{"title":"在氧化锌氧空位工程上将硝酸盐电催化转化为氨,以从受硝酸盐污染的地表水中回收氮。","authors":"Wenyang Fu, Yanjun Yin, Shuxian He, Xiangyi Tang, Yinan Liu, Fei Shen, Yan Zou, Guangming Jiang","doi":"10.1016/j.envres.2024.120279","DOIUrl":null,"url":null,"abstract":"<div><div>Nitrate pollution in surface water poses a significant threat to drinking water safety. The integration of electrocatalytic reduction reaction of nitrate (NO<sub>3</sub>RR) to ammonia with ammonia collection processes offers a sustainable approach to nitrogen recovery from nitrate-polluted surface water. However, the low catalytic activity of existing catalysts has resulted in excessive energy consumption for NO<sub>3</sub>RR. Herein, we developed a facile approach of electrochemical reduction to generate oxygen vacancy (Ov) on zinc oxide nanoparticles (ZnO<sub>1-x</sub> NPs) to enhance catalytic activity. The ZnO<sub>1-x</sub> NPs achieved a high NH<sub>3</sub>-N selectivity of 92.4% and NH<sub>3</sub>-N production rate of 1007.9 <span><math><mrow><msub><mtext>mg</mtext><mrow><msub><mtext>NH</mtext><mn>3</mn></msub><mo>‐</mo><mi>N</mi></mrow></msub></mrow></math></span> h<sup>−1</sup> m<sup>−2</sup> at −0.65 V <em>vs.</em> RHE in 22.5 mg L<sup>−1</sup> <span><math><mrow><msubsup><mtext>NO</mtext><mn>3</mn><mo>‐</mo></msubsup><mo>‐</mo><mi>N</mi></mrow></math></span>, surpassing both pristine ZnO and the majority of catalysts reported in the literature. DFT calculations with <em>in-situ</em> Raman spectroscopy and ESR analysis revealed that the presence of Ov significantly increased the affinity for the <span><math><mrow><msubsup><mtext>NO</mtext><mn>3</mn><mo>‐</mo></msubsup></mrow></math></span> (nitrate) and key intermediate of <span><math><mrow><msubsup><mtext>NO</mtext><mn>2</mn><mo>‐</mo></msubsup></mrow></math></span> (nitrite). The strong adsorption of <span><math><mrow><msubsup><mtext>NO</mtext><mn>3</mn><mo>‐</mo></msubsup></mrow></math></span> on Ov decreased the energy barrier of potential determining step (<span><math><mrow><msubsup><mtext>NO</mtext><mn>3</mn><mo>‐</mo></msubsup></mrow></math></span> →∗NO<sub>3</sub>) from 0.49 to 0.1 eV, boosting the reaction rate. Furthermore, the strong adsorption of <span><math><mrow><msubsup><mtext>NO</mtext><mn>2</mn><mo>‐</mo></msubsup></mrow></math></span> on Ov prevented its escape from the active sites, thereby minimizing <span><math><mrow><msubsup><mtext>NO</mtext><mn>2</mn><mo>‐</mo></msubsup></mrow></math></span> by-product formation and enhancing ammonia selectivity. Moreover, the NO<sub>3</sub>RR, when coupled with a membrane separation process, achieved a 100% nitrogen recycling efficiency with low energy consumption of 0.55 kWh <span><math><msubsup><mi>mol</mi><mi>N</mi><mrow><mo>−</mo><mn>1</mn></mrow></msubsup></math></span> at a flow rate below 112 mL min<sup>−1</sup> for the treatment of nitrate-polluted lake water. These results demonstrate that ZnO<sub>1-x</sub> NPs are a reliable catalytic material for NO₃RR, enabling the development of a sustainable technology for nitrogen recovery from nitrate-polluted surface water.</div></div>","PeriodicalId":312,"journal":{"name":"Environmental Research","volume":"264 ","pages":"Article 120279"},"PeriodicalIF":7.7000,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Electrocatalytic conversion of nitrate to ammonia on the oxygen vacancy engineering of zinc oxide for nitrogen recovery from nitrate-polluted surface water\",\"authors\":\"Wenyang Fu, Yanjun Yin, Shuxian He, Xiangyi Tang, Yinan Liu, Fei Shen, Yan Zou, Guangming Jiang\",\"doi\":\"10.1016/j.envres.2024.120279\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Nitrate pollution in surface water poses a significant threat to drinking water safety. The integration of electrocatalytic reduction reaction of nitrate (NO<sub>3</sub>RR) to ammonia with ammonia collection processes offers a sustainable approach to nitrogen recovery from nitrate-polluted surface water. However, the low catalytic activity of existing catalysts has resulted in excessive energy consumption for NO<sub>3</sub>RR. Herein, we developed a facile approach of electrochemical reduction to generate oxygen vacancy (Ov) on zinc oxide nanoparticles (ZnO<sub>1-x</sub> NPs) to enhance catalytic activity. The ZnO<sub>1-x</sub> NPs achieved a high NH<sub>3</sub>-N selectivity of 92.4% and NH<sub>3</sub>-N production rate of 1007.9 <span><math><mrow><msub><mtext>mg</mtext><mrow><msub><mtext>NH</mtext><mn>3</mn></msub><mo>‐</mo><mi>N</mi></mrow></msub></mrow></math></span> h<sup>−1</sup> m<sup>−2</sup> at −0.65 V <em>vs.</em> RHE in 22.5 mg L<sup>−1</sup> <span><math><mrow><msubsup><mtext>NO</mtext><mn>3</mn><mo>‐</mo></msubsup><mo>‐</mo><mi>N</mi></mrow></math></span>, surpassing both pristine ZnO and the majority of catalysts reported in the literature. DFT calculations with <em>in-situ</em> Raman spectroscopy and ESR analysis revealed that the presence of Ov significantly increased the affinity for the <span><math><mrow><msubsup><mtext>NO</mtext><mn>3</mn><mo>‐</mo></msubsup></mrow></math></span> (nitrate) and key intermediate of <span><math><mrow><msubsup><mtext>NO</mtext><mn>2</mn><mo>‐</mo></msubsup></mrow></math></span> (nitrite). The strong adsorption of <span><math><mrow><msubsup><mtext>NO</mtext><mn>3</mn><mo>‐</mo></msubsup></mrow></math></span> on Ov decreased the energy barrier of potential determining step (<span><math><mrow><msubsup><mtext>NO</mtext><mn>3</mn><mo>‐</mo></msubsup></mrow></math></span> →∗NO<sub>3</sub>) from 0.49 to 0.1 eV, boosting the reaction rate. Furthermore, the strong adsorption of <span><math><mrow><msubsup><mtext>NO</mtext><mn>2</mn><mo>‐</mo></msubsup></mrow></math></span> on Ov prevented its escape from the active sites, thereby minimizing <span><math><mrow><msubsup><mtext>NO</mtext><mn>2</mn><mo>‐</mo></msubsup></mrow></math></span> by-product formation and enhancing ammonia selectivity. Moreover, the NO<sub>3</sub>RR, when coupled with a membrane separation process, achieved a 100% nitrogen recycling efficiency with low energy consumption of 0.55 kWh <span><math><msubsup><mi>mol</mi><mi>N</mi><mrow><mo>−</mo><mn>1</mn></mrow></msubsup></math></span> at a flow rate below 112 mL min<sup>−1</sup> for the treatment of nitrate-polluted lake water. These results demonstrate that ZnO<sub>1-x</sub> NPs are a reliable catalytic material for NO₃RR, enabling the development of a sustainable technology for nitrogen recovery from nitrate-polluted surface water.</div></div>\",\"PeriodicalId\":312,\"journal\":{\"name\":\"Environmental Research\",\"volume\":\"264 \",\"pages\":\"Article 120279\"},\"PeriodicalIF\":7.7000,\"publicationDate\":\"2024-11-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Environmental Research\",\"FirstCategoryId\":\"93\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0013935124021868\",\"RegionNum\":2,\"RegionCategory\":\"环境科学与生态学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"ENVIRONMENTAL SCIENCES\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Environmental Research","FirstCategoryId":"93","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0013935124021868","RegionNum":2,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"ENVIRONMENTAL SCIENCES","Score":null,"Total":0}
Electrocatalytic conversion of nitrate to ammonia on the oxygen vacancy engineering of zinc oxide for nitrogen recovery from nitrate-polluted surface water
Nitrate pollution in surface water poses a significant threat to drinking water safety. The integration of electrocatalytic reduction reaction of nitrate (NO3RR) to ammonia with ammonia collection processes offers a sustainable approach to nitrogen recovery from nitrate-polluted surface water. However, the low catalytic activity of existing catalysts has resulted in excessive energy consumption for NO3RR. Herein, we developed a facile approach of electrochemical reduction to generate oxygen vacancy (Ov) on zinc oxide nanoparticles (ZnO1-x NPs) to enhance catalytic activity. The ZnO1-x NPs achieved a high NH3-N selectivity of 92.4% and NH3-N production rate of 1007.9 h−1 m−2 at −0.65 V vs. RHE in 22.5 mg L−1 , surpassing both pristine ZnO and the majority of catalysts reported in the literature. DFT calculations with in-situ Raman spectroscopy and ESR analysis revealed that the presence of Ov significantly increased the affinity for the (nitrate) and key intermediate of (nitrite). The strong adsorption of on Ov decreased the energy barrier of potential determining step ( →∗NO3) from 0.49 to 0.1 eV, boosting the reaction rate. Furthermore, the strong adsorption of on Ov prevented its escape from the active sites, thereby minimizing by-product formation and enhancing ammonia selectivity. Moreover, the NO3RR, when coupled with a membrane separation process, achieved a 100% nitrogen recycling efficiency with low energy consumption of 0.55 kWh at a flow rate below 112 mL min−1 for the treatment of nitrate-polluted lake water. These results demonstrate that ZnO1-x NPs are a reliable catalytic material for NO₃RR, enabling the development of a sustainable technology for nitrogen recovery from nitrate-polluted surface water.
期刊介绍:
The Environmental Research journal presents a broad range of interdisciplinary research, focused on addressing worldwide environmental concerns and featuring innovative findings. Our publication strives to explore relevant anthropogenic issues across various environmental sectors, showcasing practical applications in real-life settings.