Roy Anand, Singh Anjali, Aravindh S Assa, Servottam Swaraj, Waghmare Umesh V, Rao C N R
New Chemistry Unit, Sheikh Saqr Laboratory, School of Advance Materials, Theoretical Science Unit, Jawaharlal Nehru Centre for Advanced Scientific Research Jakkur, P. O. 560064 Bangalore India
RSC Adv. 2020 Jan 31;10(9):5134-5145. doi: 10.1039/c9ra10711h. eCollection 2020 Jan 29.
Cadmium phosphochlorides, CdPCl and CdPCl, possess cadmium atoms differently bonded to chlorine and phosphorus ligands. A combined experimental and theoretical study has been carried out to examine the effect of manganese substitution in place of cadmium in these compounds. Experimentally it is found that manganese prefers the CdPCl phase over CdPCl. First-principles calculations reveal, stabilization of CdPCl upon Mn-substitution with a significant reduction in the formation energy when Mn is substituted at Cd-sites coordinated octahedrally by Cl-ligands. Substitution of Mn at two different Cd-sites in these compounds not only alters their formation energy differently but also causes a notable change in the electronic structures. In contrast to n-type conductivity in pristine CdPCl, Mn substituted Cd Mn PCl analogues exhibit p-type conductivity with a remarkable enhancement in the photochemical HER activity and stability of the system. Photochemical properties of pristine and substituted compounds are explained by studying the nature of charge carriers and their dynamics.
氯磷酸镉（CdPCl 和 CdPCl）中的镉原子与氯和磷配体的键合方式不同。已开展了一项结合实验与理论的研究，以考察这些化合物中用锰取代镉的效果。实验发现，相较于 CdPCl，锰更倾向于进入 CdPCl 相。第一性原理计算表明，当 Mn 在由 Cl 配体八面体配位的 Cd 位点上进行取代时，CdPCl 会因 Mn 取代而稳定，形成能显著降低。在这些化合物的两个不同 Cd 位点上取代 Mn，不仅会使其形成能发生不同程度的改变，还会导致电子结构发生显著变化。与原始 CdPCl 的 n 型导电性不同，Mn 取代的 CdMnPCl 类似物表现出 p 型导电性，且光化学析氢反应活性和体系稳定性显著增强。通过研究电荷载流子的性质及其动力学，解释了原始化合物和取代化合物的光化学性质。
