Long Tairen, Zhang Yue, Cao Zexing
State Key Laboratory of Physical Chemistry of Solid Surfaces and Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 360015, China.
Huzhou Key Laboratory of Green Energy Materials and Battery Cascade Utilization, School of Intelligent Manufacturing, Huzhou College, Huzhou 313000, China.
ACS Appl Mater Interfaces. 2025 Sep 3;17(35):50035-50046. doi: 10.1021/acsami.5c12349. Epub 2025 Aug 24.
Dual-atom catalysts (DACs) have emerged as a promising platform for converting CO into valuable chemicals, addressing critical energy and environmental challenges. Here, we theoretically designed M-P/V catalysts by embedding single transition metal (M = Ir, Rh, and Co) and phosphorus atoms into defective h-BN. Extensive first-principles calculations were employed to investigate the mechanisms of CO thermal hydrogenation to HCOOH and CO cycloaddition with propylene oxide (PO) to produce propylene carbonate (PC). The metal-phosphorus dual-active sites were predicted to facilitate simultaneous activation and adsorption of CO, H, and PO, enabling detailed exploration of the reaction pathways. By combining static electronic structure calculations and microkinetic simulations, this work demonstrates that M-P/V sheets show excellent catalytic performance for both reactions under relatively mild conditions, particularly for CO hydrogenation on Co-P/V and cycloaddition on Rh-P/V. Stability analysis confirms the robustness of transition-metal-doped M-P/V systems. Notably, the binding strength of small molecules strongly correlates with metal type, and a strong linear correlation was observed between the adsorption free energies of reactive intermediates. This study offers valuable theoretical insights into the thermocatalytic mechanisms of CO hydrogenation and cycloaddition mediated by M-P/V catalysts, laying a foundation for designing multifunctional DACs to advance CO utilization technologies.
双原子催化剂（DACs）已成为一个有前景的平台，用于将CO转化为有价值的化学品，应对关键的能源和环境挑战。在此，我们通过将单过渡金属（M = Ir、Rh和Co）和磷原子嵌入有缺陷的h-BN中，从理论上设计了M-P/V催化剂。采用广泛的第一性原理计算来研究CO热加氢生成HCOOH以及CO与环氧丙烷（PO）环加成生成碳酸丙烯酯（PC）的机理。预测金属-磷双活性位点有助于同时活化和吸附CO、H和PO，从而能够详细探索反应途径。通过结合静态电子结构计算和微观动力学模拟，这项工作表明M-P/V片层在相对温和的条件下对这两个反应均表现出优异的催化性能，特别是Co-P/V上的CO加氢和Rh-P/V上的环加成反应。稳定性分析证实了过渡金属掺杂的M-P/V体系的稳健性。值得注意的是，小分子的结合强度与金属类型密切相关，并且在反应中间体的吸附自由能之间观察到了很强的线性相关性。这项研究为M-P/V催化剂介导的CO加氢和环加成的热催化机理提供了有价值的理论见解，为设计多功能DACs以推进CO利用技术奠定了基础。
