 V vs. RHE for C2 and CH4
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51 production by any of the NixGay phases studied is approximately equal to that of single crystal Cu(100), to date the
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53 lowest overpotential catalyst for C2 production,42 while the onset potential for C2 and CH4 production are 250 mV
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55 and 300 mV, respectively, more positive than that reported for polycrystalline Cu, Figure 2.4 The NixGay films
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57 prepared in this work were not single crystals, nor were they optimized to maximize activity. Hence an appropriate
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3 comparison is with the behavior of polycrystalline copper catalysts, noting that opportunities remain for improving
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5 the catalytic activity of NixGay. For example, single crystals of NiGa could possibly allow increases in Faradaic
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7 efficiencies, partial cathodic current densities, and overpotentials, similar to improvements over polycrystalline
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9 copper realized using Cu single crystals as electrocatalysts. This optimization could yield higher current densities,
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11 making NixGay a potential candidate for CO2 reduction applications. At present, the partial current densities towards
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13 highly reduced products at large overpotentials are substantially higher on Cu electrodes than on NixGay.
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15 Polycrystalline copper and the nickel-gallium films evaluated in this work both produce CH4 and C2H4 from CO2.
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17 Because the two materials produce common products, the reactions at the two surfaces likely possess some
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19 mechanistic commonalities. Both theory43 and experiments42,44 have shown the reduction of CO2 to both CH4 and
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21 C2H4 on Cu involves the reduction of CO2 to CO as the first step in the formation of products. In the electrocatalytic
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23 reduction of CO2 by NixGay films, CO was detected at <0.01 % Faradaic efficiency by GC (Figure S6), suggesting
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25 that CO may be an intermediate on the three different NixGay phases. Hence, electrolyses were performed in
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27 phosphate buffer at pH = 7 under N2, CO2, or CO. Both CO2 and CO yielded CH4, C2H4, and C2H6 (Figure S7),
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29 whereas no significant amounts of CO2 reduction products, and only H2 production, were observed under N2. These
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31 observations suggest that CO is an intermediate in at least some pathways for conversion of CO2 into these highly
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33 reduced products on both the NixGay and Cu surfaces, and that related reaction pathways for CO2 reduction may be
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35 accessible even at surfaces of two different materials (NixGay and Cu).
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37 Cyclic voltammograms (CVs) were obtained in aqueous solution by sweeping the potential from 0 V vs. the open-
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39 circuit potential (OCP) to -0.68 V vs. RHE then back to +1.12 V vs. RHE, Figure 3. Under 1 atm of CO2, on the
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41 return scan the nickel-gallium films, Figure 3a, showed a small irreversible anodic wave at +0.54 V vs. RHE. For
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43 CVs performed on NixGay after CO2 reduction electrolysis, on the return scan the anodic wave, previously observed
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45 at +0.54 V vs. RHE, was ~3x larger than observed on pristine samples. After a second cycle, the anodic wave
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47 disappeared almost completely, Figure 3. To determine the nature of this wave, CVs were conducted under an
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49 atmosphere of CO in phosphate buffer at pH 7. Under CO, a large wave was observed at +0.55 V, close to the
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51 position of the peak under CO2 suggesting the wave corresponds to CO oxidation or another chemisorbed CO2 (or
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53 CO) reduction intermediate. The more negative onset potential and lower current densities for catalysis under CO is
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55 likely caused by chemisorbed CO binding to H2O or proton reduction sites, suppressing H2 evolution, and shifting
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57 the onset to more negative electrode potentials. Upon further cycling, the peak at + 0.55 V almost completely
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3 disappeared suggesting that the rebinding of CO is a relatively slow process and does not occur on the time scale of
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5 the CV. When the electrode was immersed in solution for 3-5 min, and another CV was performed, the anodic wave
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7 reappeared implying that CO eventually rebinds. This behavior contrasts with that of Ni under the same conditions
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9 (Figure 3b). Upon cycling a Ni electrode under CO, synthesized using the same method as the NiGa but excluding
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11 Ga, an anodic wave that did not disappear upon subsequent cycling was seen at +0.59 V (Figure 3b). This behavior
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13 indicates that CO more rapidly rebinds on Ni compared to NiGa. Literature reports have found CO is tightly bound
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15 on metallic Ni and its electrochemical oxidation is seen at similar potentials.45 The introduction of Ga into the Ni
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17 films appears to destabilize the Ni-CO interaction, slowing the poisoning of the surface and greatly improving yields
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19 of highly reduced products.
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53 Figure 3. Cyclic voltammetry for (a) Ni5Ga3 films and (b) Ni in 0.1 M K2HPO4 buffered to pH = 6.8 with KH2PO4
54 under CO2 and CO at 50 mV s-1 scan rate. The anodic wave peak potentials (grey vertical lines) are shown in the
55 inset, of (a) Ni5Ga3 peak at +0.55 V and in (b) Ni peak at +0.59 V.
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3 Isotopic labeling experiments were performed to confirm that the carbon in the products was derived from CO2.
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CO2 was used as the reactant gas, and gas chromatography mass/spectrometry (GCMS) rather than a thermal
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7 conductivity detector (TCD) was used to analyze the headspace. In this experiment, 100 µL headspace aliquots were
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9 taken every few hours and analyzed for isotopically labeled products. Figure S8 shows the resulting chromatograms
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11 for several important mass fragments. Mass fragment m/z=17 corresponds to 13
CH4+, m/z=29 corresponds to
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13 13
CH213CH+ fragments from both C2H4 and C2H6 that eluted at different times, and m/z=31 corresponds to 13C2H5+
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15 from 13C2H6. Other mass fragments corresponding to 13CH4, 13C2H4, and 13C2H6 were observed, and the estimated
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17 Faradaic efficiencies for the products were similar to when 12
CO2 was used. Additionally, over the >10 h
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19 electrolysis, no decrease in the rate of 13CH4, 13C2H4, or 13C2H6 production was observed.
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Several important differences are apparent between the reactivity of polycrystalline Cu and the NixGay films. The
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potential at which production of CH4 and C2H4 begins on the polycrystalline NixGay films is several hundred mV
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more positive than on polycrystalline Cu. In the potential range from -0.5 V to -0.85 V vs. RHE, polycrystalline Cu
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largely makes only the two-electron reduction products, CO and HCOO-, whereas the NixGay films form the 8, 12,
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and 14-electron reduction products, CH4, C2H4, and C2H6 respectively, in this potential range. Additionally, the
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31 onset potentials are nearly equivalent to the best-reported catalysts to date, single crystals of Cu and oxide derived
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33 Cu.6,12,46 The oxidation of chemisorbed CO is not observed on Cu surfaces, most likely due to its weaker interaction
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35 with CO compared to that of Ni. This stronger interaction with CO, along with the possibility of tuning its strength
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37 by modifying the composition of the intermetallic, make NixGay an interesting catalyst for electrochemical CO2
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39 reduction.
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42 When large overpotentials are applied (e.g. at -1.2 V vs RHE), many catalysts exhibit higher current densities
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44 than NiGa for the production of hydrocarbons. For example, at these potentials, Cu exhibits cathodic current
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46 densities of 6 mA/cm2 as compared to the 100 µA/cm2 cathodic current densities observed for the NixGay alloys
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48 reported herein.4,11,12,46 However, the onset potential of Ni-Ga is -0.48 V for highly reduced products, with cathodic
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50 current densities >100 µA/cm2 at -0.88 V vs. RHE. These materials improve on the state-of-the-art catalysts by
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52 lowering the overpotential required to generate highly reduced products with a polycrystalline electrode. Although
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54 current densities reported here are low, high surface area electrodes, or single crystal electrodes, could generate
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56 significantly higher rates of hydrocarbon production. Additionally, these materials provide a key link between CO2
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reduction electrocatalysts and theoretically predicted high temperature CO2 hydrogenation catalysts. This link could
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3 be exploited in future CO2 reduction electrocatalysts discovery studies. Because neither Ni nor Ga alone exhibit low
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5 overpotentials for CO2 reduction, this work strikingly shows that unique and tunable reactivity can be obtained for
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7 CO2 reduction by use of metal alloys rather than their pure phases, and thus opens up new lines of investigation for
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9 the discovery of CO2 reduction electrocatalysts.
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12 Supporting Information Available:
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14 Experimental procedures, catalyst characterization, detailed product analysis, and isotopic labeling experiments are
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16 included in SI. This material is available free of charge via the Internet at http://pubs.acs.org.
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19 Author Information
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Corresponding Author
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*Email: nslewis@caltech.edu
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26 Acknowledgements
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The authors would like to thank Prof. Matthew McDowell for his help with TEM and insightful discussions, Dr.
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Ivonne Ferrer for her help with GC setup and calibration, and Dr. Kimberly Papadantonakis for help editing. This
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material is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation
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Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-
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36 SC0004993. DAT recognizes a Graduate Research Fellowship from the National Science Foundation for support
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38 and the NWA. SAF acknowledges the Resnick Sustainability Institute at Caltech for a Postdoctoral Fellowship. JCC
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40 acknowledges support from the Department of Defense through the National Defense Science & Engineering
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42 Graduate Fellowship Program. NSL acknowledges support through the Multidisciplinary University Research
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44 Initiative (MURI) under AFOSR Award No. FA9550-10-1-0572. BSB acknowledges support through the Beckman
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46 Institute of the California Institute of Technology.
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