抑制析氢反应是关键：在多孔 In55Cu45 催化剂上从 CO2 选择性电合成甲酸盐,ACS Applied Materials & Interfaces

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抑制析氢反应是关键：在多孔 In55Cu45 催化剂上从 CO2 选择性电合成甲酸盐
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2021-07-21 , DOI: 10.1021/acsami.1c07829
Motiar Rahaman ₁ , Kiran Kiran ₁ , Ivan Zelocualtecatl Montiel ₁ , Abhijit Dutta ₁ , Peter Broekmann ₁

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通过 CO ₂电还原直接电合成甲酸盐（表示为 CO ₂ RR）目前引起了极大的关注，因为甲酸盐是一种非常有价值的商品化学品，已经在广泛的应用中使用（例如，甲酸燃料电池、鞣革、橡胶生产、防腐剂和抗菌剂）。在此，我们展示了使用多孔 In ₅₅ Cu ₄₅从 CO ₂饱和碳酸氢盐水溶液通过 CO ₂ RR高选择性生产甲酸盐合金作为电催化剂。这种新型高表面积材料是通过利用动态氢气泡模板方法的电沉积工艺生产的。甲酸生产（FE的法拉第效率（FES）_甲酸盐）从未低于90％约400 mV的相对宽的电位窗口内，从-0.8到-1.2V，VS的可逆氢电极（RHE）。96.8% 的最大 FE_甲酸盐，对应于j_甲酸盐= -8.9 mA cm ^–2的部分电流密度，在 -1.0 V vs RHE 下产生。实验结果表明 CO ₂ RR 机制涉及稳定 In 上的 HCOO* 中间体。₅₅ Cu ₄₅合金表面结合有效抑制寄生析氢反应。使这种 CO ₂ RR 合金催化剂特别有价值的是它对降解和化学中毒的稳定性。在延长的 30 小时电解实验中，甲酸盐效率几乎保持不变，约为 94%，而纯 In 膜催化剂（参考基准系统）在类似的实验条件下显示甲酸盐效率从 82% 显着降低至 50%。应用相同位置扫描电子显微镜方法来证明所应用的 In ₅₅ Cu ₄₅的结构稳定性各种长度尺度的合金泡沫催化剂。我们证明了所提出的催化剂概念可以转移到技术上相关的载体材料（例如碳布气体扩散电极）而不会改变其优异的品质因数。

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Suppression of the Hydrogen Evolution Reaction Is the Key: Selective Electrosynthesis of Formate from CO2 over Porous In55Cu45 Catalysts

Direct electrosynthesis of formate through CO₂ electroreduction (denoted CO₂RR) is currently attracting great attention because formate is a highly valuable commodity chemical that is already used in a wide range of applications (e.g., formic acid fuel cells, tanning, rubber production, preservatives, and antibacterial agents). Herein, we demonstrate highly selective production of formate through CO₂RR from a CO₂-saturated aqueous bicarbonate solution using a porous In₅₅Cu₄₅ alloy as the electrocatalyst. This novel high-surface-area material was produced by means of an electrodeposition process utilizing the dynamic hydrogen bubble template approach. Faradaic efficiencies (FEs) of formate production (FE_formate) never fell below 90% within a relatively broad potential window of approximately 400 mV, ranging from −0.8 to −1.2 V vs the reversible hydrogen electrode (RHE). A maximum FE_formate of 96.8%, corresponding to a partial current density of j_formate = −8.9 mA cm^–2, was yielded at −1.0 V vs RHE. The experimental findings suggested a CO₂RR mechanism involving stabilization of the HCOO* intermediate on the In₅₅Cu₄₅ alloy surface in combination with effective suppression of the parasitic hydrogen evolution reaction. What makes this CO₂RR alloy catalyst particularly valuable is its stability against degradation and chemical poisoning. An almost constant formate efficiency of ∼94% was maintained in an extended 30 h electrolysis experiment, whereas pure In film catalysts (the reference benchmark system) showed a pronounced decrease in formate efficiency from 82% to 50% under similar experimental conditions. The identical location scanning electron microscopy approach was applied to demonstrate the structural stability of the applied In₅₅Cu₄₅ alloy foam catalysts at various length scales. We demonstrate that the proposed catalyst concept could be transferred to technically relevant support materials (e.g., carbon cloth gas diffusion electrode) without altering its excellent figures of merit.

更新日期：2021-08-04

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