岛状铜上 Cu2O 活性位点的原位负载用于将硝酸盐高效电化学还原为氨,ACS Applied Materials & Interfaces

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岛状铜上 Cu2O 活性位点的原位负载用于将硝酸盐高效电化学还原为氨
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2022-01-25 , DOI: 10.1021/acsami.1c21691
Chaochen Wang ₁ , Fan Ye ₂ , Jianhua Shen ₁ , Kan-Hao Xue ₂ , Yihua Zhu ₁ , Chunzhong Li ₁

Affiliation

电化学硝酸盐还原反应（NO ₃ RR）为低温绿色氨合成提供了一条新途径。众所周知，铜及其氧化铜催化剂对 NO ₃ RR 具有选择性，尽管它们的氧化态在催化中所起的作用尚不完全清楚。在这里，我们发现原位电化学还原调节了铜的氧化态，促进了岛状铜上Cu _{2 O 活性位点的原位负载，并研究了氧化亚铜对硝酸盐还原的影响。}我们发现氨收率的提高（法拉第效率：98.28%，选择性：96.6%）与Cu _{2的生成密切相关}O，超过了当今可用的最先进催化剂的性能。通过 X 射线光电子能谱结合离子束溅射证明了材料的多层结构的存在。使用操作拉曼光谱，我们在施加的电位下监测了催化剂表面氧化物物质的还原过程。密度泛函理论 (DFT) 计算表明，Cu(I) 的稳定存在有效地促进了*HNOH 向*HNHOH 的转化。我们优化了DFT计算的模型构建，建立了相对更可靠的反应路径，为进一步了解NO ₃ RR的反应机理提供了有力支持。

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In Situ Loading of Cu2O Active Sites on Island-like Copper for Efficient Electrochemical Reduction of Nitrate to Ammonia

Electrochemical nitrate reduction reaction (NO₃RR) offers a new pathway for low-temperature green ammonia synthesis. It is widely known that copper and its copper oxide catalysts are selective for NO₃RRs, although the role played by their oxidation state in catalysis is not fully understood. Here, we found that in situ electrochemical reduction modulates the oxidation state of copper facilitating in situ loading of Cu₂O active sites on island-like copper, and investigated the effect of cuprous oxide on nitrate reduction. We found that the improvement of ammonia yield (Faraday efficiency: 98.28%, selectivity: 96.6%) was closely related to the generation of Cu₂O, which exceeded the performance of the state-of-the-art catalysts available today. The presence of a multilayer structure of the material was demonstrated by X-ray photoelectron spectroscopy combined with ion beam sputtering. Using operando Raman spectroscopy, we monitored the reduction process of the catalyst surface oxide species at the applied potential. Density functional theory (DFT) calculations indicated that the stable presence of Cu(I) effectively promotes the conversion of *HNOH to *HNHOH. We optimized the model building for DFT calculations and established relatively more reliable reaction paths, which provided a strong support for a further understanding of the reaction mechanism of NO₃RR.

更新日期：2022-02-09

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