Inverse Kinetic Solvent Isotope Effect in TiO2 Photocatalytic Dehalogenation of Non-adsorbable Aromatic Halides: A Proton-Induced Pathway†
Dr. Wei Chang
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)
Search for more papers by this authorDr. Chunyan Sun
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)
Department of Chemistry, Shaoxing University, Zhejiang Shaoxing 312000 (China)
Search for more papers by this authorDr. Xibin Pang
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)
Search for more papers by this authorDr. Hua Sheng
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)
Search for more papers by this authorDr. Yue Li
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)
Search for more papers by this authorProf. Hongwei Ji
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)
Search for more papers by this authorProf. Wenjing Song
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)
Search for more papers by this authorProf. Chuncheng Chen
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)
Search for more papers by this authorCorresponding Author
Prof. Wanhong Ma
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)Search for more papers by this authorCorresponding Author
Prof. Jincai Zhao
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)Search for more papers by this authorDr. Wei Chang
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)
Search for more papers by this authorDr. Chunyan Sun
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)
Department of Chemistry, Shaoxing University, Zhejiang Shaoxing 312000 (China)
Search for more papers by this authorDr. Xibin Pang
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)
Search for more papers by this authorDr. Hua Sheng
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)
Search for more papers by this authorDr. Yue Li
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)
Search for more papers by this authorProf. Hongwei Ji
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)
Search for more papers by this authorProf. Wenjing Song
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)
Search for more papers by this authorProf. Chuncheng Chen
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)
Search for more papers by this authorCorresponding Author
Prof. Wanhong Ma
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)Search for more papers by this authorCorresponding Author
Prof. Jincai Zhao
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)
Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)Search for more papers by this authorWe thank the National Basic Research Program of China (973 program No. 2013CB632405), the National Science Foundation of China (Grant No. 21137004, 21221002, 21277147 and 21377134), the “Strategic Priority Research Program” of the Chinese Academy of Sciences (No. XDA09030200), and the Chinese Academy of Sciences for financial support. We also wish to thank Dr. Yun Shen and Dr. Minyang Zhuang for helpful advice.
Abstract
An efficient redox reaction between organic substrates in solution and photoinduced h+vb/e−cb on the surface of photocatalysts requires the substrates or solvent to be adsorbed onto the surface, and is consequentially marked by a normal kinetic solvent isotope effect (KSIE≥1). Reported herein is a universal inverse KSIE (0.6–0.8 at 298 K) for the reductive dehalogenation of aromatic halides which cannot adsorb onto TiO2 in a [D0]methanol/[D4]methanol solution. Combined with in situ ATR-FTIR spectroscopy investigations, a previously unknown pathway for the transformation of these aromatic halides in TiO2 photocatalysis was identified: a proton adduct intermediate, induced by released H+/D+ from solvent oxidation, accompanies a change in hybridization from sp2 to sp3 at a carbon atom of the aromatic halides. The protonation event leads these aromatic halides to adsorb onto the TiO2 surface and an ET reaction to form dehalogenated products follows.
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