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Photocatalytic 2-Iodoethanol Coupling to Produce 1,4-Butanediol Mediated by TiO2 and a Catalytic Nickel Complex |
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| Authors: | Qingchun Xu Puning Ren Yang Peng Prof. Nengchao Luo Zhuyan Gao Caixia Meng Jian Zhang Prof. Feng Wang |
| Affiliation: | 1. Henan Institute of Advanced Technology, Zhengzhou University, Zhengzhou, 450003 China These authors contributed equally to this work.;2. State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023 China University of Chinese Academy of Sciences, Beijing, 100049 China These authors contributed equally to this work.;3. School of Chemistry and Chemical Engineering, Nanchang University, Nanchang, 330031 China;4. State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023 China;5. State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023 China University of Chinese Academy of Sciences, Beijing, 100049 China;6. Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023 China;7. Henan Institute of Advanced Technology, Zhengzhou University, Zhengzhou, 450003 China |
| Abstract: | Photocatalytic 2-iodoethanol (IEO) coupling provides 1,4-butanediol (BDO) of particular interest to produce degradable polyesters. However, the reduction potential of IEO is too negative (−1.9 vs NHE) to be satisfied by most of the semiconductors, and the kinetics of transferring one electron for IEO coupling is slow. Here we design a catalytic Ni complex, which works synergistically with TiO2, realizing reductive coupling of IEO powered by photo-energy. Coordinating by terpyridine stabilizes Ni2+ from being photo-deposited to TiO2, thereby retaining the steric configuration beneficial for IEO coupling. The Ni complex can rapidly extract electrons from TiO2, generating a low-valent Ni capable of reducing IEO. The photocatalytic IEO coupling thus provides BDO in 72 % selectivity. By a stepwise procedure, BDO is obtained with 70 % selectivity from ethylene glycol. This work put forward a strategy for the photocatalytic reduction of molecules requiring strong negative potential. |
| Keywords: | 1,4-Butanediol Coupling Reactions Ethylene Glycol Nickel Photocatalysis |