Department of Chemical Engineering, Norwegian University of Science and Technology, Sem saelands vei 4, Trondheim, 7034, Norway.
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao, Shandong, 266580, P. R. China.
Adv Sci (Weinh). 2023 Mar;10(8):e2205635. doi: 10.1002/advs.202205635. Epub 2023 Jan 19.
Fine constructing the chemical environment of the central metal is vital in developing efficient single-atom catalysts (SACs). Herein, the atomically dispersed Cu on the N-doped carbon is modulated by introducing CuP moiety to CuNC SAC. Through fine-tuning with another heteroatom P, the Cu SAC shows the superior performance of ethylene oxychlorination. The Cu site activity of Cu-NPC is four times higher than the P-free Cu-NC catalyst and 25 times higher than the Ce-promoted CuCl /Al O catalyst in the long-term test (>200 h). The selectivity of ethylene dichloride can be splendidly kept at ≈99%. Combined experimental and simulation studies provide a theoretical framework for the coordination of Cu, N, and P in the complex active center and its role in effectively catalyzing ethylene oxychlorination. It integrates the oxidation and chlorination reactions with superior catalytic performance and unrivaled ability of corrosive-HCl resistance. The concept of fine constructing with another heteroatom is anticipated to provide with inspiration for rational catalyst design and expand the applications of carbon-based SACs in heterogeneous catalysis.
精细构建中心金属的化学环境对于开发高效的单原子催化剂（SACs）至关重要。在此，通过引入 CuP 部分来调节氮掺杂碳上原子分散的 Cu，从而调制 CuNC SAC。通过与另一个杂原子 P 的精细调整，Cu SAC 显示出乙烯氧氯化反应的优异性能。在长期测试（>200 h）中，Cu-NPC 的 Cu 位活性是无 P 的 Cu-NC 催化剂的四倍，是 Ce 促进的 CuCl /Al O 催化剂的 25 倍。乙烯二氯乙烷的选择性可以极好地保持在 ≈99%。实验和模拟研究的结合为复杂活性中心中 Cu、N 和 P 的配位及其在有效催化乙烯氧氯化反应中的作用提供了理论框架。它将氧化和氯化反应与卓越的催化性能以及对腐蚀性-HCl 的无与伦比的耐受力相结合。用另一个杂原子精细构建的概念有望为合理的催化剂设计提供灵感，并扩展基于碳的 SAC 在多相催化中的应用。
