Hua Wen , Wen Duan , Li Guo , Qi Wang , Xin Fu , Yuhui Wang , Ruqi Li , Binbin Jin , Rui Du , Chunming Yang , Danjun Wang
{"title":"在化学键合的 Ni/Cd0.7Mn0.3S 肖特基异质结中引导电荷转移，用于选择性光催化氧化苯甲醇结构的有机平台分子，并与氢进化反应相结合","authors":"Hua Wen , Wen Duan , Li Guo , Qi Wang , Xin Fu , Yuhui Wang , Ruqi Li , Binbin Jin , Rui Du , Chunming Yang , Danjun Wang","doi":"10.1016/j.apcatb.2023.123641","DOIUrl":null,"url":null,"abstract":"<div><p><span><span>Solar-energy-driven half-reactions coupling is a vital photocatalysis strategy to simultaneously realize low-value organic platform molecules value-added conversion and </span>hydrogen production. It is essential to design photocatalyst with appropriate band structures and efficient spatial separation of photogenerated hole/electron pairs (h</span><sup>+</sup>/e<sup>-</sup>) to drive reduction/oxidation half-reactions, respectively. Herein, chemical-bonded Ni/Cd<sub>0.7</sub>Mn<sub>0.3</sub><span>S Schottky junction was constructed via hydrothermal-chemical reduction method for sunlight-driven catalytic selective dehydrogenation oxidization of benzyl alcohol (BA) coupling with hydrogen evolution reaction (HER). The optimal 8% Ni/Cd</span><sub>0.7</sub>Mn<sub>0.3</sub>S exhibited excellent BA conversion rate (77%), benzaldehyde (BAD) yield (2.88 mmol·g<sup>−1</sup>·h<sup>−1</sup>), selectivity (99%) and HER activity (2.94 mmol·g<sup>−1</sup>·h<sup>−1</sup><span>). The selective oxidation of BA and its para-substituents (-CH</span><sub>3</sub>, -OCH<sub>3</sub>, -Br, -NO<sub>2</sub>) proceeded a carbon-centred radical mechanism via the cleavage of α<sub>C-H</sub> bond. Furthermore, the Ni/Cd<sub>0.7</sub>Mn<sub>0.3</sub><span>S exhibits excellent selective oxidation of the other organic platform molecules with benzyl alcohol structure, such as 5-hydroxymethylfurfural (HMF) and vanillyl alcohol (VAL), </span><em>etc</em>, validating that the chemical-bonded Ni/Cd<sub>0.7</sub>Mn<sub>0.3</sub>S possess the excellent performance in α<sub>C-H</sub> bond activation of benzyl alcohol structure unit. By combining experiment and DFT calculation results, the Ni-S bond formed at Ni/Cd<sub>0.7</sub>Mn<sub>0.3</sub>S interface can accelerate the directing charge transfer, thus boosting the organic platform molecules selective oxidation coupling with HER.</p></div>","PeriodicalId":244,"journal":{"name":"Applied Catalysis B: Environmental","volume":null,"pages":null},"PeriodicalIF":20.2000,"publicationDate":"2023-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Directing charge transfer in a chemical-bonded Ni/Cd0.7Mn0.3S Schottky heterojunction for selective photocatalytic oxidation of benzyl alcohol structural organic platform molecules coupled with hydrogen evolution reaction\",\"authors\":\"Hua Wen , Wen Duan , Li Guo , Qi Wang , Xin Fu , Yuhui Wang , Ruqi Li , Binbin Jin , Rui Du , Chunming Yang , Danjun Wang\",\"doi\":\"10.1016/j.apcatb.2023.123641\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p><span><span>Solar-energy-driven half-reactions coupling is a vital photocatalysis strategy to simultaneously realize low-value organic platform molecules value-added conversion and </span>hydrogen production. It is essential to design photocatalyst with appropriate band structures and efficient spatial separation of photogenerated hole/electron pairs (h</span><sup>+</sup>/e<sup>-</sup>) to drive reduction/oxidation half-reactions, respectively. Herein, chemical-bonded Ni/Cd<sub>0.7</sub>Mn<sub>0.3</sub><span>S Schottky junction was constructed via hydrothermal-chemical reduction method for sunlight-driven catalytic selective dehydrogenation oxidization of benzyl alcohol (BA) coupling with hydrogen evolution reaction (HER). The optimal 8% Ni/Cd</span><sub>0.7</sub>Mn<sub>0.3</sub>S exhibited excellent BA conversion rate (77%), benzaldehyde (BAD) yield (2.88 mmol·g<sup>−1</sup>·h<sup>−1</sup>), selectivity (99%) and HER activity (2.94 mmol·g<sup>−1</sup>·h<sup>−1</sup><span>). The selective oxidation of BA and its para-substituents (-CH</span><sub>3</sub>, -OCH<sub>3</sub>, -Br, -NO<sub>2</sub>) proceeded a carbon-centred radical mechanism via the cleavage of α<sub>C-H</sub> bond. Furthermore, the Ni/Cd<sub>0.7</sub>Mn<sub>0.3</sub><span>S exhibits excellent selective oxidation of the other organic platform molecules with benzyl alcohol structure, such as 5-hydroxymethylfurfural (HMF) and vanillyl alcohol (VAL), </span><em>etc</em>, validating that the chemical-bonded Ni/Cd<sub>0.7</sub>Mn<sub>0.3</sub>S possess the excellent performance in α<sub>C-H</sub> bond activation of benzyl alcohol structure unit. By combining experiment and DFT calculation results, the Ni-S bond formed at Ni/Cd<sub>0.7</sub>Mn<sub>0.3</sub>S interface can accelerate the directing charge transfer, thus boosting the organic platform molecules selective oxidation coupling with HER.</p></div>\",\"PeriodicalId\":244,\"journal\":{\"name\":\"Applied Catalysis B: Environmental\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":20.2000,\"publicationDate\":\"2023-12-30\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Applied Catalysis B: Environmental\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0926337323012845\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Applied Catalysis B: Environmental","FirstCategoryId":"1","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0926337323012845","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Directing charge transfer in a chemical-bonded Ni/Cd0.7Mn0.3S Schottky heterojunction for selective photocatalytic oxidation of benzyl alcohol structural organic platform molecules coupled with hydrogen evolution reaction
Solar-energy-driven half-reactions coupling is a vital photocatalysis strategy to simultaneously realize low-value organic platform molecules value-added conversion and hydrogen production. It is essential to design photocatalyst with appropriate band structures and efficient spatial separation of photogenerated hole/electron pairs (h+/e-) to drive reduction/oxidation half-reactions, respectively. Herein, chemical-bonded Ni/Cd0.7Mn0.3S Schottky junction was constructed via hydrothermal-chemical reduction method for sunlight-driven catalytic selective dehydrogenation oxidization of benzyl alcohol (BA) coupling with hydrogen evolution reaction (HER). The optimal 8% Ni/Cd0.7Mn0.3S exhibited excellent BA conversion rate (77%), benzaldehyde (BAD) yield (2.88 mmol·g−1·h−1), selectivity (99%) and HER activity (2.94 mmol·g−1·h−1). The selective oxidation of BA and its para-substituents (-CH3, -OCH3, -Br, -NO2) proceeded a carbon-centred radical mechanism via the cleavage of αC-H bond. Furthermore, the Ni/Cd0.7Mn0.3S exhibits excellent selective oxidation of the other organic platform molecules with benzyl alcohol structure, such as 5-hydroxymethylfurfural (HMF) and vanillyl alcohol (VAL), etc, validating that the chemical-bonded Ni/Cd0.7Mn0.3S possess the excellent performance in αC-H bond activation of benzyl alcohol structure unit. By combining experiment and DFT calculation results, the Ni-S bond formed at Ni/Cd0.7Mn0.3S interface can accelerate the directing charge transfer, thus boosting the organic platform molecules selective oxidation coupling with HER.
期刊介绍：
Applied Catalysis B: Environment and Energy (formerly Applied Catalysis B: Environmental) is a journal that focuses on the transition towards cleaner and more sustainable energy sources. The journal's publications cover a wide range of topics, including:
1.Catalytic elimination of environmental pollutants such as nitrogen oxides, carbon monoxide, sulfur compounds, chlorinated and other organic compounds, and soot emitted from stationary or mobile sources.
2.Basic understanding of catalysts used in environmental pollution abatement, particularly in industrial processes.
3.All aspects of preparation, characterization, activation, deactivation, and regeneration of novel and commercially applicable environmental catalysts.
4.New catalytic routes and processes for the production of clean energy, such as hydrogen generation via catalytic fuel processing, and new catalysts and electrocatalysts for fuel cells.
5.Catalytic reactions that convert wastes into useful products.
6.Clean manufacturing techniques that replace toxic chemicals with environmentally friendly catalysts.
7.Scientific aspects of photocatalytic processes and a basic understanding of photocatalysts as applied to environmental problems.
8.New catalytic combustion technologies and catalysts.
9.New catalytic non-enzymatic transformations of biomass components.
The journal is abstracted and indexed in API Abstracts, Research Alert, Chemical Abstracts, Web of Science, Theoretical Chemical Engineering Abstracts, Engineering, Technology & Applied Sciences, and others.
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