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构建具有高效界面电荷转移的S型mCN@mPDIP分子异质结用于光催化有氧氧化合成。

Engineering S-scheme mCN@mPDIP molecular heterojunction with highly efficient interface charge transfer for photocatalytic aerobic oxidation synthesis.

作者信息

Nie Yina, Ma Yang-Ai, Wei Lele, Wu Mingxia, Zhao Xia, Liu Lin, Wan Jun

机构信息

College of Chemistry & Chemical Engineering, Shaanxi Key Laboratory of Chemical Reaction Engineering, Research Institute of Comprehensive Energy Industrial Technology, Yan'an University, Yan'an 716000, China.

Shaanxi Key Laboratory of Catalysis, School of Chemistry and Environment Science, Shaanxi University of Technology, Hanzhong 723001, China.

出版信息

J Colloid Interface Sci. 2025 Jan;677(Pt A):873-882. doi: 10.1016/j.jcis.2024.08.014. Epub 2024 Aug 5.

DOI:10.1016/j.jcis.2024.08.014
PMID:39126805
Abstract

The construction of S-scheme heterojunctions, which offers a promising approach for spatially separating photogenerated charge carriers with high redox potentials and multimolecular activation, represents a viable modification strategy in photocatalytic applications. However, the prevalent insufficient contact areas between two components result in low interface charge transfer efficiency, thereby impeding the photocatalytic performance of such heterostructures. Herein, we address this limitation by introducing a unique mCN@mPDIP molecular heterojunction through a pH-triggered molecule self-assembly eutectoid technique, enabling intimate interface contact and promoting highly efficient interfacial charge transfer following an S-scheme mechanism. Consequently, the mCN@mPDIP molecular heterojunction achieves significantly improved charge separation efficiency and higher concentration of active carriers compared to typical bCN-bPDIP bulk heterojunction and nCN/nPDIP nano heterojunction. Combined with the effective sulfide activation on mPDIP sites and O activation on mCN sites, the resulting mCN@mPDIP demonstrates outstanding activity in the photocatalytic aerobic oxidation of sulfides into sulfoxides without any redox mediators.

摘要

S型异质结的构建为光生电荷载流子的空间分离提供了一种很有前景的方法,具有高氧化还原电位和多分子活化作用,是光催化应用中一种可行的改性策略。然而,两种组分之间普遍存在接触面积不足的问题,导致界面电荷转移效率较低,从而阻碍了这种异质结构的光催化性能。在此,我们通过pH触发的分子自组装共析技术引入独特的mCN@mPDIP分子异质结来解决这一限制,实现紧密的界面接触,并按照S型机制促进高效的界面电荷转移。因此,与典型的bCN-bPDIP体相异质结和nCN/nPDIP纳米异质结相比,mCN@mPDIP分子异质结实现了显著提高的电荷分离效率和更高浓度的活性载流子。结合mPDIP位点上有效的硫化物活化和mCN位点上的氧活化,所得的mCN@mPDIP在光催化硫化物有氧氧化成亚砜的反应中表现出优异的活性,无需任何氧化还原介质。

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