铜泡沫对二氧化碳电化学还原的影响

Yuan-Gee Lee, Hui-Hsuan Chiao, Yu-Ching Weng, C. Lay
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摘要

与平面铜片不同,我们采用了泡沫铜来探索特定多孔结构对特定区域膨胀的影响。通过形态学研究,我们发现泡沫结构在特定位置上优于片状结构。在表面积的实际测量中,我们发现吸附剂会适当地聚集,从而导致传输路径受阻。由于聚结的吸附剂堵塞了泡沫深层的通道,因此低估了铜泡沫的具体位置。为了探索电还原的质子化过程,我们采用碳酸盐电解质作为对照组,与实验组碳酸氢盐电解质形成对比。在碳酸盐电解质中,经 XPS 光谱验证,主要中间产物是 CO 分子。在碳酸氢盐电解质中,中间体 CO 消失了;取而代之的是氢化成碳氢化合物中间体 CHO*。我们还发现,碳酸氢根离子抑制了泡沫铜深层结构中的电催化,因为它的高分子量中间产物在扩散路径中积聚。此外,我们还发现,当电极结构从片状转变为泡沫状时,电极上的氧化价从 Cu2O 上升到了 CuO。循环伏安图显示了一系列电还原后果:在低还原电位下,水分解释放出氢;在高还原电位下,产生甲酸和 CO;在高还原电位下,从 -1.4 V 到 -1.8 V 之间形成 CH4 和 C2H4。
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The Influence of the Cu Foam on the Electrochemical Reduction of Carbon Dioxide
Unlike the flat Cu sheet, we employed Cu foam to explore the specific porous effect on the expanding specific area. We found that the foam structure is superior to the sheet feature in the specific location from the morphology investigation. In the practical measurement of surface area, we found that the adsorbate could aptly agglomerate, resulting in a consequential block in the transport path. The specific location of the Cu foam was underestimated because the channels of the deep foam layer were blocked by the agglomerated adsorbate. To explore the protonation process of the electro-reduction, we adopted the carbonate electrolyte as the control group in contrast to the experimental group, the bicarbonate electrolyte. In the carbonate electrolyte, the primary intermediate was shown to be CO molecules, as verified using XPS spectra. In the bicarbonate electrolyte, the intermediate CO disappeared; instead, it was hydrogenated as a hydrocarbon intermediate, CHO*. The bicarbonate ion was also found to suppress electrocatalysis in the deep structure of the Cu foam because its high-molecular-weight intermediates accumulated in the diffusion paths. Furthermore, we found a promotion of the oxidation valence on the electrode from Cu2O to CuO, when the electrode structure transformed from sheet to foam. Cyclic voltammograms demonstrate a succession of electro-reduction consequences: at low reduction potential, hydrogen liberated by the decomposition of water; at elevated reduction potential, formic acid and CO produced; and at high reduction potential, CH4 and C2H4 were formed from −1.4 V to −1.8 V.
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