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

IF 20.2 1区化学 Q1 CHEMISTRY, PHYSICAL Applied Catalysis B: Environmental Pub Date : 2023-12-30 DOI:10.1016/j.apcatb.2023.123641

Hua Wen , Wen Duan , Li Guo , Qi Wang , Xin Fu , Yuhui Wang , Ruqi Li , Binbin Jin , Rui Du , Chunming Yang , Danjun Wang

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Abstract

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/Cd_0.7Mn_0.3S 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/Cd_0.7Mn_0.3S 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 α_C-H bond. Furthermore, the Ni/Cd_0.7Mn_0.3S 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/Cd_0.7Mn_0.3S possess the excellent performance in α_C-H bond activation of benzyl alcohol structure unit. By combining experiment and DFT calculation results, the Ni-S bond formed at Ni/Cd_0.7Mn_0.3S interface can accelerate the directing charge transfer, thus boosting the organic platform molecules selective oxidation coupling with HER.

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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

太阳能驱动的半反应耦合是同时实现低价值有机平台分子增值转化和制氢的重要光催化策略。设计具有适当能带结构和高效空间分离光生空穴/电子对（h+/e-）的光催化剂，以分别驱动还原/氧化半反应至关重要。本文通过水热化学还原法构建了化学键合的 Ni/Cd0.7Mn0.3S 肖特基结，用于阳光驱动的苯甲醇（BA）选择性脱氢氧化与氢进化反应（HER）耦合催化。最佳的 8%Ni/Cd0.7Mn0.3S具有优异的苯甲醇转化率（77%）、苯甲醛（BAD）产率（2.88 mmol-g-1-h-1）、选择性（99%）和氢进化反应活性（2.94 mmol-g-1-h-1）。BA 及其对位取代基（-CH3、-OCH3、-Br、-NO2）的选择性氧化是通过αC-H 键裂解的碳中心自由基机制进行的。此外，Ni/Cd0.7Mn0.3S 对其他具有苄醇结构的有机平台分子，如 5-hydroxymethylfurfural (HMF)和香草醇 (VAL) 等也表现出良好的选择性氧化作用，验证了化学键合的 Ni/Cd0.7Mn0.3S 在活化苄醇结构单元的 αC-H 键方面具有优异的性能。结合实验和 DFT 计算结果，Ni/Cd0.7Mn0.3S 界面形成的 Ni-S 键可加速定向电荷转移，从而促进有机平台分子选择性氧化与 HER 的耦合。

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来源期刊

Applied Catalysis B: Environmental 环境科学-工程：化工

CiteScore

38.60

自引率

6.30%

发文量

1117

审稿时长

24 days

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.