Toward High-Performance Electrochemical Ammonia Synthesis by Circumventing the Surface H-Mediated N2 Reduction.

IF 8.5 Q1 CHEMISTRY, MULTIDISCIPLINARY
JACS Au Pub Date : 2024-09-25 eCollection Date: 2024-10-28 DOI:10.1021/jacsau.4c00741
Zhe Chen, Tao Wang
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引用次数: 0

Abstract

The rapid performance decay with potentials is a significant obstacle to achieving an efficient electrocatalytic N2 reduction reaction (eNRR), which is typically attributed to competition from hydrogen evolution. However, the potential-dependent competitive behavior and reaction mechanism are still under debate. Herein, we theoretically defined N2 adsorption, H mediation, and H2 evolution as three crucial regions along the potentials by revisiting the potential-dependent competitive adsorption between N2 and H on FeN4 and RuN4 catalysts. We revealed that the surface H-mediated mechanism makes eNRR feasible at low potentials but introduces sluggish reaction kinetics, showing a double-edged sword nature. In view of this, we proposed a new possibility to achieve high-performance NH3 synthesis by circumventing the H-mediated mechanism, where the ideal catalyst should have a wide potential interval with N2-dominated adsorption to trigger direct eNRR. Using this mechanistic insight as a new criterion, we proposed a theoretical protocol for eNRR catalyst screening, but almost none of the theoretically reported electrocatalysts passed the assessment. This work not only illustrates the intrinsic mechanism behind the low-performance dilemma of eNRR but also points out a possible direction toward designing promising catalysts with high selectivity and high current density.

通过规避表面 H 介导的 N2 还原,实现高性能电化学氨合成。
性能随电位的快速衰减是实现高效电催化 N2 还原反应 (eNRR) 的一个重大障碍,通常归因于氢气进化的竞争。然而,与电位相关的竞争行为和反应机理仍存在争议。在此,我们通过重新审视 N2 和 H 在 FeN4 和 RuN4 催化剂上与电位相关的竞争吸附,从理论上将 N2 吸附、H 介导和 H2 演化定义为沿电位的三个关键区域。我们发现,表面 H 媒介机制使 eNRR 在低电位下可行,但却带来了反应动力学的迟缓,显示出双刃剑的性质。有鉴于此,我们提出了绕过 H 介导机制实现高性能 NH3 合成的新可能性,即理想的催化剂应具有较宽的电位区间,以 N2 吸附为主,从而直接引发 eNRR。利用这一机理洞察作为新标准,我们提出了 eNRR 催化剂筛选的理论方案,但理论上报道的电催化剂几乎无一通过评估。这项工作不仅说明了 eNRR 低性能困境背后的内在机理,还为设计具有高选择性和高电流密度的有前途催化剂指明了可能的方向。
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
CiteScore
9.10
自引率
0.00%
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10 weeks
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