Preparation of ethylene/ethanol by electrocatalytic reduction of CO<sub>2</sub> with porous Cu<sub>2</sub>O cube

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Abstract Cu₂O catalyst can effectively electrochemically reduce carbon dioxide to multi carbon C₂₊ products. The composition and structure of the catalyst are important factors affecting the catalytic activity and selectivity of C₂₊ products. The purpose of this study was to investigate the effect of porous structure of Cu₂O catalyst on the selectivity of C₂ products for electrochemical reduction of CO₂. Firstly, Cu₂O cubes with porous structure (P-Cu₂O) were prepared by acid etching solid Cu₂O cubes (S-Cu₂O). SEM, TEM, XRD, XPS, CV and other characterization results show that the composition of S-Cu₂O and P-Cu₂O is the same, and they are mixed Cu valence: Cu⁰ and Cu⁺. The morphology of both is about 180 nm cube, while P-Cu₂O has irregular cavity porous structure. The electrochemical characterization results show that the electrochemical active surface area of P-Cu₂O is about 1.75 times that of S-Cu₂O, and the interfacial charge transfer resistance is lower than that of S-Cu₂O. Linear voltammetric scanning (LSV) results in N₂ and CO₂ atmosphere showed that P-Cu₂O had higher CO₂ catalytic activity. The electrocatalytic reduction of CO₂ was carried out under different potentials in the gas diffusion electrode flow cell system. The effects of porous structure on CO₂ reduction activity and C₂ product selectivity were investigated. The results showed that when the potential was -1.0 V vs. RHE and the electrolyte was 2 mol·L^-1 KOH, the CO₂ reduction product selectivity of P-Cu₂O was 37.7% (C₂H₄: 25.6%, C₂H₅OH: 12.1%), and the partial current density was 20.9 mA·cm^-2, which was ~28% higher than that of S-Cu₂O. The deep conversion of key intermediate ^*CO was calculated by ^*COR/[^*COR/CO_(g)]. The results showed that the deep conversion of ^*CO of P-Cu₂O was significantly higher than that of S-Cu₂O. In conclusion, the improvement of the selectivity of P-Cu₂O for C₂ products is attributed to: the porous structure makes P-Cu₂O have high active surface area, provides more CO₂ reduction active sites and promotes the formation of CO; the structure of the cavity is conducive to increase the local concentration of ^*CO and accelerate the dimerization of ^*CO to produce C₂ product. This study is of great significance for the design and development of Cu₂O based high-efficiency catalysts for electrocatalytic reduction of carbon dioxide to multi carbon products.

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	CAO Guangwei
	CAO Xuerui
	WANG Hua

Keywords： electroreduction CO₂ Cu-based catalysts porous structure C₂ products

Received 2022-05-01;

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CAO Guangwei, CAO Xuerui, WANG Hua.Preparation of ethylene/ethanol by electrocatalytic reduction of CO₂ with porous Cu₂O cube[J] Chemcial Industry and Engineering, 2023,V40(6): 15-27

[1] RUIZ-LÓPEZ E, GANDARA-LOE J, BAENA-MORENO F, et al. Electrocatalytic CO₂ conversion to C₂ products: Catalysts design, market perspectives and techno-economic aspects[J]. Renewable and Sustainable Energy Reviews, 2022, 161: 112329-112355
[2] 刘丹, 马哲, 刘梦晓, 等. CO₂的电驱动还原[J]. 化学工业与工程, 2021, 38(5): 1-12 LIU Dan, MA Zhe, LIU Mengxiao, et al. Electricity-driven CO₂ reduction[J]. Chemical Industry and Engineering, 2021, 38(5): 1-12(in Chinese)
[3] ZHONG Y, WANG S, LI M, et al. Rational design of copper-based electrocatalysts and electrochemical systems for CO₂ reduction: From active sites engineering to mass transfer dynamics[J]. Materials Today Physics, 2021, 18: 100354-100381
[4] YE W, GUO X, MA T. A review on electrochemical synthesized copper-based catalysts for electrochemical reduction of CO₂ to C₂₊products[J]. Chemical Engineering Journal, 2021, 414: 128825-128841
[5] MA W, XIE S, LIU T, et al. Electrocatalytic reduction of CO₂ to ethylene and ethanol through hydrogen-assisted C—C coupling over fluorine-modified copper[J]. Nature Catalysis, 2020, 3(6): 478-487
[6] ZHENG Y, VASILEFF A, ZHOU X L, et al. Understanding the roadmap for electrochemical reduction of CO₂ to multi-carbon oxygenates and hydrocarbons on copper-based catalysts[J]. Journal of the American Chemical Society, 2019, 141(19): 7646-7659
[7] XIAO C, ZHANG J. Architectural design for enhanced C₂ product selectivity in electrochemical CO₂ reduction using Cu-based catalysts: A review[J]. ACS Nano, 2021, 15(5): 7975-8000
[8] WANG Y, ZHU Y, NIU C. Surface and length effects for aqueous electrochemical reduction of CO₂ as studied over copper nanowire arrays[J]. Journal of Physics and Chemistry of Solids, 2020, 144: 109507-109513
[9] JUNG H, LEE S, LEE C, et al. Electrochemical fragmentation of Cu₂O nanoparticles enhancing selective C—C coupling from CO₂ reduction reaction[J]. Journal of the American Chemical Society, 2019, 141(11): 4624-4633
[10] CHEN Y, FAN Z, WANG J, et al. Ethylene selectivity in electrocatalytic CO₂ reduction on Cu nanomaterials: A crystal phase-dependent study[J]. Journal of the American Chemical Society, 2020, 142(29): 12760-12766
[11] FAN M, GARBARINO S, TAVARES A C, et al. Progress in the electrochemical reduction of CO₂ on hierarchical dendritic metal electrodes[J]. Current Opinion in Electrochemistry, 2020, 23: 145-153
[12] CHOU T, CHANG C, YU H, et al. Controlling the oxidation state of the Cu electrode and reaction intermediates for electrochemical CO₂ reduction to ethylene[J]. Journal of the American Chemical Society, 2020, 142(6): 2857-2867
[13] DUTTA A, RAHAMAN M, LUEDI N C, et al. Morphology matters: Tuning the product distribution of CO₂ electroreduction on oxide-derived Cu foam catalysts[J]. ACS Catalysis, 2016, 6(6): 3804-3814
[14] RASHID N, BHAT M A, INGOLE P P. Dendritic copper microstructured electrodeposits for efficient and selective electrochemical reduction of carbon dioxide into C1 and C2 hydrocarbons[J]. Journal of CO₂ Utilization, 2020, 38: 385-397
[15] LV J, JOUNY M, LUC W, et al. A highly porous copper electrocatalyst for carbon dioxide reduction[J]. Advanced Materials, 2018, 30(49): 1803111-1803119
[16] YANG K, KO W R, LEE J H, et al. Morphology-directed selective production of ethylene or ethane from CO₂ on a Cu mesopore electrode[J]. Angewandte Chemie (International Ed in English), 2017, 56(3): 796-800
[17] ZHUANG T, PANG Y, LIANG Z, et al. Copper nanocavities confine intermediates for efficient electrosynthesis of C3 alcohol fuels from carbon monoxide[J]. Nature Catalysis, 2018, 1(12): 946-951
[18] YU Z, WU S, CHEN L, et al. Promoting the electrocatalytic reduction of CO₂ on ultrathin porous bismuth nanosheets with tunable surface-active sites and local pH environments[J]. ACS Applied Materials & Interfaces, 2022, 14(8): 10648-10655
[19] GIRI S D, MAHAJANI S M, SURESH A K, et al. Electrochemical reduction of CO₂ on activated copper: Influence of surface area[J]. Materials Research Bulletin, 2020, 123: 110702-110710
[20] CAO X, CAO G, LI M, et al. Enhanced ethylene formation from carbon dioxide reduction through sequential catalysis on Au decorated cubic Cu₂O electrocatalyst[J]. European Journal of Inorganic Chemistry, 2021, 2021(24): 2353-2364
[21] TSAI Y H, CHIU C Y, HUANG M. Fabrication of diverse Cu₂O nanoframes through face-selective etching[J]. The Journal of Physical Chemistry C, 2013, 117(46): 24611-24617
[22] LI Q, LI M, ZHANG S, et al. Tuning Sn-Cu catalysis for electrochemical reduction of CO₂ on partially reduced oxides SnO_x-CuO_x-modified Cu electrodes[J]. Catalysts, 2019, 9(5): 476-489
[23] LI Z, YADAV R M, SUN L, et al. CuO/ZnO/C electrocatalysts for CO₂-to-C²⁺ products conversion with high yield: On the effect of geometric structure and composition[J]. Applied Catalysis A: General, 2020, 606: 117829-117836
[24] WU M, ZHU C, WANG K, et al. Promotion of CO₂ electrochemical reduction via Cu nanodendrites[J]. ACS Applied Materials & Interfaces, 2020, 12(10): 11562-11569
[25] ALTAF N, LIANG S Y, HUANG L, et al. Electro-derived Cu-Cu₂O nanocluster from LDH for stable and selective C₂ hydrocarbons production from CO₂ electrochemical reduction[J]. Journal of Energy Chemistry, 2020, 48: 169-180
[26] BO J, LI M, ZHU X, et al. Bamboo-like N-doped carbon nanotubes encapsulating M(Co, Fe)-Ni alloy for electrochemical production of syngas with potential-independent CO/H₂ ratios[J]. Frontiers of Chemical Science and Engineering, 2022, 16(4): 498-510
[27] ZHANG J, LUO W, ZVTTEL A. Crossover of liquid products from electrochemical CO₂ reduction through gas diffusion electrode and anion exchange membrane[J]. Journal of Catalysis, 2020, 385: 140-145
[28] RABIEE H, GE L, ZHANG X, et al. Gas diffusion electrodes (GDEs) for electrochemical reduction of carbon dioxide, carbon monoxide, and dinitrogen to value-added products: A review[J]. Energy & Environmental Science, 2021, 14(4): 1959-2008
[29] TOMBOC G M, CHOI S, KWON T, et al. Potential link between Cu surface and selective CO₂ electroreduction: Perspective on future electrocatalyst designs[J]. Advanced Materials (Deerfield Beach, Fla), 2020, 32(17): 190398-190422
[30] NITOPI S, BERTHEUSSEN E, SCOTT S B, et al. Progress and perspectives of electrochemical CO₂ reduction on copper in aqueous electrolyte[J]. Chemical Reviews, 2019, 119(12): 7610-7672
[31] WANG M, ZHANG S, LI M, et al. Facile synthesis of hierarchical flower-like Ag/Cu₂O and Au/Cu₂O nanostructures and enhanced catalytic performance in electrochemical reduction of CO₂[J]. Frontiers of Chemical Science and Engineering, 2020, 14(5): 813-823
[32] GUO W, SHIM K, ODONGO NGOME F O, et al. Highly active coral-like porous silver for electrochemical reduction of CO₂ to CO[J]. Journal of CO₂ Utilization, 2020, 41: 101242-101250
[33] 韩真真, 王华, 王静, 等. 多孔锡电极的制备及其用于CO₂电化学还原性能[J]. 化学工业与工程, 2016, 33(5): 8-13 HAN Zhenzhen, WANG Hua, WANG Jing, et al. Fabrication of porous tin and its application to electroreduction of CO₂[J]. Chemical Industry and Engineering, 2016, 33(5): 8-13(in Chinese)
[34] JIANG K, HUANG Y, ZENG G, et al. Effects of surface roughness on the electrochemical reduction of CO₂ over Cu[J]. ACS Energy Letters, 2020, 5(4): 1206-1214
[35] LIU B, CAI C, YANG B, et al. Intermediate enrichment effect of porous Cu catalyst for CO₂ electroreduction to C2 fuels[J]. Electrochimica Acta, 2021, 388: 138552-138559
[36] YANG P, ZHANG X, GAO F, et al. Protecting copper oxidation state via intermediate confinement for selective CO₂ electroreduction to C²⁺ fuels[J]. Journal of the American Chemical Society, 2020, 142(13): 6400-6408
[37] LYU Z, ZHU S, XIE M, et al. Controlling the surface oxidation of Cu nanowires improves their catalytic selectivity and stability toward C²⁺ products in CO₂ reduction[J]. Angewandte Chemie (International Ed in English), 2021, 60(4): 1909-1915
[38] WEEKES D M, SALVATORE D A, REYES A, et al. Electrolytic CO₂ Reduction in a flow cell[J]. Accounts of Chemical Research, 2018, 51(4): 910-918