Ti3C2/In4SnS8肖特基异质结用于高效光催化生成H2O2和Cr(Ⅵ)还原

引用本文: 周彤, 刘雪, 赵亮, 乔明涛, 雷琬莹. Ti₃C₂/In₄SnS₈肖特基异质结用于高效光催化生成H₂O₂和Cr(Ⅵ)还原[J]. 物理化学学报, 2024, 40(10): 230902. doi: 10.3866/PKU.WHXB202309020 shu

Citation: Tong Zhou, Xue Liu, Liang Zhao, Mingtao Qiao, Wanying Lei. Efficient Photocatalytic H₂O₂ Production and Cr(Ⅵ) Reduction over a Hierarchical Ti₃C₂/In₄SnS₈ Schottky Junction[J]. Acta Physico-Chimica Sinica, 2024, 40(10): 230902. doi: 10.3866/PKU.WHXB202309020 shu

Ti₃C₂/In₄SnS₈肖特基异质结用于高效光催化生成H₂O₂和Cr(Ⅵ)还原

周彤 ^{1, †,} ,
刘雪 ^{2, †,} ,
赵亮 ^1, ,
乔明涛 ^1, ,
雷琬莹 ^{1,
,}

1.
西安建筑科技大学材料科学与工程学院, 西安 710055
2.
中国农业科学院烟草研究所, 山东青岛 266101

通讯作者: 雷琬莹, leiwy@xauat.edu.cn

基金项目:
国家自然科学基金 51902243

国家自然科学基金 2302112

陕西省教育厅重点科研计划项目 22JY039

陕西省教育厅重点科研计划项目 22JY037

中央非营利科研机构基础研究经费 1610232023008

农业科技创新计划 ASTIP-TRIC07

摘要: 人工光合成是一种先进的技术，可以利用太阳能作为唯一驱动能源，将水和氧气转化成双氧水(H₂O₂)。然而，目前常用的光催化体系的性能受制于其光吸收能力有限，载流子分离效率低以及表面反应能力弱等问题。在本文研究中，采用原位水热法，成功地在少层Ti₃C₂片表面生长厚度为5–10 nm的立方相In₄SnS₈ nm片(E_g = 2.16 eV)，形成了一种具有三明治结构的Ti₃C₂/In₄SnS₈纳米复合材料。Ti₃C₂和In₄SnS₈之间较大的界面面积及紧密的界面接触有助于载流子在体系中的迁移。X射线衍射仪(XRD)、透射电子显微镜(TEM)，和X射线光电子能谱(XPS)证实了Ti₃C₂/In₄SnS₈纳米复合材料的成功构建。能带结构包括价带顶端和Mott-Schottky曲线表明此2D/2D异质结形成了肖特基异质结，有助于载流子的快速分离，并从In₄SnS₈转移至Ti₃C₂表面，避免了电子从Ti₃C₂回流至In₄SnS₈。荧光光谱分析和光/电测试结果证明了Ti₃C₂和In₄SnS₈的复合有效抑制了载流子的复合。其中，7 wt% Ti₃C₂/In₄SnS₈复合材料表现出最佳的可见光催化性能，H₂O₂生成速率为1.998 µmol∙L⁻¹∙min^‒1，比单独In₄SnS₈高2.2倍。此外，Ti₃C₂/In₄SnS₈表现出多功能应用，对Cr(Ⅵ)的还原速率为19.8 × 10⁻³ min^‒1，比单一In₄SnS₈性能高约4倍。Ti₃C₂/In₄SnS₈复合材料在经过五次循环实验测试后表现优异的稳定性，其形貌、晶体结构和组成在反应后未发生改变。通过深层次的分析包括捕获实验、气氛实验和电子顺磁共振，证明了H₂O₂生成的途径包括两种：一种是两步单电子还原路径，另一种是一步两电子水氧化路径。本研究为设计高效、多功能的催化体系提供了一种新的思路。

关键词:

English

Efficient Photocatalytic H₂O₂ Production and Cr(Ⅵ) Reduction over a Hierarchical Ti₃C₂/In₄SnS₈ Schottky Junction

1.
College of Materials and Science, Xi'an University of Architecture and Technology, Xi'an 710055, China
2.
Institute of Tobacco Research, Chinese Academy of Agricultural Sciences, Qingdao 266101, Shandong Province, China

Corresponding author: Wanying Lei, Email: leiwy@xauat.edu.cn

Received Date: 12 September 2023
Accepted Date: 19 October 2023
Revised Date: 18 October 2023
Available Online: 15 October 2024
Fund Project:
the National Natural Science Foundation of China

the National Natural Science Foundation of China

Key Research Project of Shaanxi Education Department

Key Research Project of Shaanxi Education Department

the Fundamental Research Funds for Central Non-Profit Scientific Institution

the Agricultural Science and Technology Innovation Program
^†These authors contributed equally to this work.

Abstract: Artificial photosynthesis is an appealing approach for generating hydrogen peroxide (H₂O₂) from H₂O and O₂ with solar energy as the sole energy input. However, the current catalyst systems commonly face challenges such as the limited optical absorption, poor electron-hole pair separation efficiency, and restricted surface reactivity, which hinders the overall photoactivity. Here, we immobilize cubic-phase ultrathin In₄SnS₈ nanosheets (E_g = 2.16 eV) with thickness of 5–10 nm on the surface of few-layer Ti₃C₂ to develop a sandwich-like hierarchical structure of Ti₃C₂/In₄SnS₈ nanohybrid via in situ hydrothermal strategy. The enlarged interfacial area and close contact between Ti₃C₂ and In₄SnS₈ benefit for carrier transportation among nanohybrids. Characterization through X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) corroborates the successful construction of Ti₃C₂/In₄SnS₈ nanostructures. Band structures investigation including valence band maximum and Mott-Schottky plots reveals the formation of Schottky junction in this 2D/2D heterostructure, that favors for ultrafast charge carrier separation and transportation from In₄SnS₈ to Ti₃C₂ and preventing the electrons backflow from Ti₃C₂ to In₄SnS₈. Photoluminescene analysis and photo/electrochemical measurements prove that the combination of Ti₃C₂ and In₄SnS₈ accelerates the transportation of photoexcited electron-hole pairs and efficiently suppresses charge carrier recombination. Unsurprisingly, 7 wt% Ti₃C₂/In₄SnS₈ catalysts exhibit the highest visible-light-driven photoreactivity with H₂O₂ production rates of 1.998 µmol∙L⁻¹∙min^‒1 that is 2.2 times larger than that of single In₄SnS₈. Additionally, Ti₃C₂/In₄SnS₈ demonstrates a multifunctional capability in Cr(Ⅵ) reduction with the greatest reaction rates of 19.8 × 10⁻³ min^‒1 that is almost 4-fold larger than that of individual semiconductor. Moreover, the nanohybrids exhibit excellent photostability after 5 cycles testing in both reaction systems. The morphology, crystal structure and composition for Ti₃C₂/In₄SnS₈ remain unaltered after photoreaction. A comprehensive analysis including trapping agents and atmosphere experiments as well as electron paramagnetic resonance demonstrates that the H₂O₂ evolution pathway consists of two channels: a two-step successive 1e^‒ oxygen reduction reaction and a one-step 2e^‒ water oxidation reaction. This work may provide a viable protocol for designing efficient and multifunctional photocatalytic systems for solar-to-chemical energy conversion.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

Ti₃C₂/In₄SnS₈肖特基异质结用于高效光催化生成H₂O₂和Cr(Ⅵ)还原

通讯作者: 雷琬莹, leiwy@xauat.edu.cn

English

Efficient Photocatalytic H₂O₂ Production and Cr(Ⅵ) Reduction over a Hierarchical Ti₃C₂/In₄SnS₈ Schottky Junction

Corresponding author: Wanying Lei, Email: leiwy@xauat.edu.cn

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