Reshalaiti Hailili, Zelong Li, Xu Lu, Hua Sheng, Detlef W. Bahnemann and Jincai Zhao
{"title":"用于可见光氮氧化物去除的超薄缺陷异质结:微观结构与反应机制之间的相关性","authors":"Reshalaiti Hailili, Zelong Li, Xu Lu, Hua Sheng, Detlef W. Bahnemann and Jincai Zhao","doi":"10.1039/D4EN00362D","DOIUrl":null,"url":null,"abstract":"<p >Successful integration of defective heterojunctions is a proven effective strategy for promoting carrier separations and strengthening surface-interface redox reactions. Dipole moment variations are beneficial for charge carrier separation due to enlarged polarizations, especially within defective ones. Herein, motivated by the dipole variations in BiVO<small><sub>4</sub></small> and the unique layered structure of BiOCl, defective BiVO<small><sub>4</sub></small>/BiOCl heterojunctions were designed and integrated. The as-integrated samples displayed unique nanosheets with thicknesses decreasing from 7.24 to 2.77 nm, resulting in the simultaneous formation of stable surface defects. The heterojunctions were investigated for the removal of dilute NO (∼ppb) under visible light and exhibited 1.85- and 2.05-folds enhanced efficiencies (75%), synchronous inhibition of NO<small><sub>2</sub></small> (16.7% selectivity) and a more positive DeNO<small><sub><em>x</em></sub></small> index (0.36) than their constituent monomers. The improved activities and stabilities of surface defects were further examined by multi-run NO removal and EPR. The NO conversion products were validated by <em>in situ</em> DRIFTS investigation, which showed remarkable NO oxidation into NO<small><sub>3</sub></small><small><sup>−</sup></small> and synchronous NO<small><sub>2</sub></small> inhibition in thinner defective BiVO<small><sub>4</sub></small>/BiOCl. Mechanistic investigations indicated that surface defects in heterojunctions not only contributed to the improved light absorption and massive production of active species by coupling suitable band alignments, prolonging the carrier lifetime (3.55 ns to 7.52 ns) but also facilitated strong interfacial electric field contact at the junction interface of monomers, which enabled the construction of a direct Z-scheme charge transfer mechanism for NO removal.</p>","PeriodicalId":73,"journal":{"name":"Environmental Science: Nano","volume":null,"pages":null},"PeriodicalIF":5.8000,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Ultrathin defective heterojunction for visible light NO removal: correlation between microstructure and reaction mechanisms†\",\"authors\":\"Reshalaiti Hailili, Zelong Li, Xu Lu, Hua Sheng, Detlef W. 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The heterojunctions were investigated for the removal of dilute NO (∼ppb) under visible light and exhibited 1.85- and 2.05-folds enhanced efficiencies (75%), synchronous inhibition of NO<small><sub>2</sub></small> (16.7% selectivity) and a more positive DeNO<small><sub><em>x</em></sub></small> index (0.36) than their constituent monomers. The improved activities and stabilities of surface defects were further examined by multi-run NO removal and EPR. The NO conversion products were validated by <em>in situ</em> DRIFTS investigation, which showed remarkable NO oxidation into NO<small><sub>3</sub></small><small><sup>−</sup></small> and synchronous NO<small><sub>2</sub></small> inhibition in thinner defective BiVO<small><sub>4</sub></small>/BiOCl. 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Ultrathin defective heterojunction for visible light NO removal: correlation between microstructure and reaction mechanisms†
Successful integration of defective heterojunctions is a proven effective strategy for promoting carrier separations and strengthening surface-interface redox reactions. Dipole moment variations are beneficial for charge carrier separation due to enlarged polarizations, especially within defective ones. Herein, motivated by the dipole variations in BiVO4 and the unique layered structure of BiOCl, defective BiVO4/BiOCl heterojunctions were designed and integrated. The as-integrated samples displayed unique nanosheets with thicknesses decreasing from 7.24 to 2.77 nm, resulting in the simultaneous formation of stable surface defects. The heterojunctions were investigated for the removal of dilute NO (∼ppb) under visible light and exhibited 1.85- and 2.05-folds enhanced efficiencies (75%), synchronous inhibition of NO2 (16.7% selectivity) and a more positive DeNOx index (0.36) than their constituent monomers. The improved activities and stabilities of surface defects were further examined by multi-run NO removal and EPR. The NO conversion products were validated by in situ DRIFTS investigation, which showed remarkable NO oxidation into NO3− and synchronous NO2 inhibition in thinner defective BiVO4/BiOCl. Mechanistic investigations indicated that surface defects in heterojunctions not only contributed to the improved light absorption and massive production of active species by coupling suitable band alignments, prolonging the carrier lifetime (3.55 ns to 7.52 ns) but also facilitated strong interfacial electric field contact at the junction interface of monomers, which enabled the construction of a direct Z-scheme charge transfer mechanism for NO removal.
期刊介绍:
Environmental Science: Nano serves as a comprehensive and high-impact peer-reviewed source of information on the design and demonstration of engineered nanomaterials for environment-based applications. It also covers the interactions between engineered, natural, and incidental nanomaterials with biological and environmental systems. This scope includes, but is not limited to, the following topic areas:
Novel nanomaterial-based applications for water, air, soil, food, and energy sustainability
Nanomaterial interactions with biological systems and nanotoxicology
Environmental fate, reactivity, and transformations of nanoscale materials
Nanoscale processes in the environment
Sustainable nanotechnology including rational nanomaterial design, life cycle assessment, risk/benefit analysis