Lin Yunxiang, Yang Li, Jiang Hongliang, Zhang Youkui, Bo Yanan, Liu Ping, Chen Shuangming, Xiang Bin, Li Guang, Jiang Jun, Xiong Yujie, Song Li
National Synchrotron Radiation Laboratory, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, Anhui 230029, China.
Institute of Physical Science and Information Technology, School of Physics and Materials Science, Anhui University, Hefei, Anhui 230601, China.
J Phys Chem Lett. 2020 Mar 5;11(5):1746-1752. doi: 10.1021/acs.jpclett.0c00134. Epub 2020 Feb 18.
Recent years have witnessed various in-depth research efforts on self-reconstruction behavior toward electrocatalysis. Tracking the phase transformation and evolution of true active sites is of great significance for the development of self-reconstructed electrocatalysts. Here, the optimized atomic sulfur-doped bismuth nanobelt (S-Bi) is fabricated via an electrochemical self-reconstruction evolved from BiS. Advanced technologies have demonstrated that the nonmetallic S atoms have been doped into the lattice Bi frame, leading to the reconstruction of local electronic structure of Bi. The as-prepared S-Bi nanobelt exhibits a remarkable NH generation rate of 10.28 μg h mg and Faradaic efficiency of 10.48%. Density functional theory calculations prove that the S doping can significantly lower the energy barrier of the rate-determining step and enlarge the N≡N bond for further dissociation toward N fixation. This work not only establishes insights into the evolution process of electrochemically derived self-reconstruction but also unravels the root of the N reduction reaction mechanism associated with the atomic nonmetal dopants.
近年来，人们对电催化的自重构行为进行了各种深入的研究。追踪真正活性位点的相变和演化对于自重构电催化剂的发展具有重要意义。在此，通过从BiS演化而来的电化学自重构制备了优化的原子硫掺杂铋纳米带（S-Bi）。先进技术表明，非金属S原子已掺杂到晶格Bi框架中，导致Bi的局部电子结构发生重构。所制备的S-Bi纳米带表现出显著的NH生成速率，为10.28 μgh mg，法拉第效率为10.48%。密度泛函理论计算证明，S掺杂可以显著降低速率决定步骤的能垒，并扩大N≡N键以进一步解离实现氮固定。这项工作不仅深入了解了电化学衍生自重构的演化过程，还揭示了与原子非金属掺杂剂相关的氮还原反应机制的根源。
