School of Chemistry and Chemical Engineering, Inner Mongolia Engineering and Technology Research Center for Catalytic Conversion and Utilization of Carbon Resource Molecules and Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot, 010021, P. R. China.
School of Chemical and Biomedical Engineering, Nanyang Technological University, Singapore, 637459, Singapore.
Small. 2021 Oct;17(40):e2102413. doi: 10.1002/smll.202102413. Epub 2021 Sep 7.
Molybdenum phosphide (MoP) is regarded as one of the most promising alternatives to noble-metal based electrocatalysts for efficient hydrogen evolution reaction (HER) due to its similar d-band electronic structure to noble metals and tunable features associated with phase and composition. However, it still remains a great challenge to construct MoP electrocatalysts with abundant active sites that possess ideal H binding strength to promote catalytic performance. In this work, it is found that by anchoring a rare earth compound, cerium phosphate (CePO ) on MoP (CePO /MoP), the stabilized Ce in CePO can significantly boost the formation of oxygen vacancies in ceria (CeO ) in situ formed on CePO surface during HER, which effectively regulates the d-band electronic density-of-states of MoP, increases the numbers of active sites, and promotes the vectorial electron transfer, therefore greatly enhancing the HER performance of MoP. The optimized CePO /MoP/carbon cloth (CC) electrocatalyst exhibits a significantly improved HER performance with an overpotential of 48 mV at 10 mA cm and a Tafel slope of 38 mV dec , about two times better than the HER performance of MoP catalyst without CePO (with an overpotential >80 mV dec at 10 mA cm ), very close to commercial Pt/C catalyst.
磷化钼(MoP)由于其与贵金属相似的 d 带电子结构以及与相和组成相关的可调特性,被认为是高效析氢反应(HER)中替代贵金属基电催化剂最有前途的材料之一。然而,构建具有丰富活性位点且具有理想 H 结合强度以促进催化性能的 MoP 电催化剂仍然是一个巨大的挑战。在这项工作中,人们发现通过将稀土化合物磷酸铈(CePO )锚定在 MoP(CePO /MoP)上,CePO 表面原位形成的 CeO 中 Ce 的稳定可以显著促进 HER 过程中 CeO 中氧空位的形成,这有效地调节了 MoP 的 d 带电子态密度,增加了活性位点的数量,并促进了定向电子转移,从而极大地提高了 MoP 的 HER 性能。优化后的 CePO /MoP/碳纤维布(CC)电催化剂在 10 mA cm 处具有明显改善的 HER 性能,过电位为 48 mV,塔菲尔斜率为 38 mV dec ,比没有 CePO 的 MoP 催化剂(在 10 mA cm 处过电位 >80 mV dec )提高了约两倍,非常接近商业 Pt/C 催化剂。