The investigation of highly efficient catalysts for the electrochemical reduction of carbon dioxide (ER-CO2) is the most critical challenge to commercialize conversion and utilization of CO2. Herein we propose a new and very promising catalyst, high crystallinity Sn crystals on Ni foam (Sn@f-Ni), for the electroreduction reaction of CO2 in potassium bicarbonate aqueous solution. The catalyst is fabricated in situ on a pretreated Ni foam substrate through a galvanostatic electrodeposition strategy. SEM and XRD demonstrate that high crystallinity Sn crystals, with an average size of 2-3 μm, evenly dispersed on the Ni foam support can be reproducibly obtained. Electrochemical measurements demonstrate that the Sn@f-Ni electrode at the deposition current of 15 mA exhibits superior performance in promoting the ER-CO2. Tafel measurements show that except for electrodes with a deposition current of 5 mA, the Tafel slopes of the other four electrodes are all above 100 mV dec-1, which is consistent with a rate-determining initial electron transfer to CO2 to form a surface adsorbed intermediate, a mechanism that is commonly invoked for metal electrodes. A stable composition of syngas can be obtained by electrolysis at -1.7 V potential (vs. Ag/AgCl), indicating that the Sn surface with high crystallinity conforms to the Heyrovsky-Volmer mechanism at a potential of -1.7 V. The ratio of CO and H2 generation was about 1 : 2, meaning it could be used as syngas for preparing some valuable fuels. This work provided an efficient method to convert the surplus CO2 to valuable syngas.
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