{"title":"无铅钙钛矿Cs2AgBiBr6/WO3-X的氧空位增强光催化C(sp3)-H键氧化","authors":"Taoran Chen, Tian Qin, Hongli Sun, Chenliang Su","doi":"10.1007/s12598-025-03400-0","DOIUrl":null,"url":null,"abstract":"<div><p>Photocatalytic oxidation of toluene to valuable benzaldehyde offers a promising pathway for sustainable production of fine chemicals and pharmaceuticals. In this process, photogenerated holes play a crucial role in C(sp<sup>3</sup>)-H bond dissociation. However, the photocatalytic performance of current photocatalysts is often hindered by the low separation and transfer efficiency of photogenerated charges. In this work, we presented a perovskite-based heterostructure via in situ growth of defective WO<sub>3-<i>x</i></sub> nanosheets on Cs<sub>2</sub>AgBiBr<sub>6</sub> nanoparticles for photocatalytic toluene transformation. In situ Fourier transform infrared spectroscopy tests proved the introduction of oxygen-deficient WO<sub>3-<i>x</i></sub> component enhanced the chemisorption of molecular oxygen. The in situ electron paramagnetic resonance and 4-chloro-7-nitro-1,2,3-benzoxadiazole fluorescence measurements further confirmed the presence of oxygen vacancies, and the formation of heterostructure synergistically accelerated the formation of the superoxide radicals and the transfer of photogenerated charge carriers. Under visible light irradiation, Cs<sub>2</sub>AgBiBr<sub>6</sub>/WO<sub>3-<i>x</i></sub> photocatalyst could effectively oxidize toluene toward benzaldehyde with a conversion rate of 9020 μmol g<sup>−1</sup> h<sup>−1</sup>, which was a 3.5-fold increase over that of the unmodified Cs<sub>2</sub>AgBiBr<sub>6</sub>. </p><h3>Graphical abstract</h3>\n<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 9","pages":"6354 - 6365"},"PeriodicalIF":11.0000,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Oxygen vacancy in lead-free perovskite Cs2AgBiBr6/WO3-X for enhanced photocatalytic C(sp3)-H bond oxidation\",\"authors\":\"Taoran Chen, Tian Qin, Hongli Sun, Chenliang Su\",\"doi\":\"10.1007/s12598-025-03400-0\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Photocatalytic oxidation of toluene to valuable benzaldehyde offers a promising pathway for sustainable production of fine chemicals and pharmaceuticals. In this process, photogenerated holes play a crucial role in C(sp<sup>3</sup>)-H bond dissociation. However, the photocatalytic performance of current photocatalysts is often hindered by the low separation and transfer efficiency of photogenerated charges. In this work, we presented a perovskite-based heterostructure via in situ growth of defective WO<sub>3-<i>x</i></sub> nanosheets on Cs<sub>2</sub>AgBiBr<sub>6</sub> nanoparticles for photocatalytic toluene transformation. In situ Fourier transform infrared spectroscopy tests proved the introduction of oxygen-deficient WO<sub>3-<i>x</i></sub> component enhanced the chemisorption of molecular oxygen. The in situ electron paramagnetic resonance and 4-chloro-7-nitro-1,2,3-benzoxadiazole fluorescence measurements further confirmed the presence of oxygen vacancies, and the formation of heterostructure synergistically accelerated the formation of the superoxide radicals and the transfer of photogenerated charge carriers. Under visible light irradiation, Cs<sub>2</sub>AgBiBr<sub>6</sub>/WO<sub>3-<i>x</i></sub> photocatalyst could effectively oxidize toluene toward benzaldehyde with a conversion rate of 9020 μmol g<sup>−1</sup> h<sup>−1</sup>, which was a 3.5-fold increase over that of the unmodified Cs<sub>2</sub>AgBiBr<sub>6</sub>. </p><h3>Graphical abstract</h3>\\n<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>\",\"PeriodicalId\":749,\"journal\":{\"name\":\"Rare Metals\",\"volume\":\"44 9\",\"pages\":\"6354 - 6365\"},\"PeriodicalIF\":11.0000,\"publicationDate\":\"2025-06-30\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Rare Metals\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s12598-025-03400-0\",\"RegionNum\":1,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Rare Metals","FirstCategoryId":"88","ListUrlMain":"https://link.springer.com/article/10.1007/s12598-025-03400-0","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
Oxygen vacancy in lead-free perovskite Cs2AgBiBr6/WO3-X for enhanced photocatalytic C(sp3)-H bond oxidation
Photocatalytic oxidation of toluene to valuable benzaldehyde offers a promising pathway for sustainable production of fine chemicals and pharmaceuticals. In this process, photogenerated holes play a crucial role in C(sp3)-H bond dissociation. However, the photocatalytic performance of current photocatalysts is often hindered by the low separation and transfer efficiency of photogenerated charges. In this work, we presented a perovskite-based heterostructure via in situ growth of defective WO3-x nanosheets on Cs2AgBiBr6 nanoparticles for photocatalytic toluene transformation. In situ Fourier transform infrared spectroscopy tests proved the introduction of oxygen-deficient WO3-x component enhanced the chemisorption of molecular oxygen. The in situ electron paramagnetic resonance and 4-chloro-7-nitro-1,2,3-benzoxadiazole fluorescence measurements further confirmed the presence of oxygen vacancies, and the formation of heterostructure synergistically accelerated the formation of the superoxide radicals and the transfer of photogenerated charge carriers. Under visible light irradiation, Cs2AgBiBr6/WO3-x photocatalyst could effectively oxidize toluene toward benzaldehyde with a conversion rate of 9020 μmol g−1 h−1, which was a 3.5-fold increase over that of the unmodified Cs2AgBiBr6.
期刊介绍：
Rare Metals is a monthly peer-reviewed journal published by the Nonferrous Metals Society of China. It serves as a platform for engineers and scientists to communicate and disseminate original research articles in the field of rare metals. The journal focuses on a wide range of topics including metallurgy, processing, and determination of rare metals. Additionally, it showcases the application of rare metals in advanced materials such as superconductors, semiconductors, composites, and ceramics.
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