On-Surface Modification of Copper Cathodes by Copper(I)-Catalyzed Azide Alkyne Cycloaddition and CO2 Reduction in Organic Environments
On-Surface Modification of Copper Cathodes by Copper(I)-Catalyzed Azide Alkyne Cycloaddition and CO2 Reduction in Organic Environments
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DOI：
10.3389/fchem.2019.00860
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发表时间：
2019-12
影响因子：
5.5
通讯作者：
Ryota Igarashi;Ryuji Takeuchi;Kazuyuki Kubo;Tsutomu Mizuta;S. Kume
中科院分区：
文献类型：
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作者：
Ryota Igarashi;Ryuji Takeuchi;Kazuyuki Kubo;Tsutomu Mizuta;S. Kume
在这项研究中，将有机结构引入到铜阴极上，以诱导其电催化CO2还原活性的变化。通过铜基底阳极氧化激活的铜（I）催化叠氮-炔环加成反应（CuAAC）使单体前体聚合，将难溶有机聚合物作为薄层分布在铜表面上。所得结构具有铜表面原子，可用于参与CO2还原反应-与紧密接触的有机结构相当-并通过CO2还原过程稳定有机层的吸附。与传统的铸造改性体系相比，表面改性的铜阴极的CO2还原性能表现出改善的CO2还原超过H2释放。防止有机部分在金属表面上形成密集堆积的组装体对于促进铜原子上的CO2还原过程似乎是重要的。抑制H2的产生，高甲烷/乙烯比，和搅拌的影响表明，提高CO2还原活性不仅是一个结果，铜原子重组伴随着反复阳极氧化改性;有机层也显然起着重要的作用，在质子转移和CO2积累到铜表面。
In this study, organic structures were introduced onto copper cathodes to induce changes in their electrocatalytic CO2 reduction activity. Poorly soluble organic polymers were distributed onto the copper surface as a thin layer by polymerizing monomeric precursors via a copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) activated by anodization of the copper substrate. The resulting structure possesses copper surface atoms that are available to participate in the CO2 reduction reaction—comparable to close-contact organic structures—and stabilize the adsorption of organic layers through the CO2 reduction process. The CO2 reduction performance of the on-surface modified copper cathode exhibited improved CO2 reduction over H2 evolution compared with traditional cast modification systems. Preventing organic moieties from forming densely packed assemblies on the metal surface appears to be important to promote the CO2 reduction process on the copper atoms. The suppression of H2 evolution, a high methane/ethylene ratio, and the influence of stirring demonstrate that the improved CO2 reduction activity is not only a result of the copper atom reorganization accompanied by repeating anodization for modification; the organic layer also apparently plays an important role in proton transfer and CO2 accumulation onto the copper surface.