清华大学李亚栋团队报道了红磷上原子分散金辅助C-C偶联用于CO₂光还原成C2H6。相关研究成果发表在2022年11月22日出版的国际知名学术期刊《美国化学会杂志》。

单原子催化剂在将CO₂光催化转化为C2产物方面表现出巨大潜力，但气态多碳烃产物的生成仍然具有挑战性。以前，单个原子的载体由多个元素组成，这使得C–C耦合变得困难，因为单个原子位点的配位环境是多样的且难以控制。

该文中，研究人员通过在红磷上植入Au单原子（Au1/RP）来控制C–C耦合，红磷是由单一元素组成的具有均匀结构、较低电负性和更好吸收CO₂能力的载体。Au单核附近富含电子的磷原子可以作为CO₂活化的活性位点。Au单原子可以有效降低C–C偶联的能量势垒，促进C2H6形成的反应动力学。值得注意的是，Au1/RP的C2H6选择性和转换频率分别达到96%和7.39 h^–1，而无需牺牲剂，这几乎是迄今为止C2化学合成的最佳光催化剂。

该研究将为CO₂转化为C2产物的高效光催化剂的设计提供新的思路。

附：英文原文

Title: Atomically Dispersed Au-Assisted C–C Coupling on Red Phosphorus for CO2 Photoreduction to C2H6

Author: Honghui Ou, Guosheng Li, Wei Ren, Boju Pan, Guanghui Luo, Zhuofeng Hu, Dingsheng Wang, Yadong Li

Issue&Volume: November 22, 2022

Abstract: Single-atom catalysts have exhibited great potential in the photocatalytic conversion of CO2 to C2 products, but generation of gaseous multi-carbon hydrocarbon products is still challenging. Previously, supports of a single atom consist of multiple elements, making C–C coupling difficult because the coordination environment of single-atom sites is diversified and difficult to control. Here, we steer C–C coupling by implanting an Au single atom on the red phosphorus (Au1/RP), support with uniform structure composed of a single element, lower electronegativity, and better ability to absorb CO2. The electron-rich phosphorus atoms near the Au single atoms can function as active sites for CO2 activation. The Au single atom can effectively reduce the energy barrier of C–C coupling, boosting the reaction kinetics of the formation of C2H6. Notably, the C2H6 selectivity and turnover frequency of Au1/RP reach 96% and 7.39 h–1 without a sacrificial agent, respectively, which almost represents the best photocatalyst for C2 chemical synthesis to date. This research will provide new ideas for the design of high-efficiency photocatalysts for CO2 conversion to C2 products.

DOI: 10.1021/jacs.2c09424

Source: https://pubs.acs.org/doi/10.1021/jacs.2c09424