Electrochemical Ammonia Oxidation Catalyzed by a Ruthenium Complex with a Dangling Sulfonate Group

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-05-08 DOI:10.1021/acscatal.5c01166

Huatian Xiong, Jing Yang, Jun Li, Yuanyuan Cai, Feiyang Zhang, Jia-Yi Chen, Rong-Zhen Liao, Licheng Sun, Biaobiao Zhang

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Abstract

The goal of realizing a direct ammonia fuel cell and using ammonia as a hydrogen carrier motivates the development of electrocatalysts for the oxidation of ammonia to nitrogen. Herein, we report [Ru(bds)(4-methylpyridine)₂] (Ru-bds-Mepy, bds = 2,2′-bipyridine-6,6′-disulfonate) as an efficient electrocatalyst for ammonia oxidation to nitrogen. The decent ammonia oxidation performance of Ru-bds-Mepy was demonstrated by cyclic voltammetry (k_obs of 51.47 s^–1) and bulk electrolysis (turnover number of 390). The hydrogen bond interaction between the coordination ammonia and the dangling sulfonate group was observed in the crystal structure and further demonstrated by density functional theory (DFT) calculations. Kinetic studies indicate that Ru-bds-Mepy exhibits first-order kinetics with respect to both catalyst and ammonia concentration. Then, DFT calculations suggest the potential of N–N bond formation via the nucleophilic attack of NH₃ on the Ru^VI nitride complex in a barrierless and rapid way. This study contributes an efficient ammonia oxidation catalyst with a record-high turnover number.

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悬空磺酸基钌配合物催化的电化学氨氧化反应

实现直接氨燃料电池和利用氨作为氢载体的目标激发了氨氧化制氮电催化剂的发展。本文报道了[Ru(bds)（4-甲基吡啶）2]（Ru-bds- mepy, bds = 2,2 ' -联吡啶-6,6 ' -二磺酸盐）作为氨氧化制氮的高效电催化剂。循环伏安法（kobs为51.47 s-1）和本体电解法（周转数为390）证明Ru-bds-Mepy具有良好的氨氧化性能。在晶体结构中观察到配位氨与悬空磺酸基之间的氢键相互作用，并通过密度泛函理论（DFT）计算进一步证实。动力学研究表明，Ru-bds-Mepy在催化剂和氨浓度方面均表现为一级动力学。然后，DFT计算表明，通过NH3对RuVI氮化物配合物的亲核攻击，可以无障碍、快速地形成N-N键。本研究提供了一种高效的氨氧化催化剂，具有创纪录的高周转率。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.