Laser-Prepared CuZn Alloy Catalyst for Selective Electrochemical

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Laser-Prepared CuZn Alloy Catalyst for Selective Electrochemical Reduction of CO2 to Ethylene Yi Feng, Zhe Li, Hui Liu, Cunku Dong, Jiaqi Wang, Sergei A. Kulinich, and Xi-Wen Du Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.8b02837 • Publication Date (Web): 19 Oct 2018 Downloaded from http://pubs.acs.org on October 20, 2018

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Laser-Prepared CuZn Alloy Catalyst for Selective Electrochemical Reduction of CO2 to Ethylene

Yi Feng,† Zhe Li,† Hui Liu,† Cunku Dong, † Jiaqi Wang, † Sergei A. Kulinich,*‡ and Xiwen Du*†

†

Institute of New Energy Materials, School of Materials Science and Engineering, Tianjin

University, Tianjin 300072, China

‡

Research Institute of Science and Technology, Tokai University, Hiratsuka, Kanagawa 259-1292,

Japan

ABSTRACT: Laser ablation in liquid was used to prepare homogenous copper-zinc alloy catalysts that exhibited excellent selectivity for C2H4 in CO2 electro-reduction, with Faradaic efficiency values as high as 33.3% at a potential of -1.1 V (vs. RHE). The high proximity of Cu and Zn atoms on the catalyst’s surface was found to facilitate both the stabilization of the CO* intermediate and its transfer from Zn atoms to their Cu neighbors, where further dimerization and protonation occurs to give rise to a large amount of ethylene product. The new homogenous nanocatalyst, along with the mechanism

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proposed for its performance, may be very helpful for in-depth understanding of processes related to carbon dioxide electro-reduction and conversion.

KEYWORDS: CO2 electro-reduction, alloy catalyst, ethylene, laser ablation in liquid

Electrochemical reduction of CO2 into fuels is a promising strategy to mitigate both fossil energy shortage and CO2 emission problems, in which the key point is developing efficient catalysts with high yield of high-energy-density products.1-5 The electrocatalysts commonly used for CO2 reduction are transition metals and their compounds, among which those based on Ag and Au are highly selective to produce carbon monoxide;6-8 Co and Pb were reported to have good selectivity for formic acid;9,10 Zn showed good performance for CO, HCOOH and syngas at different overpotential;11-15 and Cu is the most effective catalyst capable of producing various products including hydrocarbons (such as methane, ethylene and ethanol).16-18 At the same time, Cu catalysts were found to suffer the problem of poor selectivity, which resulted in their rather low


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Faradaic efficiency (FE) for hydrocarbons with high energy density.16-18, Therefore, development of novel catalysts with high FE for hydrocarbons is a very challenging and timely task. Since CO2 reduction involves multiple electron and proton coupling steps, the reaction pathways, as well as the final products, depend on the binding energy of key intermediates on the catalyst surface.19 Therefore, the selectivity of products can be modified and improved by manipulating the morphology, surface state, and chemical and phase composition of the catalyst.16,20 Recently, bimetallic catalysts have attracted much attention, as their electronic structure (and thus binding energy) can be easily modified by varying composition21,22, which may lead to remarkable enhancement in product selectivity.23 For instance, Rasul et al. reported a bimetal Cu-In catalyst that converted CO2 into CO with FE as high as 90% at -0.5 V vs. RHE.24 In another study, Guo and co-workers prepared Cu3Pt alloy with good selectivity toward CH4.25 Of all metallic catalysts for CO2 reduction, those based on Cu and Zn are both eco-friendly and cost-efficient. Nanomaterials of Zn are known for their high selectivity to CO,12-15 while Cu nanostructures were found to be capable of converting CO* intermediate to hydrocarbon products.16-18 Hence, it was expected that a bimetallic CuZn nanomaterial with proper morphology would give rise to hydrocarbons via “relay catalysis” of its Zn and Cu components. More specifically, CO intermediates could firstly form at its Zn sites, after which would be transferred to


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adjacent Cu sites where they would further evolve into hydrocarbon products. In this scenario, Cu and Zn atoms should be distributed homogenously within catalyst nanoparticles (NPs) in order to facilitate the CO transfer. Several previous works reported on CuZn alloy catalysts prepared by electroplating or vacuum sealing evaporation method, which resulted in CO or HCOOH as the main product (i.e., with much lower energy density).26-30 The finding could probably be attributed to the use of Zn-rich alloys with much lower Cu contents, which decreased the adsorption strength for both surface CO2* and CO* species.28 Some Cu and Cu-Zn bimetal electrocatalysts, along with their activity toward ethylene, are listed in Supporting Information (Table S1). Recently, oxide-derived metals, such as Cu and Ag, were proved to have good catalytic properties toward CO2 electro-reduction.31-33 However, copper oxide and zinc oxide are not mutually soluble, and it is a big challenge to obtain homogenous copper-zinc oxides and then reduce them into homogenous CuZn nanocatalyst via oxide-derived processes.34,35 Pulsed laser ablation in liquid (PLAL) is a simple and easy-to-use technique for NP preparation in which laser pulses heat solid target immersed into liquid medium and produce various NPs with unique morphology and chemistry.36-40 In the present work, for the first time, we adopt this technique to prepare a homogenous CuZn catalyst. More specifically, we employed a nanosecond pulsed laser to ablate a CuZn alloy target immersed in water, which led to mixed CuZn oxide (CuZnO) NPs


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with homogenous elemental distribution. The prepared CuZnO NPs were then reduced to a homogenous CuZn nanocatalyst via electro-reduction, as illustrated in Fig. 1. The reduced homogenous CuZn catalyst was found to show attractive catalytic selectivity to ethylene, achieving FE values as high as 33.3% at the potential of -1.1 V (vs. RHE). The homogenous distribution of Cu and Zn atoms thus makes it possible for CO* produced by Zn sites to be transferred easily to the nearest Cu sites where it converts to C2H4. At the same time, the abundant CO* makes it easier to form C2 rather than C1 products, while the proximity of Zn atoms can weaken the adsorption of C2H4 on their Cu neighbors, in which both components reach synergy and contribute to improved catalytic activity and selectivity.


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Figure 1. Schematic illustration of preparing NPs of CuZnO, Cu2O and ZnO by laser ablation in water followed by their subsequent electro-reduction to Cu-Zn, Cu and Zn NPs. The atomic ratio of Cu-Zn was 4:1.

Figure 2a displays transmission electron microscopy (TEM) images of the CuZnO NPs where spherical NPs are seen to be from 7 to 15 nm in diameter (see also Fig. S1). High resolution TEM (HRTEM) images showed polycrystalline structure in such CuZnO NPs (Fig. 2b), suggesting their polycrystalline structure which was also confirmed by Fast Fourier Transform (FFT) pattern in Fig. 2b (inset). According to energy-dispersive X-ray spectroscopy (EDS) mapping, Cu, Zn and O atoms were uniformly distributed in the CuZnO NPs (Figs. 2c). The X-ray diffraction (XRD) pattern in Fig. 2d implies that Zn atoms are embedded into the Cu2O lattice, which makes the peaks of the latter phase somewhat wider. Importantly, after electro-reduction at -1.6 V (vs. RHE), Cu and Zn atoms were found to be still well dispersed in the NPs (Fig. S2).


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Figure 2. (a) TEM image, (b) HRTEM image with FFT pattern as insert, and (c) HAADF image and EDSmapping of CuZnO NPs. (d) XRD patterns, (e, f) XPS spectra of Cu2O/ZnO, ZnO, Cu2O and CuZnO NPs.

For comparison, we also performed laser ablation of Cu and Zn targets in water. TEM, XRD, EDS, and X-ray photoelectron spectroscopy (XPS) analyses indicate that the products were pure Cu2O and ZnO NPs, respectively (Figs.2d-2f and Figs.S3-S5). The as-prepared Cu2O and ZnO NPs were then mixed with the atomic Cu/Zn ratio of 4:1 to obtain a ZnO/Cu2O sample (Fig. S6). After electro-reduction, the pure ZnO and Cu2O products turned into pure Zn and Cu NPs, while the mixed ZnO/Cu2O sample transformed into a phase-separated Cu-Zn mixture rather than a homogenous structure, see XRD patterns in Fig. S7. The electrochemical reduction of CO2 was performed under atmospheric conditions in CO2-saturated 0.1 M KHCO3 aqueous solution (Fig. S8). The product FE values observed on the CuZn alloy and Cu-Zn mixture, as well as the performance of the former catalyst over time, are presented in Fig.3 (see more details in Table S2 and Figs. S9-S11). The results permit to conclude that C2H4 was selectively produced on the CuZn alloy catalyst (Fig.3a). As the potential became more negative, the FE for C2H4 reach as high as 33.3 % at -1.1 V (vs. RHE) (see also Fig. S11a). Note that this FE value was not achieved on any other catalysts tested in this study. (Fig. 3c) Under the same conditions, the main products obtained over the Cu-Zn mixture were CO and H2, with only small amounts of C2H4 and C2H5OH detected (Fig. 3b). At the same time, the mono-metallic Cu catalyst generated a wide range of products (C2H5OH, C2H4, CH4, and C2H6 being the major ones, Fig. S11c) and the Zn NPs demonstrated a good catalytic selectivity to CO (Fig. S11d). Figure 3c compares the FE of C2H4 achieved on different catalysts (CuZn alloy, Cu-Zn mixture and pure Cu),


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showing that the homogenous CuZn material has a significant selectivity to C2H4 in comparison with the Cu-Zn mixture counterpart. Moreover, for the CuZn alloy catalyst, the increase in FE of C2H4 was accompanied with the simultaneous decrease in FE of CO (Fig. 3a), suggesting that CO* was an important intermediate species during CO2 electro-reduction to C2H4 on this catalyst.

Figure 3. Electro-reduction performance of the catalysts. FE values of the products on (a) CuZn alloy and (b) Cu-Zn mixture catalysts. (c) FE values of ethylene and carbon monoxide obtained on CuZn alloy (orange line), Cu-Zn mixture (purple line) and Cu NPs (sky-blue line). (d) Total current density and FE of ethylene and carbon monoxide on CuZn alloy catalyst at -1.1 V (vs. RHE) after electroreduction for 15h.

The stability of catalytic performance of the novel CuZn catalyst over time was evaluated as a next step. Figure 3d presents how its total current density (gray symbols), as well as FE for C2H4 (orange symbols) and CO (purple symbols) behaved over as long as 15 h of non-stop process. All the three trends are well seen to demonstrate no noticeable decline, indicating that the catalyst was stable and did not degrade during the experiment.


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The above results imply that a homogenous CuZnO material was produced via the PLAL approach, which then upon electro-reduction provided homogeneous CuZn alloy NPs, and the latter reduced NPs demonstrated a high catalytic selectivity for C2H4. In parallel to the main product discussed in the present work (CuZn NPs with the Cu/Zn ratio of 4:1), we also prepared similar materials with varied Cu/Zn ratios (1:1, 3:1, 5:1 and 7:1) to see the effect of composition on the catalyst’s activity (Fig. S12). The best catalytic performance with the highest FE of C2H4 was documented for the sample with the Cu/Zn ratio of 4:1 (Fig. S13). It is believed that a relatively high fraction of surface Cu atoms is favorable for C-C coupling, which is why C2H4 was selectively produced on the homogenous CuZn alloy with its Cu/Zn ratio ~4:1. When the fraction of surface Cu atoms was reduced, the catalyst tended to perform similar to metallic Zn, generating CO as its major product. Finally, at relatively higher fractions of Cu, the FE of C2H4 decreased as the catalyst began gradually to behave similar to pure metallic Cu (which is known for its poor selectivity). At the same time, the Cu-Zn mixture materials were found to show low selectivity for hydrocarbons (see Table S1 and Fig.S15). This could be due to a much lower number of adjacent Cu and Zn atoms in such mechanically mixed hybrid Cu-Zn nanomaterials. To verify this assumption, we prepared a series of such mixed Cu2O/ZnO nanomaterials with their Cu/Zn ratios varying as 1:1, 3:1, 4:1, 5:1 and 7:1 (Fig. S14). Compared with the homogeneous CuZn alloy, there is a much smaller number of adjacent Cu and Zn atoms on the surface of such mechanically mixed nanomaterials. That is why, changes in the Cu/Zn ratio of these materials are seen in Fig. S15 to have a much stronger effect on their products. At lower ratios of Cu/Zn (below 4:1), CO was the major product, similar to the case of the CuZn alloy catalyst. This may be due to a stronger adsorption of CO2 on Zn atoms, which leads to a more probable desorption of CO* species in the form of CO rather than their transfer to neighbor Cu atoms, the latter being less available in this case. Again, similar to the homogeneous CuZn alloy, when the Cu/Zn ratio in the mixture materials was as high as 7:1, the number of products increased. However, the homogenous CuZn alloy with


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the same ratio still showed a much higher selectivity to C2H4 (see Fig. S13e). This further stresses out the importance of the homogenous structure for selective CO2 conversion to C2H4. Based on the previous studies, Zn atoms are known to be active sites where CO* species are formed.34,

42-44

And indeed, our PLAL-produced (and then electro-reduced) Zn NPs showed an

excellent selectivity for CO (Fig. S11b). It is also known that CO is the key intermediate in the process of CO2 electro-reduction45,46, and the binding strength of the CO* intermediate has a significant effect on the selectivity of hydrocarbons produced over the surface of pure Cu47,48. Copper atoms were reported to have a stronger adsorption energy of the CO* intermediate, if compared with their Zn counterparts. As a result, this facilitates further formation of hydrocarbons, which was confirmed by abundant products generated on the mono-metallic Cu NPs electroreduced from PLAL-generated Cu2O NPs (Fig. S11a). Some previous work suggested that the CO* dimerization has a low barrier at high surface coverage of this species, and that is why C2H4 is often produced on Cu49-51. Yeo and co-workers used both experiment and DFT simulations, concluding that a high surface coverage of CO* is key for the selective formation of C2H4. Recent reports also proved that the introduction of Ag could increase the chance of CO formation and further formation of various C2 products52-54. For the homogenous CuZn catalyst reported in this study, we believe that the Zn sites were responsible for generation of a large number of CO species. Then, the CO* intermediate could be easily transferred to their Cu neighbors34, where the dimerization of such CO* species facilitated C2H4 production49. As shown in Fig. 4, once CO2 molecules approach the catalyst surface, they can be captured by Zn atoms, where they are first reduced to COOH* and then to CO*. Yet, the reduced intermediate CO* is not strongly bound to the Zn site and tends to be transferred to adjacent Cu sites where its adsorption is stronger.34 The high surface coverage with CO*, along with the rather weak nature of the Cu-CO* bonding, are believed to reduce the barrier of CO* dimerization51. It was also reported that the dimerization process is geometry-sensitive, as charge transfer on the catalyst surface is dependent on surface atom arrangement51,55. The homogeneous Cu and Zn distribution realized in


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the laser- prepared (and then electro-reduced) CuZn alloy NPs is favorable for proper molecular spacing and small steric hindrance effect of CO* species adsorbed on their active Cu sites, thus lowering the barrier of dimerization and promoting the formation of C2 products. After dimerization, as depicted in Fig.4, a series of protonation processes proceeds on Cu atoms, which converts the dimerized COCOH species into CCO, OC2H3 and finally C2H4.

Figure 4. Mechanism of catalytic CO2 reduction on the surface of metallic Cu-Zn NPs.

In summary, for the first time, we prepared CuZn alloy catalysts with very high surface homogeneity, for which pulsed laser ablation in water was used followed by electro-reduction of as-prepared homogenous oxide nanomaterials into alloy nanostructure. The novel material, when used for CO2 reduction, demonstrated good selectivity for C2H4 product, reaching Faradaic efficiency values as high as 33.3%. We demonstrate that the very homogeneous surface distribution of Cu and Zn atoms is responsible for the material’s catalytic performance favorable for C2H4 production. Namely, the high proximity of Cu and Zn


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atoms on the catalyst’s surface provides both the stabilization of the CO* intermediate and its transfer from Zn atoms to their Cu neighbors, where further dimerization and selective formation of ethylene molecule occurs.

ASSOCIATED CONTENT Supporting Information. Materials, detailed synthetic procedures, characterization methods and additional experimental results. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Authors * E-mail: [email protected] * E-mail: [email protected]

ORCID Cunku Dong: 0000-0001-8277-6707 Sergei A. Kulinich: 0000-0002-1365-9221 Xiwen Du: 0000-0002-2811-147X

ACKNOWLEDGMENTS


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This work was supported by the National Basic Research Program of China (2014CB931703), the Natural Science Foundation of China (Nos. 51671141, 51571149, and 51471115)

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SYNOPSIS TOC


Laser-Prepared CuZn Alloy Catalyst for Selective Electrochemical

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