Manipulating the interactions between N-intermediates and one-dimensional conjugated coordination polymers to boost electroreduction of nitrate to ammonia
{"title":"Manipulating the interactions between N-intermediates and one-dimensional conjugated coordination polymers to boost electroreduction of nitrate to ammonia","authors":"","doi":"10.1016/S1872-2067(24)60059-8","DOIUrl":null,"url":null,"abstract":"<div><p>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<sup>–1</sup> cm<sup>–2</sup> 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 Δ<em>G</em> required for converting *NO to *NHO is reduced and the further hydrogenation is promoted. Additionally, the adsorption energies toward NH<sub>3</sub> are also effectively reduced by metal ions substitution, accelerating the desorption of generated and adsorbed NH<sub>3</sub>, making the turnover of catalysts more frequent.</p></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":null,"pages":null},"PeriodicalIF":15.7000,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chinese Journal of Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1872206724600598","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, APPLIED","Score":null,"Total":0}
引用次数: 0
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.
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.