物理化学学报 >> 2024, Vol. 40 >> Issue (10): 2312007.doi: 10.3866/PKU.WHXB202312007

所属专题： 太阳燃料光催化剂

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H2O及其中间体在缺电子Mn(3+δ)+位的自发增强吸附及其促进光催化产H2O2性能

尹鑫宇1, 石海洋1, 王玉1, 王雪飞1,*(), 王苹1, 余火根2,*()   

  1. 1 武汉理工大学材料科学与工程学院和化学化工与生命科学学院, 武汉 430070
    2 中国地质大学(武汉)材料与化学学院, 太阳燃料实验室, 武汉 430078
  • 收稿日期:2023-12-06 修回日期:2024-01-10 录用日期:2024-01-10 发布日期:2024-03-13
  • 通讯作者: Email: xuefei@whut.edu.cn (王雪飞)yuhuogen@cug.edu.cn (余火根)
  • 基金资助:
    国家自然科学基金(22178276); 国家自然科学基金(U22A20147); 国家自然科学基金(52073263); 湖北省自然科学基金(2022CFA001)

Spontaneously Improved Adsorption of H2O and Its Intermediates on Electron-Deficient Mn(3+δ)+ for Efficient Photocatalytic H2O2 Production

Xinyu Yin1, Haiyang Shi1, Yu Wang1, Xuefei Wang1,*(), Ping Wang1, Huogen Yu2,*()   

  1. 1 School of Materials Science and Engineering, and School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan 430070, China
    2 Laboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan 430078, China
  • Received:2023-12-06 Revised:2024-01-10 Accepted:2024-01-10 Published:2024-03-13
  • Contact: Email: xuefei@whut.edu.cn (Xuefei Wang)yuhuogen@cug.edu.cn (Huogen Yu)
  • Supported by:
    the National Natural Science Foundation of China(22178276); the National Natural Science Foundation of China(U22A20147); the National Natural Science Foundation of China(52073263); the Natural Science Foundation of Hubei Province of China(2022CFA001)

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摘要：

过渡金属羟基氧化物已被证明是水氧化反应的可靠助催化剂。然而，在水氧化过程中它们对H2O及其中间产物的吸附能力不足，极大制约了水氧化速率的提高。在本研究中，H2O及其中间体在MnOOH助剂的缺电子Mn(3+δ)+上的自发增强吸附可以极大地促进水的快速氧化，从而在纯水体系中实现高效的光催化H2O2生成。首先，无定型MnOOH通过定向光诱导氧化方法选择性地沉积在AuPd改性的单晶BiVO4光催化剂的(110)面上，从而制备了AuPd/BiVO4/MnOOH光催化剂。光催化实验表明，所制备的AuPd/BiVO4/MnOOH (0.5%)光催化剂的H2O2产生速率达到214 μmol∙L−1，并表现出良好的稳定性和重现性。密度泛函理论计算和X射线光电子能谱表征表明，MnOOH的自由电子可以有效地转移到BiVO4上，诱导缺电子Mn位(Mn(3+δ)+)的产生，从而自发地促进H2O及其中间体的吸附，增强四电子WOR反应，导致H2O2的高效生成。本文关于助催化剂与主体催化剂之间强相互作用的工作为其它高效催化材料的合理设计提供了一种新的思路。

关键词: 光催化, H2O2生产, MnOOH助催化剂, 单晶BiVO4, H2O吸附

Abstract:

Transitional metal oxyhydroxides have been demonstrated to be the reliable cocatalysts for water oxidation reaction. However, their insufficient adsorption ability for H2O and its intermediate products during water oxidation greatly restricts the improvement of water oxidation rate. In this study, a spontaneously improved adsorption of H2O and its intermediates on the electron-deficient Mn(3+δ)+ of MnOOH cocatalyst can greatly promote the rapid water oxidation to realize the efficient photocatalytic H2O2 production in a pure water system. In this case, amorphous MnOOH is selectively deposited on the (110) facet of AuPd-modified single-crystal BiVO4 photocatalyst via the directionally photoinduced oxidation approach to produce AuPd/BiVO4/MnOOH photocatalyst. Photocatalytic experiments exhibit that the as-prepared AuPd/BiVO4/MnOOH (0.5%) photocatalyst obtains the boosted H2O2-evolution rate of 214 μmol∙L−1 as well as exhibits an outstanding stability and reproducibility. Density functional theory calculations and X-ray photoelectron spectroscopy (XPS) characterization reveal that the free electrons of MnOOH can effectively transfer to BiVO4 to induce the generation of electron-deficient Mn sites (Mn(3+δ)+), which spontaneously promotes the adsorption of H2O and its intermediates for enhancing 4-electron water oxidation reaction, resulting in an efficient H2O2 production. The present work about the strong interaction between cocatalyst and bulk catalyst provides a fresh idea for the rational design of highly efficient catalytic materials.

Key words: Photocatalysis, H2O2-production, MnOOH cocatalyst, Single-crystal BiVO4, H2O-adsorption