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超分子工程提高氧化铜电催化 CO 还原活性。

Supramolecular Engineering to Improve Electrocatalytic CO Reduction Activity of Cu O.

机构信息

Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, 210023, Nanjing, P. R. China.

Collaborative Innovation Center of Atmospheric Environment and Equipment Technology, Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, School of Environmental Science and Engineering, Nanjing University of Information Science & Technology, 210044, Nanjing, P. R. China.

出版信息

ChemSusChem. 2021 Apr 22;14(8):1847-1852. doi: 10.1002/cssc.202100431. Epub 2021 Mar 23.

Abstract

Electrochemical conversion of CO into value-added fuels and feedstocks attracts worldwide attention to mitigate energy and environmental problems. However, pursuing highly efficient electrocatalyst is still a challenge. In this study, cuprous oxide (Cu O) modified by cucurbit[6]urils (Q[6]), a kind of rigid macromolecule, is found to act as an efficient supramolecular inorganic nanocomposite catalyst for the electrochemical CO reduction reaction (CO RR) to C fuels. This catalyst affords a high total faradaic efficiency (FE ) of 93.96 % at a potential of -0.7 V vs. reversible hydrogen electrode and over 85 % from -0.6 to -0.9 V in 0.5 M KHCO , which is higher than that of pure Cu O (39.89 %). The enhancements in selectivity and activity for CO RR could significantly benefit from the strong CO adsorption capacity and hydrophobic nature of the cavity of Q[6], which simultaneously trap gaseous reactants near the catalyst to tune the local environment and limit the diffusion of water molecules. This study provides a strategy to adjust catalytic environments through supramolecular engineering.

摘要

电化学将 CO 转化为高附加值燃料和原料,引起了全世界对缓解能源和环境问题的关注。然而,追求高效的电催化剂仍然是一个挑战。在这项研究中,发现葫芦[6]脲(Q[6])修饰的氧化亚铜(CuO)作为一种高效的超分子无机纳米复合材料催化剂,可用于电化学 CO 还原反应(CO RR)生成 C 燃料。该催化剂在-0.7 V 相对于可逆氢电极的电位下,总法拉第效率(FE)高达 93.96%,在 0.5 M KHCO3 中,从-0.6 到-0.9 V 的电位下,FE 超过 85%,高于纯 CuO(39.89%)。CO RR 的选择性和活性的提高,主要得益于 Q[6]空腔的强 CO 吸附能力和疏水性,它可将气态反应物捕获在催化剂附近,以调节局部环境并限制水分子的扩散。这项研究提供了一种通过超分子工程来调节催化环境的策略。

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