Manipulating the interactions between N-intermediates and one-dimensional conjugated coordination polymers to boost electroreduction of nitrate to ammonia

IF 15.7 1区 化学 Q1 CHEMISTRY, APPLIED
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Abstract

Electrocatalytic reduction of nitrate to ammonia (NITRR) is a promising strategy to remove nitrate pollutants and generate ammonia under mild conditions. However, the low conversion rate of nitrate and insufficient ammonia production rate severely limits the development of NITRR. Manipulating the adsorption of N-intermediates on the surface of catalyst greatly affects the activity and the selectivity of catalytic reaction. Herein, four one-dimensional π-d conjugated coordination polymers (1D CCPs) are synthesized and applied to NITRR. The selectivity and activity of NITRR are well improved by metal ion substitutions, which regulate the adsorption towards generated intermediates. The ammonia production rate reaches 2.28 mg h–1 cm–2 over Cu-BTA in 2 h, comparable to recent works at low nitrate concentrations, and the conversion rate of nitrate up to 96.74% in four hours with 79.46% ammonia selectivity. Density functional theory calculations reveal that Cu-BTA had electron-richer Cu center, causing the enhanced free energy of *NO and the attenuation of N=O bond. Therefore, the ΔG required for converting *NO to *NHO is reduced and the further hydrogenation is promoted. Additionally, the adsorption energies toward NH3 are also effectively reduced by metal ions substitution, accelerating the desorption of generated and adsorbed NH3, making the turnover of catalysts more frequent.

操纵 N-中间体与一维共轭配位聚合物之间的相互作用,促进硝酸盐到氨的电还原反应
电催化硝酸盐还原成氨(NITRR)是一种在温和条件下去除硝酸盐污染物并生成氨的可行策略。然而,硝酸盐转化率低和氨生成率不足严重限制了 NITRR 的发展。操纵催化剂表面对 N 介质的吸附会极大地影响催化反应的活性和选择性。本文合成了四种一维π-d共轭配位聚合物(1D CCPs),并将其应用于 NITRR。通过金属离子的置换,NITRR 的选择性和活性得到了很好的改善。Cu-BTA 在 2 小时内的氨生产率达到 2.28 毫克/小时-1 厘米-2,与最近在低浓度硝酸盐条件下的研究结果相当;硝酸盐在 4 小时内的转化率高达 96.74%,氨选择性为 79.46%。密度泛函理论计算显示,Cu-BTA 具有更强电子的 Cu 中心,导致 *NO 自由能增强,N=O 键衰减。因此,将 *NO 转化为 *NHO 所需的ΔG 降低了,从而促进了进一步的氢化。此外,金属离子的取代也有效降低了对 NH3 的吸附能,加速了生成和吸附的 NH3 的解吸,使催化剂的周转更加频繁。
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
Chinese Journal of Catalysis
Chinese Journal of Catalysis 工程技术-工程:化工
CiteScore
25.80
自引率
10.30%
发文量
235
审稿时长
1.2 months
期刊介绍: The journal covers a broad scope, encompassing new trends in catalysis for applications in energy production, environmental protection, and the preparation of materials, petroleum chemicals, and fine chemicals. It explores the scientific foundation for preparing and activating catalysts of commercial interest, emphasizing representative models.The focus includes spectroscopic methods for structural characterization, especially in situ techniques, as well as new theoretical methods with practical impact in catalysis and catalytic reactions.The journal delves into the relationship between homogeneous and heterogeneous catalysis and includes theoretical studies on the structure and reactivity of catalysts.Additionally, contributions on photocatalysis, biocatalysis, surface science, and catalysis-related chemical kinetics are welcomed.
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