中国科学技术大学熊宇杰团队通过掺杂调节氧空位局部电子结构改变光催化固氮的氢化途径。相关研究成果发表在2021年5月7日出版的国际知名学术期刊《德国应用化学》。

为了避免直接N [[EQUATION]] N键断裂的能耗步骤，已经开发了通过缔合途径在温和条件操作的光催化N2固定。然而，全面了解催化剂的精细结构是如何影响和改变缔合途径（即交替与远端）的，这是一项基本而富有挑战性的任务，它最终是显著促进实际应用的关键。

该文中，研究人员将铁掺杂剂引入到二氧化钛纳米纤维中以稳定氧空位并同时调整其局部电子结构。原位表征与第一性原理模拟综合研究表明，Fe掺杂对局域电子结构的调制使N2的加氢从缔合交替途径转变为缔合远端途径。

该研究为合理控制光催化固氮反应途径提供了新的思路。

附：英文原文

Title: Altering Hydrogenation Pathways in Photocatalytic Nitrogen Fixation by Tuning Local Electronic Structure of Oxygen Vacancy with Dopant

Author: Yanan Bo, Haiyun Wang, Yunxiang Lin, Tian Yang, Run Ye, Yu Li, Canyu Hu, Pengye Du, Yangguang Hu, Zhi Liu, Ran Long, Chao Gao, Bangjiao Ye, Li Song, Xiaojun Wu, Yujie Xiong

Issue&Volume: 2021-05-07

Abstract: To avoid the energy‐consuming step of direct N [[EQUATION]] N bond cleavage, photocatalytic N2 fixation undergoing the associative pathways has been developed for mild‐condition operation. However, it is a fundamental yet challenging task to gain comprehensive understanding on how the associative pathways (i.e., alternating vs. distal) are influenced and altered by the fine structure of catalysts, which eventually holds the key to significantly promote the practical implementation. Herein, we introduce Fe dopants into TiO2 nanofibers to stabilize oxygen vacancies and simultaneously tune their local electronic structure. The combination of in‐situ characterizations with first‐principles simulations reveals that the modulation of local electronic structure by Fe dopants turns the hydrogenation of N2 from associative alternating pathway to associative distal pathway. This work provides fresh hints for rationally controlling the reaction pathways toward efficient photocatalytic nitrogen fixation.

DOI: 10.1002/anie.202104001

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202104001