Li Zhiqiang, Xu Shikai, Chu Kainian, Yao Ge, Xu Yang, Niu Ping, Yang Yang, Zheng Fangcai
Institutes of Physical Science and Information Technology, Anhui University, Hefei, 230601, People's Republic of China.
Key Laboratory of Structure and Functional Regulation of Hybrid Materials, Anhui University, Ministry of Education, Hefei, 230601, People's Republic of China.
Inorg Chem. 2020 Sep 21;59(18):13741-13748. doi: 10.1021/acs.inorgchem.0c02103. Epub 2020 Sep 10.
Developing earth-abundant and highly efficient nonprecious metal catalysts for hydrogen evolution reaction (HER) is critical for the storage and conversion of renewable energy sources. Molybdenum carbide (MoC) has been extensively investigated as one of the most promising nonprecious electrocatalysts for boosting HER because of its low cost, high electrical conductivity, good chemical structure, and similar electronic structure to that of Pt. However, MoC always exhibits the negative hydrogen-binding energy, which can largely prevent adsorbed H desorption during the HER process. Herein, we report P- and Ni-dual-doped MoC in porous nitrogen-doped carbon (P/Ni-MoC) as an electrocatalyst for the HER, exhibiting excellent activity and durability with a low overpotential of 165 mV at 10 mA cm in alkaline electrolyte. Density functional theory (DFT) calculations proved that P and Ni acted as the anion and cation, respectively, to synergistically tune the electronic properties of MoC to decrease the negative hydrogen-binding energy, endowing the catalyst with excellent catalytic performance for the HER.
开发用于析氢反应（HER）的储量丰富且高效的非贵金属催化剂对于可再生能源的存储和转化至关重要。碳化钼（MoC）因其低成本、高电导率、良好的化学结构以及与铂相似的电子结构，作为最有前景的非贵金属电催化剂之一，已被广泛研究用于促进析氢反应。然而，MoC总是表现出负的氢结合能，这在很大程度上会阻止析氢反应过程中吸附氢的脱附。在此，我们报道了多孔氮掺杂碳中的磷和镍双掺杂MoC（P/Ni-MoC）作为析氢反应的电催化剂，在碱性电解质中，在10 mA cm时具有165 mV的低过电位，表现出优异的活性和耐久性。密度泛函理论（DFT）计算证明，磷和镍分别作为阴离子和阳离子，协同调节MoC的电子性质以降低负的氢结合能，赋予该催化剂优异的析氢反应催化性能。
