Curvature-Dependent Selectivity of CO2 Electrocatalytic Reduction on Cobalt Porphyrin Nanotubes

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• 作者：Guizhi Zhu ; Yawei Li ; Haiyan Zhu ; Haibin Su ; Siew Hwa Chan ; Qiang Sun
• 刊名：ACS Catalysis
• 出版年：2016
• 出版时间：September 2, 2016
• 年：2016
• 卷：6
• 期：9
• 页码：6294-6301
• 全文大小：547K
• 年卷期：0
• ISSN：2155-5435

文摘

The selective electrocatalytic conversion of CO₂ into useful products is a major challenge in facilitating a closed carbon cycle. Here, on the basis of first-principles calculations combined with computational hydrogen electrode model, we report a curvature-dependent selectivity of CO₂ reduction on cobalt–porphyrin nanotubes which are thermodynamically stable, displaying tunable geometric and electronic properties with tube radius. We have found that CO production is preferred on nanotubes with larger diameter, and the predicted current density from microkinetics is larger than that on Au, the best metal catalyst for CO production from CO₂ electroreduction. In contrast, highly curved nanotubes with small radii tend to further catalyze CO reduction to CH₄ gas and the overpotential is much lower in comparison with the cases on Cu surfaces. The selectivity and the feasibility of synthesis make cobalt–porphyrin nanotubes very promising for CO₂ conversion.