中国科学技术大学曾杰团队报道了空心多壳结构铜上的纳米约束工程实现高效电催化C-C耦合。相关论文发表在2021年11月25日出版的《德国应用化学》。

纳米约束通过显著改变扩散动力学，以确保高局部浓度的C1中间体进行碳二聚，为促进电催化C-C耦合提供了一种很有前景的解决方案。

在有限元模拟结果的指导下，研究人员通过Ostwald熟化法合成了一系列壳数可调的Cu₂O空心多壳结构（HoMSs）。当用于CO₂电还原（CO2RR）时，原位形成的Cu HOMs显示出壳数与C2+产物选择性之间正相关，在中性电解质中，当转化率为513.7±0.7 mA cm^-2时，达到最大C2+法拉第效率77.0±0.3%。机理研究阐明了HoMSs的限制效应，即铜壳层的叠加导致腔体内局部CO吸附质的更高覆盖率，从而增强了二聚作用。

该研究工作为高效C-C偶联催化剂的精细设计提供了有价值的见解。

附：英文原文

Title: Nanoconfinement Engineering over Hollow Multi-Shell Structured Copper towards Efficient Electrocatalytical C-C coupling

Author: Chunxiao Liu, Menglu Zhang, Jiawei Li, Weiqing Xue, Tingting Zheng, Chuan Xia, Jie Zeng

Issue&Volume: 2021-11-25

Abstract: Nanoconfinement provides a promising solution to promote electrocatalytic C-C coupling, by dramatically altering the diffusion kinetics to ensure a high local concentration of C1 intermediates for carbon dimerization. Herein, under the guidance of finite-element method simulations results, a series of Cu2O hollow multi-shell structures (HoMSs) with tunable shell numbers were synthesized via Ostwald ripening. When applied in CO2 electroreduction (CO2RR), the in-situ formed Cu HoMSs showed a positive correlation between shell numbers and selectivity for C2+ products, reaching a maximum C2+ Faradaic efficiency of 77.0 ± 0.3% at a conversion rate of 513.7 ± 0.7 mA cm-2 in neutral electrolyte. Mechanism studies clarified the confinement effect of HoMSs that superposition of Cu shells leads to a higher coverage of localized CO adsorbate inside the cavity for enhanced dimerization. This work provides valuable insights for delicate design of efficient C-C coupling catalysts.

DOI: 10.1002/anie.202113498

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202113498