Engineering Fluorine Doping and Ru–Schottky Interfaces in TiO2 for Efficient Photocatalytic CO2 Reduction with H2O

Sichun Ling; Ke Tang; Yafei Zheng; Bo Su; Xiahui Lin; Xue Feng Lu; Yidong Hou; Zhengxin Ding; Sibo Wang

doi:10.1007/s12209-025-00457-x

Transactions of Tianjin University ›› :1 -10. DOI: 10.1007/s12209-025-00457-x

Research Article

research-article

Engineering Fluorine Doping and Ru–Schottky Interfaces in TiO₂ for Efficient Photocatalytic CO₂ Reduction with H₂O

Sichun Ling ¹^,²
, Ke Tang ¹^,²
, Yafei Zheng ¹^,²
, Bo Su ¹^,²
, Xiahui Lin ³
, Xue Feng Lu ¹^,²
, Yidong Hou ¹^,²
, Zhengxin Ding ¹^,²^,^a
, Sibo Wang ¹^,²^,^b

Author information +

¹State Key Laboratory of Chemistry for NBC Hazards Protection, College of Chemistry, Fuzhou University, 350116, Fuzhou, China

²State Key Laboratory of Photocatalysis On Energy and Environment, College of Chemistry, Fuzhou University, 350116, Fuzhou, China

³College of Environment and Safety Engineering, Fuzhou University, 350108, Fuzhou, China

Corresponding author:

zxding@fzu.edu.cn

sibowang@fzu.edu.cn

Sichun Ling

Sichun Ling is a master student at the College of Chemistry, Fuzhou University. Her research focuses on catalysts structural design and reaction mechanism study of solar-driven CO2 reduction and oxidative methane coupling.

Ke Tang

Ke Tang is a master student at the College of Chemistry, Fuzhou University. His research focuses on photocatalysts and photothermal calcium base energy storage materials study.

Yafei Zheng

Yafei Zheng is a master student at the College of Chemistry, Fuzhou University. Her research focuses on photocatalytic CO2 reduction study.

Bo Su

Bo Su is a postdoctoral researcher at the College of Chemistry, Fuzhou University. His research focuses on solar-driven CO2 reduction and methane conversion.

Xiahui Lin

Xiahui Lin is an Assistant Professor at the College of Environment and Safety Engineering, Fuzhou University. Her research focuses on photocatalytic CO2 reduction study.

Xue Feng Lu

Xue Feng Lu is a Professor at the State Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou University. He has long been engaged in the design and synthesis of electrochemical energy materials and their application in water electrolysis, fuel cells, zinc-air batteries and other fields.

Yidong Hou

Yidong Hou is a Professor at the State Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou University. He is mainly engaged in basic and applied research of photo (electro) catalysis (degradation of organic pollutants, water decomposition and CO2 reduction, etc.).

Zhengxin Ding

Zhengxin Ding is a Professor at the State Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou University. He received his PhD under the supervision of Prof. Xianzhi Fu at Fuzhou University in 2005, and was recruited at Fuzhou University as a Researcher in 2012. His main research interests are photocatalytic CO₂ reduction and water splitting. He has published 120 peer-reviewed papers with more than 10,000 citations and an H-index of 52. He also obtained 41 national invention patents.

Sibo Wang

Sibo Wang is a Professor at the State Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou University. He obtained his PhD degree from Fuzhou University in 2016, and then went to Nanyang Technological University for postdoctoral research. In 2020, he was recruited at Fuzhou University as a Professor through the Global Recruitment Program of China. His main research interests are solar-driven CO₂ reduction, water splitting and alkane conversion. He has published over 140 peer-reviewed papers with more than 18,000 citations and an H-index of 62, and was selected as a Highly Cited Researcher by Clarivate from 2020 to 2025.

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Abstract

Photocatalytic CO₂ reduction using H₂O as the electron donor offers a sustainable pathway for carbon–neutral fuel synthesis; however, its efficiency is limited by sluggish charge separation and insufficient CO₂ activation. Herein, we develop a ruthenium-decorated, fluorine-doped TiO₂ photocatalyst (Ru/F-TiO₂) that overcomes these limitations through spatially directed charge modulation and cooperative electronic engineering. Fluorine doping introduces oxygen vacancies that narrow the bandgap and form surface Ti‒F bonds, suppressing charge recombination. Simultaneously, Ru nanoparticles serve as efficient CO₂ adsorption and activation centers while introducing additional surface defects that further strengthen CO₂ binding. The strong coupling between Ru and semiconductor forms a Schottky junction, establishing a strong built-in electric field that promotes directional electron migration toward Ru sites and hole accumulation on F-TiO₂. Consequently, Ru/F-TiO₂ exhibits outstanding activity and durability, delivering CO and CH₄ production rates of 124.8 and 19.8 μmol/(g·h), respectively. In situ diffuse reflectance infrared Fourier-transform spectroscopy analysis reveals key proton-coupled, multi-electron intermediates, elucidating the reaction pathway. This study demonstrates that the synergistic integration of non-metal doping and metal cocatalyst engineering provides a powerful strategy to regulate charge dynamics and boost solar-driven CO₂ conversion.

Keywords

CO₂ conversion / Photocatalysis / TiO₂ / Schottky junction / F-doping

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Sichun Ling, Ke Tang, Yafei Zheng, Bo Su, Xiahui Lin, Xue Feng Lu, Yidong Hou, Zhengxin Ding, Sibo Wang. Engineering Fluorine Doping and Ru–Schottky Interfaces in TiO₂ for Efficient Photocatalytic CO₂ Reduction with H₂O. Transactions of Tianjin University 1-10 DOI:10.1007/s12209-025-00457-x

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