Zhang Lili, Ding Liang-Xin, Chen Gao-Feng, Yang Xianfeng, Wang Haihui
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640, China.
Analytical and Testing Center, South China University of Technology, Guangzhou, 510640, China.
Angew Chem Int Ed Engl. 2019 Feb 25;58(9):2612-2616. doi: 10.1002/anie.201813174. Epub 2019 Jan 14.
Constructing efficient catalysts for the N reduction reaction (NRR) is a major challenge for artificial nitrogen fixation under ambient conditions. Herein, inspired by the principle of "like dissolves like", it is demonstrated that a member of the nitrogen family, well-exfoliated few-layer black phosphorus nanosheets (FL-BP NSs), can be used as an efficient nonmetallic catalyst for electrochemical nitrogen reduction. The catalyst can achieve a high ammonia yield of 31.37 μg h mg under ambient conditions. Density functional theory calculations reveal that the active orbital and electrons of zigzag and diff-zigzag type edges of FL-BP NSs enable selective electrocatalysis of N to NH via an alternating hydrogenation pathway. This work proves the feasibility of using a nonmetallic simple substance as a nitrogen-fixing catalyst and thus opening a new avenue towards the development of more efficient metal-free catalysts.
构建用于氮还原反应（NRR）的高效催化剂是环境条件下人工固氮面临的一项重大挑战。在此，受“相似相溶”原理的启发，研究表明氮族元素的一员——充分剥离的少层黑磷纳米片（FL-BP NSs）可作为电化学氮还原的高效非金属催化剂。该催化剂在环境条件下可实现31.37 μg h mg的高氨产率。密度泛函理论计算表明，FL-BP NSs的锯齿形和扩散锯齿形边缘的活性轨道和电子能够通过交替氢化途径实现N到NH的选择性电催化。这项工作证明了使用非金属单质作为固氮催化剂的可行性，从而为开发更高效的无金属催化剂开辟了一条新途径。
