Lu Lu, Sun Mingzi, Wu Tong, Lu Qiuyang, Chen Baian, Chan Cheuk Hei, Wong Hon Ho, Huang Bolong
Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Kowloon, Hong Kong SAR, China.
Research Centre for Carbon-Strategic Catalysis, The Hong Kong Polytechnic University, Kowloon, Hong Kong SAR, China.
Front Chem. 2023 Jun 14;11:1197010. doi: 10.3389/fchem.2023.1197010. eCollection 2023.
Transition metal (TM) single atom catalysts (SACs) are of great potential for photocatalytic H production because of their abundant catalytic active sites and cost-effectiveness. As a promising support material, red phosphorus (RP) based SACs are still rarely investigated. In this work, we have carried out systematic theoretical investigations by anchoring TM atoms (Fe, Co, Ni, Cu) on RP for efficient photocatalytic H generation. Our density functional theory (DFT) calculations have revealed that 3d orbitals of TM locate close to the Fermi level to guarantee efficient electron transfer for photocatalytic performances. Compared with pristine RP, the introduction of single atom TM on the surface exhibit narrowed bandgaps, resulting in easier spatial separation for photon-generated charge carriers and an extended photocatalytic absorption window to the NIR range. Meanwhile, the HO adsorptions are also highly preferred on the TM single atoms with strong electron exchange, which benefits the subsequent water-dissociation process. Due to the optimized electronic structure, the activation energy barrier of water-splitting has been remarkably reduced in RP-based SACs, revealing their promising potential for high-efficiency H production. Our comprehensive explorations and screening of novel RP-based SACs will offer a good reference for further designing novel photocatalysts for high-efficiency H generation.
过渡金属（TM）单原子催化剂（SACs）因其丰富的催化活性位点和成本效益，在光催化产氢方面具有巨大潜力。作为一种有前景的载体材料，基于红磷（RP）的SACs仍鲜有研究。在这项工作中，我们通过将TM原子（Fe、Co、Ni、Cu）锚定在RP上，对高效光催化产氢进行了系统的理论研究。我们的密度泛函理论（DFT）计算表明，TM的3d轨道靠近费米能级，以确保光催化性能的有效电子转移。与原始RP相比，表面引入单原子TM后带隙变窄，使得光生电荷载流子的空间分离更容易，并且光催化吸收窗口扩展到近红外范围。同时，在具有强电子交换的TM单原子上，HO吸附也非常有利，这有利于随后的水分解过程。由于电子结构的优化，基于RP的SACs中水分解的活化能垒显著降低，显示出它们在高效产氢方面的巨大潜力。我们对新型基于RP的SACs的全面探索和筛选将为进一步设计高效产氢的新型光催化剂提供很好的参考。
