{"title":"用于光诱导二氧化碳转化的普鲁士蓝模拟玻璃。","authors":"Soracha Kosasang, Nattapol Ma, Sarawoot Impeng, Sareeya Bureekaew, Yuji Namiki, Masahiko Tsujimoto, Taya Saothayanun, Hiroki Yamada and Satoshi Horike*, ","doi":"10.1021/jacs.4c03149","DOIUrl":null,"url":null,"abstract":"<p >Crystal-to-glass transformation is a powerful approach to modulating the chemical and physical properties of crystals. Here we demonstrate that the glass transformation of cobalt hexacyanoferrate crystals, one of the Prussian blue analogues, increased the concentration of open metal sites and altered the electronic state while maintaining coordination geometries and short-range ordering in the structure. The compositional and structural changes were characterized by X-ray absorption fine structure, energy dispersive X-ray spectroscopy, and X-ray total scattering. The changes contribute to the flat band potential of the glass becoming closer to the redox potential of CO<sub>2</sub> reduction. The valence band energy of the glass also shifts, resulting in lower band gap energy. Both the increased open metal sites and the optimal electronic structure upon vitrification enhance photocatalytic activity toward CO<sub>2</sub>-to-CO conversions (9.9 μmol h<sup>–1</sup> CO production) and selectivity (72.4%) in comparison with the crystalline counterpart (3.9 μmol h<sup>–1</sup> and 42.8%).</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4000,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Prussian Blue Analogue Glasses for Photoinduced CO2 Conversion\",\"authors\":\"Soracha Kosasang, Nattapol Ma, Sarawoot Impeng, Sareeya Bureekaew, Yuji Namiki, Masahiko Tsujimoto, Taya Saothayanun, Hiroki Yamada and Satoshi Horike*, \",\"doi\":\"10.1021/jacs.4c03149\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Crystal-to-glass transformation is a powerful approach to modulating the chemical and physical properties of crystals. Here we demonstrate that the glass transformation of cobalt hexacyanoferrate crystals, one of the Prussian blue analogues, increased the concentration of open metal sites and altered the electronic state while maintaining coordination geometries and short-range ordering in the structure. The compositional and structural changes were characterized by X-ray absorption fine structure, energy dispersive X-ray spectroscopy, and X-ray total scattering. The changes contribute to the flat band potential of the glass becoming closer to the redox potential of CO<sub>2</sub> reduction. The valence band energy of the glass also shifts, resulting in lower band gap energy. Both the increased open metal sites and the optimal electronic structure upon vitrification enhance photocatalytic activity toward CO<sub>2</sub>-to-CO conversions (9.9 μmol h<sup>–1</sup> CO production) and selectivity (72.4%) in comparison with the crystalline counterpart (3.9 μmol h<sup>–1</sup> and 42.8%).</p>\",\"PeriodicalId\":49,\"journal\":{\"name\":\"Journal of the American Chemical Society\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":14.4000,\"publicationDate\":\"2024-06-24\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of the American Chemical Society\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/jacs.4c03149\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/jacs.4c03149","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
摘要
晶体到玻璃的转化是调节晶体化学和物理特性的有力方法。在这里,我们证明了普鲁士蓝类似物之一的六氰基铁酸钴晶体的玻璃化转变在保持配位几何和短程有序结构的同时,增加了开放金属位点的浓度并改变了电子状态。通过 X 射线吸收精细结构、能量色散 X 射线光谱和 X 射线全散射对成分和结构变化进行了表征。这些变化使玻璃的平带电位变得更接近二氧化碳还原的氧化还原电位。玻璃的价带能也发生了变化,导致带隙能降低。与晶体对应物(3.9 μmol h-1 和 42.8%)相比,玻璃化后增加的开放金属位点和最佳电子结构提高了光催化活性,实现了 CO2 到 CO 的转化(9.9 μmol h-1 CO 生成量)和选择性(72.4%)。
Prussian Blue Analogue Glasses for Photoinduced CO2 Conversion
Crystal-to-glass transformation is a powerful approach to modulating the chemical and physical properties of crystals. Here we demonstrate that the glass transformation of cobalt hexacyanoferrate crystals, one of the Prussian blue analogues, increased the concentration of open metal sites and altered the electronic state while maintaining coordination geometries and short-range ordering in the structure. The compositional and structural changes were characterized by X-ray absorption fine structure, energy dispersive X-ray spectroscopy, and X-ray total scattering. The changes contribute to the flat band potential of the glass becoming closer to the redox potential of CO2 reduction. The valence band energy of the glass also shifts, resulting in lower band gap energy. Both the increased open metal sites and the optimal electronic structure upon vitrification enhance photocatalytic activity toward CO2-to-CO conversions (9.9 μmol h–1 CO production) and selectivity (72.4%) in comparison with the crystalline counterpart (3.9 μmol h–1 and 42.8%).
期刊介绍:
The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.