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Published on: February 11, 2016
A controlled non-radical chlorine activation pathway on hematite photoanodes for efficient oxidative chlorination
Daojian Tang1,2, Lei Wu1,2, Liubo Li3
1Key Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences Beijing 100190 P. R. China yczhang@iccas.ac.cn.
Abstract:
Photo(electro)catalytic chlorine oxidation has emerged as a useful method for chemical transformation and environmental remediation. However, the reaction selectivity usually remains low due to the high activity and non-selectivity characteristics of free chlorine radicals. In this study, we report a photoelectrochemical (PEC) strategy for achieving controlled non-radical chlorine activation on hematite (α-Fe2O3) photoanodes. High selectivity (up to 99%) and faradaic efficiency (up to 90%) are achieved for the chlorination of a wide range of aromatic compounds and alkenes by using NaCl as the chlorine source, which is distinct from conventional TiO2 photoanodes. A comprehensive PEC study verifies a non-radical "Cl+" formation pathway, which is facilitated by the accumulation of surface-trapped holes on α-Fe2O3 surfaces. The new understanding of the non-radical Cl- activation by semiconductor photoelectrochemistry is expected to provide guidance for conducting selective chlorine atom transfer reactions.
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