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Catalysts 2020, 10, 1287 9 of 25 Moreover, metal-free nitrogen-doped carbon materials have also been reported recently to be capable of ethanol production from CO2. Table 2. Summary of the main electrocatalysts with the ability to convert CO2 into ethanol. Electrocatalyst Cu nanowire (7 μm in length) Nanoporous Cu Oxide-derived Cu foil Electro-redeposited Cu Cu nanocubes Cu nanocubes with exposed (100) facets Grain-boundary-rich Cu Cu2O film 3D dendritic Cu-Cu2O Multihollow Cu2O Cu-on-Cu3 N B-doped oxide-derived-Cu B-doped Cu Cu2S-Cu-V core-shell nanoparticles F-modified Cu Ce(OH)x -doped-Cu Polycrystalline Cu electrode with N-tolylpyridinium chloride additive Cu electrode with N,N’-ethylene-phenanthrolinium dibromide 1-octadecanethiol-modified dentritic Cu electrode FeTPP[Cl]-functionalized Cu electrode Cu63.9 Au36.1 Cu55 Ag45 CuAg alloy wire CuAg poly Cu wire Cu85Ag15 foam CuPd Cu4 Zn ZnO@CuO-derived CuZn ZnO@CuO-derived CuZn Cu2O nanoparticles/carbon Cu nanoparticles/N-doped carbon HKUST-1-derived Cu/C N-doped porous carbon-supported Cu nanoparticles N-doped graphene quantum dots Cylindrical mesoporous N-doped carbon Hierarchical porous N-doped carbon B, N-co-doped nanodimond 3.1.1. Modified Cu Electrolyte 0.1 M KHCO3 1 M KOH (flow cell) 0.1 M CsHCO3 0.1 M KHCO3 0.1 M KHCO3 0.25 M KHCO3 1 M KOH (flow cell) 0.1 M KHCO3 0.1 M KCl 2 M KOH (flow cell) 0.1 M KHCO3 0.1 M KHCO3 0.1 M KCl 1 M KOH (flow cell) 1 M KOH (flow cell) 1 M KOH (flow cell) 0.1 M KHCO3 0.1 M KHCO3 0.1 M CsHCO3 1 M KHCO3 (flow cell) 0.5 M KHCO3 0.1 M KHCO3 1 M KOH (flow cell) 1 M KOH (flow cell) 1 M KOH (flow cell) 0.5 M KHCO3 1 M KOH (flow cell) 0.1 M KHCO3 1 M KOH (flow cell) 0.1 M KHCO3 0.1 M KHCO3 0.1 M KHCO3 0.1 M KHCO3 0.2 M KHCO3 1 M KOH (flow cell) 0.1 M KHCO3 0.1 M KHCO3 0.1 M NaHCO3 Potential (V vs. RHE) −1.1 −0.67 −1.0 −1.1 −1.1 −0.95 −1.3 −0.99 −0.4 −0.61 −0.95 −1.05 −1.1 −0.92 −0.54 −0.7 −1.1 −1.07 −1.1 −0.82 −0.41 −1.4 −0.7 −0.75 −0.7 −1.0 −0.75 −1.05 −0.68 V −1.15 −1.1 −1.2 −0.5 −1.05 −0.75 −0.56 −0.56 −1.0 EtOH FE Ref. (%) 4 [52] 17 [53] 18 [54] 12 [55] 10 [56] 13 [57] 32 [58] 16 [45] 32 [59] 27 [60] 19 [61] 20 [62] 27 [63] 25 [64] 16 [65] 43 [66] 31 [67] 15 [68] 17 [69] 41 [70] 12 [71] 25.5 [72] 25 [73] 20 [73] 27 [73] 33.7 [74] 15 [75] 29.1 [44] 41.4 [76] 32 [76] 12 [77] 63 [41] 35 [78] 64.6 [79] 16 [80] 77 [81] 78 [82] 93.2 [83] The morphology and structure of metallic Cu catalyst significantly affect the product distribution and selectivity of CO2 reduction. For example, the in situ deposited Cu nanodendrites exhibited increased selectivity toward the formation of ethylene compared to the polycrystalline Cu [84]. It is known that the Cu (111) surfaces preferentially catalyze the methane formation, while the Cu (100) surfaces favor the formation of ethylene [40]. Hence, several strategies, such as controlling morphology, size or the exposed facet of the Cu catalyst, could be employed to attempt to produce the desired ethanol from CO2 reduction. For instance, Smith and his co-workers prepared Cu nanowire arrays by electroreduction of Cu(OH)2 and CuO nanowire arrays on Cu foil substrates [52]. On these electrocatalysts, the selectivity of hydrocarbon products at a fixed potential can be tuned by alteringPDF Image | Advances in Clean Fuel Ethanol Production from CO2 Reduction
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