TiO2 Nanoparticles Enabling Photocatalytic Desulfurization for C–C Coupling Reaction Using Visible Light

IF 7.5 Q2 NANOSCIENCE & NANOTECHNOLOGY

ACS Nanoscience Au Pub Date : 2026-06-17 Epub Date: 2026-02-27 DOI:10.1021/acsnanoscienceau.6c00020

Shea Stewart, Matas Simukaitis, H. Christopher Fry, Chengjun Sun, Yugang Sun

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Abstract

We uncover a surface-mediated mechanism for visible-light-driven photocatalytic desulfurization of thiols on titanium dioxide (TiO₂) nanoparticles under LED illumination (>420 nm). Combined diffuse reflectance, infrared, and cryogenic electron paramagnetic resonance spectroscopy verify the formation of a surface thiol–Ti charge-transfer complex that introduces visible-light absorption into an otherwise UV-active reaction system. Selective photoexcitation of this surface complex drives interfacial charge transfer, directly activating the adsorbed thiol and inducing C–S bond scission without the band gap excitation of TiO₂. The resulting carbon-centered radical intermediates are intercepted by styrene to form C–C coupling products. These results uncover a distinct surface-mediated photocatalytic mechanism in which charge-transfer complex formation governs both light absorption and chemical activation, providing a mechanistic framework for extending visible-light reactivity to wide-bandgap metal oxide photocatalysts.

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TiO2纳米粒子在可见光下催化C-C偶联反应脱硫

我们揭示了在LED照明（>420 nm）下，二氧化钛（TiO2）纳米颗粒上硫醇的可见光驱动光催化脱硫的表面介导机制。结合漫反射、红外和低温电子顺磁共振光谱验证了表面硫醇-钛电荷转移复合物的形成，该复合物将可见光吸收引入到其他紫外线活跃的反应体系中。该表面复合物的选择性光激发驱动界面电荷转移，直接激活吸附的硫醇并诱导C-S键断裂，而不需要TiO2的带隙激发。生成的以碳为中心的自由基中间体被苯乙烯截获，形成C-C偶联产物。这些结果揭示了一个独特的表面介导的光催化机制，其中电荷转移复合物的形成控制着光吸收和化学活化，为将可见光反应性扩展到宽带隙金属氧化物光催化剂提供了一个机制框架。

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来源期刊

ACS Nanoscience Au 材料科学、纳米科学-

CiteScore

4.20

自引率

0.00%

发文量

期刊介绍： ACS Nanoscience Au is an open access journal that publishes original fundamental and applied research on nanoscience and nanotechnology research at the interfaces of chemistry biology medicine materials science physics and engineering.The journal publishes short letters comprehensive articles reviews and perspectives on all aspects of nanoscience and nanotechnology:synthesis assembly characterization theory modeling and simulation of nanostructures nanomaterials and nanoscale devicesdesign fabrication and applications of organic inorganic polymer hybrid and biological nanostructuresexperimental and theoretical studies of nanoscale chemical physical and biological phenomenamethods and tools for nanoscience and nanotechnologyself- and directed-assemblyzero- one- and two-dimensional materialsnanostructures and nano-engineered devices with advanced performancenanobiotechnologynanomedicine and nanotoxicologyACS Nanoscience Au also publishes original experimental and theoretical research of an applied nature that integrates knowledge in the areas of materials engineering physics bioscience and chemistry into important applications of nanomaterials.