物理化学学报 >> 2025, Vol. 41 >> Issue (7): 100081.doi: 10.1016/j.actphy.2025.100081

所属专题： 光催化中的S型异质结

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具有富电子Ptδ−壳层的空心AgPt@Pt核壳催化剂：提升光催化H2O2生成选择性与活性

王玉1, 石海洋2, 陈子涵1, 陈峰1, 王苹1, 王雪飞1,*()   

  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, 湖北 武汉 430070
    2 三峡大学水利与环境学院, 湖北 宜昌 443002
  • 收稿日期:2025-02-12 修回日期:2025-03-08 录用日期:2025-03-17 发布日期:2025-05-22
  • 通讯作者: Email: xuefei@whut.edu.cn (王雪飞)
  • 基金资助:
    国家自然科学基金(22178276); 国家资助博士后研究人员计划(GZC20240888); 武汉理工大学国家大学生创新创业训练计划(S202410497023)

Hollow AgPt@Pt core-shell cocatalyst with electron-rich Ptδ− shell for boosting selectivity of photocatalytic H2O2 production for faceted BiVO4

Yu Wang1, Haiyang Shi2, Zihan Chen1, Feng Chen1, Ping Wang1, Xuefei Wang1,*()   

  1. 1 School of Materials Science and Engineering, and School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan 430070, Hubei Province, China
    2 College of Hydraulic and Environmental Engineering, China Three Gorges University, Yichang 443002, Hubei Province, China
  • Received:2025-02-12 Revised:2025-03-08 Accepted:2025-03-17 Published:2025-05-22
  • Contact: Email: xuefei@whut.edu.cn (Xuefei Wang)
  • Supported by:
    the National Natural Science Foundation of China(22178276); the Postdoctoral Fellowship Program of CPSF(GZC20240888); the National College Students' Innovation and Entrepreneurship Training Program at Wuhan University of Technology(S202410497023)

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摘要：

铂(Pt)作为优异的氧还原助催化剂，在光催化产H2O2方面具有巨大潜力。然而，Pt对O2的吸附能力过强，易使O―O键裂解，从而降低2电子氧还原反应(ORR)生成H2O2的选择性。在本研究中，通过调节助剂结构改变Pt的电子结构，从而削弱Pt―O键的强度。本文通过两步光沉积法在BiVO4的(010)面上连续修饰了铂和银助催化剂。由于在此过程中存在置换反应，最终合成了一种具有中空AgPt合金核和富电子Ptδ−壳(AgPt@Pt)结构的协同催化剂。光催化实验结果表明：修饰空心结构AgPt@Pt助剂的BiVO4产生H2O2的速率达到了1021.5 μmol∙L−1，且其对应的量子效率(AQE)为5.07%，是Pt/BiVO4光催化剂(35.7 μmol∙L−1)的28.6倍。此外，密度泛函理论计算和X射线光电子能谱表征表明：AgPt合金向Pt壳转移电子，生成富电子的Ptδ−活性位点，进而增加了AgPt@Pt助催化剂中Pt―Oads反键轨道的占有率。这种电子再分布削弱了O2在Pt上的吸附强度，促进了2电子ORR反应，并显著提高了H2O2的生成效率。这一合成策略为制备具有更高H2O2选择性的铂基纳米助催化剂提供了可靠的方法。

关键词: 光催化, 富电子Ptδ-, O2吸附, H2O2, BiVO4

Abstract:

Platinum (Pt) is an excellent oxygen reduction cocatalyst with great potential for the photocatalytic production of H2O2. However, its catalytic efficiency is limited by the strong adsorption of O2, which facilitates O―O bond cleavage and reduces selectivity for the 2-electron oxygen reduction reaction (ORR). Fortunately, the strength of the Pt―O bond can be weakened by adjusting the structure of the cocatalyst to modify the electronic structure of Pt. In this paper, Pt and Ag cocatalysts are successively modified on the (010) facet of BiVO4 through a two-step photodeposition method. Due to the occurrence of a displacement reaction during the process, a synergistic catalyst with a hollow AgPt alloy core and an electron-rich Ptδ− shell (AgPt@Pt) structure is ultimately synthesized. Photocatalytic experiments demonstrated that the H2O2 production from BiVO4 modified with hollow AgPt@Pt reached an impressive 1021.5 μmol∙L−1. This corresponds to an AQE of 5.1%, which is 28.6 times higher than that of the Pt/BiVO4 photocatalyst with only 35.7 μmol∙L−1. Furthermore, research results show that AgPt can transfer electrons to the Pt shell to generate electron-rich Ptδ− active sites, thus increasing the antibonding orbital occupancy of Pt―Oads in AgPt@Pt catalysts. This electron redistribution weakens the adsorption strength of O2 on Pt, promoting the 2-electron ORR and facilitating the efficient generation of H2O2. This synthesis strategy offers a versatile approach for preparing other Pt-based nano-alloy cocatalysts with improved activity for the selective reduction of O2 to H2O2.

Key words: Photocatalysis, Electron-rich Ptδ-, O2-adsorption, H2O2, BiVO4