{"title":"组成工程化Cd-Mo-Se合金量子点用于光催化H2O2生成和Cr(VI)还原,详细的机理和影响参数。","authors":"Jyotirmayee Sahu, Sriram Mansingh, Bhagyashree Priyadarshini Mishra, Deeptimayee Prusty and Kulamani Parida","doi":"10.1039/D3DT02555A","DOIUrl":null,"url":null,"abstract":"<p >With the exceptional advantages of safety, greenness, and low cost, photocatalytic H<small><sub>2</sub></small>O<small><sub>2</sub></small> generation has kindled a wonderful spark, although being severely hampered by the terrible photoinduced exciton recombination, migration, and surface decomposition. Here, employing reflux method, the Cd–Mo–Se quantum dots of varying molar ratios of Cd and Mo were synthesized using thioglycolic acid as the capping ligand to regulate their growth. This type of metal alloying promotes rapid charge migration, improves light harvesting, and reduces the rate of charge recombination. The improved optoelectronic properties and boosted activity of Cd-rich ternary CMSe-1 QDs led to the observed exceptional photocatalytic H<small><sub>2</sub></small>O<small><sub>2</sub></small> yield of 1403.5 μmol g<small><sup>−1</sup></small> h<small><sup>−1</sup></small> (solar to chemical conversion efficiency, 0.27%) under visible light, outperforming the other ternary and Se-based QD photocatalysts. Additionally, CMSe-1 shows 93.6% (2 h) hazardous Cr(<small>VI</small>) photoreduction. The enhanced catalytic performance of CMSe-1 corresponds to effective charge carrier separation and transfer efficiency, well supported by PL, TRPL, and electrochemical measurements. Photocatalytic H<small><sub>2</sub></small>O<small><sub>2</sub></small> production was also studied under varying experimental conditions and the scavenger test suggests a superoxide radical intermediate 2-step single electron reduction pathway. The catalyst-assisted Cr(<small>VI</small>) reduction is substantiated by the zero-order kinetics as well as the determination of the pH<small><sub>PZC</sub></small> value. The catalyst can be employed for a maximum of four times while retaining its activity, according to the photostability and reusability test outcomes. This research presents interesting approaches for producing ternary QDs and modified systems for efficient photocatalytic H<small><sub>2</sub></small>O<small><sub>2</sub></small> production and Cr(<small>VI</small>) reduction.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 44","pages":" 16525-16537"},"PeriodicalIF":3.5000,"publicationDate":"2023-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2023/dt/d3dt02555a?page=search","citationCount":"0","resultStr":"{\"title\":\"Compositionally engineered Cd–Mo–Se alloyed QDs toward photocatalytic H2O2 production and Cr(vi) reduction with a detailed mechanism and influencing parameters†\",\"authors\":\"Jyotirmayee Sahu, Sriram Mansingh, Bhagyashree Priyadarshini Mishra, Deeptimayee Prusty and Kulamani Parida\",\"doi\":\"10.1039/D3DT02555A\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >With the exceptional advantages of safety, greenness, and low cost, photocatalytic H<small><sub>2</sub></small>O<small><sub>2</sub></small> generation has kindled a wonderful spark, although being severely hampered by the terrible photoinduced exciton recombination, migration, and surface decomposition. Here, employing reflux method, the Cd–Mo–Se quantum dots of varying molar ratios of Cd and Mo were synthesized using thioglycolic acid as the capping ligand to regulate their growth. This type of metal alloying promotes rapid charge migration, improves light harvesting, and reduces the rate of charge recombination. The improved optoelectronic properties and boosted activity of Cd-rich ternary CMSe-1 QDs led to the observed exceptional photocatalytic H<small><sub>2</sub></small>O<small><sub>2</sub></small> yield of 1403.5 μmol g<small><sup>−1</sup></small> h<small><sup>−1</sup></small> (solar to chemical conversion efficiency, 0.27%) under visible light, outperforming the other ternary and Se-based QD photocatalysts. Additionally, CMSe-1 shows 93.6% (2 h) hazardous Cr(<small>VI</small>) photoreduction. The enhanced catalytic performance of CMSe-1 corresponds to effective charge carrier separation and transfer efficiency, well supported by PL, TRPL, and electrochemical measurements. Photocatalytic H<small><sub>2</sub></small>O<small><sub>2</sub></small> production was also studied under varying experimental conditions and the scavenger test suggests a superoxide radical intermediate 2-step single electron reduction pathway. The catalyst-assisted Cr(<small>VI</small>) reduction is substantiated by the zero-order kinetics as well as the determination of the pH<small><sub>PZC</sub></small> value. The catalyst can be employed for a maximum of four times while retaining its activity, according to the photostability and reusability test outcomes. This research presents interesting approaches for producing ternary QDs and modified systems for efficient photocatalytic H<small><sub>2</sub></small>O<small><sub>2</sub></small> production and Cr(<small>VI</small>) reduction.</p>\",\"PeriodicalId\":71,\"journal\":{\"name\":\"Dalton Transactions\",\"volume\":\" 44\",\"pages\":\" 16525-16537\"},\"PeriodicalIF\":3.5000,\"publicationDate\":\"2023-10-25\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.rsc.org/en/content/articlepdf/2023/dt/d3dt02555a?page=search\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Dalton Transactions\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2023/dt/d3dt02555a\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2023/dt/d3dt02555a","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Compositionally engineered Cd–Mo–Se alloyed QDs toward photocatalytic H2O2 production and Cr(vi) reduction with a detailed mechanism and influencing parameters†
With the exceptional advantages of safety, greenness, and low cost, photocatalytic H2O2 generation has kindled a wonderful spark, although being severely hampered by the terrible photoinduced exciton recombination, migration, and surface decomposition. Here, employing reflux method, the Cd–Mo–Se quantum dots of varying molar ratios of Cd and Mo were synthesized using thioglycolic acid as the capping ligand to regulate their growth. This type of metal alloying promotes rapid charge migration, improves light harvesting, and reduces the rate of charge recombination. The improved optoelectronic properties and boosted activity of Cd-rich ternary CMSe-1 QDs led to the observed exceptional photocatalytic H2O2 yield of 1403.5 μmol g−1 h−1 (solar to chemical conversion efficiency, 0.27%) under visible light, outperforming the other ternary and Se-based QD photocatalysts. Additionally, CMSe-1 shows 93.6% (2 h) hazardous Cr(VI) photoreduction. The enhanced catalytic performance of CMSe-1 corresponds to effective charge carrier separation and transfer efficiency, well supported by PL, TRPL, and electrochemical measurements. Photocatalytic H2O2 production was also studied under varying experimental conditions and the scavenger test suggests a superoxide radical intermediate 2-step single electron reduction pathway. The catalyst-assisted Cr(VI) reduction is substantiated by the zero-order kinetics as well as the determination of the pHPZC value. The catalyst can be employed for a maximum of four times while retaining its activity, according to the photostability and reusability test outcomes. This research presents interesting approaches for producing ternary QDs and modified systems for efficient photocatalytic H2O2 production and Cr(VI) reduction.
期刊介绍:
Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.