College of Environmental Sciences and Engineering, Dalian Maritime University, Dalian 116024, China.
Laboratory of Plasma Physical Chemistry, Dalian University of Technology, Dalian 116024, China.
Int J Mol Sci. 2023 Jun 22;24(13):10487. doi: 10.3390/ijms241310487.
Plasmonic gold (Au) and Au-based nanocatalysts have received significant attention over the past few decades due to their unique visible light (VL) photocatalytic features for a wide variety of chemical reactions in the fields of environmental protection. However, improving their VL photocatalytic activity via a rational design is prevalently regarded as a grand challenge. Herein we boosted the VL photocatalysis of the TiO-supported Au-Cu nanocatalyst by applying O plasma to treat this bimetallic plasmonic nanocatalyst. We found that O plasma treatment led to a strong interaction between the Au and Cu species compared with conventional calcination treatment. This interaction controlled the size of plasmonic metallic nanoparticles and also contributed to the construction of AuCu-TiO interfacial sites by forming AuCu alloy nanoparticles, which, thus, enabled the plasmonic Au-Cu nanocatalyst to reduce the Schottky barrier height and create numbers of highly active interfacial sites. The catalyst's characterizations and density functional theory (DFT) calculations demonstrated that boosted VL photocatalytic activity over O plasma treated Au-Cu/TiO nanocatalyst arose from the favorable transfer of hot electrons and a low barrier for the reaction between CO and O with the construction of large numbers of AuCu-TiO interfacial sites. This work provides an efficient approach for the rational design and development of highly active plasmonic Au and Au-based nanocatalysts and deepens our understanding of their role in VL photocatalytic reactions.
在过去的几十年中,由于等离子体金(Au)和基于 Au 的纳米催化剂在环境保护领域的各种化学反应中具有独特的可见光(VL)光催化特性,因此受到了极大的关注。然而,通过合理的设计来提高其 VL 光催化活性被普遍认为是一个巨大的挑战。在此,我们通过应用 O 等离子体处理负载 TiO2 的 Au-Cu 纳米催化剂来提高其 VL 光催化性能。我们发现,与传统的煅烧处理相比,O 等离子体处理导致 Au 和 Cu 物种之间存在强烈的相互作用。这种相互作用控制了等离子体金属纳米颗粒的尺寸,并通过形成 AuCu 合金纳米颗粒促进了 AuCu-TiO 界面位点的构建,从而使等离子体 Au-Cu 纳米催化剂能够降低肖特基势垒高度并产生大量高活性的界面位点。催化剂的表征和密度泛函理论(DFT)计算表明,O 等离子体处理的 Au-Cu/TiO 纳米催化剂 VL 光催化活性的提高源于热电子的有效转移以及 CO 和 O 之间反应的低能垒,这是通过构建大量的 AuCu-TiO 界面位点实现的。这项工作为设计和开发高效的等离子体 Au 和基于 Au 的纳米催化剂提供了一种有效的方法,并加深了我们对它们在 VL 光催化反应中作用的理解。