Liu Yunni, Tao Yinghao, Lu Zhaobing, Teng Jing, Hao Weiju, Lin Jun, Li Guisheng
Department of Chemistry, Renmin University of China, Beijing 100872, P. R. China.
School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai 200093, P. R. China.
Dalton Trans. 2023 Aug 22;52(33):11631-11637. doi: 10.1039/d3dt00686g.
The electrocatalytic nitrogen reduction reaction (NRR) to ammonia is a promising technology to store renewable energy and mitigate greenhouse gas emissions. However, it usually suffers from low ammonia yield and selectivity because of the lack of efficient electrocatalysts. Herein, we report that the construction of metal phosphide heterojunctions is an efficient strategy for NRR activity enhancement. A CoP-MoP heterojunction electrocatalyst, which is fabricated by a facile NaCl template-assisted strategy, exhibits a favorable ammonia yield rate of 77.8 μg h mg (38.9 μg h cm) and a high faradaic efficiency of 11.16% at -0.50 V the reversible hydrogen electrode. The high NRR electrocatalytic activity can be attributed to the electronic coupling effects and interfacial synergistic effects of CoP and MoP at the heterojunction interface, which accelerates the electron transfer rate. Moreover, Mo doping changes the d-band centers of metal sites on the CoP surface, which is conducive to N adsorption and promotes N* adsorption in the competition of occupying active sites, thus inhibiting the HER. This work manifests the high potential of phosphide electrocatalysts and opens an alternative route toward NRR electrocatalysis.
电催化氮还原反应（NRR）制氨是一种储存可再生能源和减少温室气体排放的有前景的技术。然而，由于缺乏高效的电催化剂，该反应通常存在氨产率和选择性较低的问题。在此，我们报道构建金属磷化物异质结是提高NRR活性的有效策略。通过简便的NaCl模板辅助策略制备的CoP-MoP异质结电催化剂，在相对于可逆氢电极-0.50 V时，表现出77.8 μg h mg（38.9 μg h cm）的良好氨产率和11.16%的高法拉第效率。高NRR电催化活性可归因于CoP和MoP在异质结界面处的电子耦合效应和界面协同效应，这加速了电子转移速率。此外，Mo掺杂改变了CoP表面金属位点的d带中心，有利于N的吸附，并在占据活性位点的竞争中促进N*吸附，从而抑制析氢反应（HER）。这项工作展示了磷化物电催化剂的巨大潜力，并为NRR电催化开辟了一条替代途径。
