浙江工业大学化学工程学院庄桂林课题组的一项最新研究提出了多通道光子激发C-C耦合在混合水/乙腈溶剂中的CO₂还原。相关论文于2025年2月10日发表在《德国应用化学》杂志上。

本文采用从头算非绝热分子动力学（NAMD）模拟和密度泛函理论（DFT）计算相结合的方法，从理论上揭示了Co-负载单层黑磷（BP）催化剂Co@BP光场下C-C耦合的详细动态过程。特别地，Co@BP具有优异的光触媒性能：稳定性高、光生载体寿命长、还原性强。热力学结果表明，在无溶剂条件下对HCOOH （Ea = 0.29 eV）的选择性为99.99%，而在溶液条件下对CH2CH2 （Ea=0.33eV）的选择性为99.34%，两者的催化性能存在显著差异。慢生长MD模拟结果表明，水/乙腈混合溶剂（H₂O/ACN）有利于C²⁺产物的形成，且H₂O/ACN混合溶剂的最佳配比（1:9）有利于CO₂转化为CH₂CH₂。在光照射下，该研究组发现多通道光子使吸附的CHO*与附近活性位点的CHO偶联，进一步在溶液中形成C2中间体。这项工作强调了反应介质对光生载体动力学的重要性，并提供了光催化CO₂转化中调节产物选择性的策略。

据了解，设计用于二氧化碳还原反应（CO₂RR）的有效光催化剂需要对实际条件下的动态光催化机制有精确的理解。溶剂，光场)。

附：英文原文

Title: Multichannel Photon-Stimulated C-C Coupling for CO₂ Reduction in a Mixed Water/Acetonitrile Solvent

Author: Fu-Li Sun, Cun-biao Lin, Zhi-rui Luo, Qing Chen, Wen-xian Chen, Gui-lin Zhuang

Issue&Volume: 2025-02-10

Abstract: Designing effective photocatalysts for carbon dioxide reduction reaction (CO2RR) requires a precise understanding of the dynamically photocatalytic mechanism under real conditions (e.g. solvent, light field). Herein, we coupled ab-initio non-adiabatic molecular dynamics (NAMD) simulation and density functional theory (DFT) calculation to theoretically reveal the detailed dynamic process for C-C Coupling under light field on Co-supported monolayer black phosphorus (BP) catalyst Co@BP. Specially, Co@BP features excellent property for photocatalyst: high stability, long-lived photogenerated carriers and stronger reducing ability. Thermodynamically, it shown that a dramatic difference in catalytic properties with 99.99% selectivity for HCOOH in solvent-free condition (Ea = 0.29 eV) and 99.34% selectivity for CH2CH2 in solution (Ea = 0.33 eV). Slow-growth based MD simulation results uncover that mixed solvent of water/acetonitrile (H2O/ACN) is beneficial for the formation of C2+ product and the optimal ratio H2O/ACN (1:9) mixture solvent for the conversion of CO2 to CH2CH2. Under light irradiation, we found that multichannel photons enable adsorbed CHO* to couple with CHO species diffusing from nearby active sites, further forming C2 intermediates in solution. This work highlights the importance of the reaction medium on the photogenerative carrier dynamics and offers a strategy to regulate product selectivity in photocatalytic CO2 conversion.

DOI: 10.1002/anie.202500270

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202500270