Integrating photocatalytic reduction of CO2 with selective oxidation of tetrahydroisoquinoline over InP–In2O3 Z-scheme p-n junction  

作　　者：Bohang Zhao Yi Huang Dali Liu Yifu Yu Bin Zhang 

机构地区：[1]Department of Chemistry,Tianjin Key Laboratory of Molecular Optoelectronic Sciences,School of Science,Tianjin University,Tianjin 300072,China [2]Institute of Molecular Plus,Tianjin University,Tianjin 300072,China [3]Collaborative Innovation Center of Chemical Science and Engineering,Tianjin 300072,China

出　　处：《Science China Chemistry》2020年第1期28-34,共7页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(21422104);the Natural Science Foundation of Tianjin City(17JCJQJC44700,16JCZDJC30600)

摘　　要：The development of a facile strategy to construct stable hierarchal porous heterogeneous photocatalysts remains a great challenge for efficient CO2 reduction.Additionally,hole-trapping sacrificial agents(e.g.,triethanolamine,triethylamine,and methanol)are mostly necessary,which produce useless chemicals,and thus cause costs/environmental concerns.Therefore,utilizing oxidation ability of holes to develop an alternative photooxidation reaction to produce value-added chemicals,especially coupled with CO2 photoreduction,is highly desirable.Here,an in situ partial phosphating method of In2O3 is reported for synthesizing In P–In2O3 p-n junction.A highly selective photooxidation of tetrahydroisoquinoline(THIQ)into value-added dihydroisoquinoline(DHIQ)is to replace the hole driven oxidation of typical sacrificial agents.Meanwhile,the photoelectrons of In P–In2O3 p-n junction can induce the efficient photoreduction of CO2 to CO with high selectivity and stability.The evolution rates of DHIQ and CO are 2 and 3.8 times higher than those of the corresponding In2O3 n-type precursor,respectively.In situ irradiated X-ray photoelectron spectroscopy and electron spin resonance are utilized to confirm that the direct Z-scheme mechanism of In P–In2O3 p-n junction accelerate the efficient separation of photocarriers.The development of a facile strategy to construct stable hierarchal porous heterogeneous photocatalysts remains a great challenge for efficient CO2 reduction. Additionally, hole-trapping sacrificial agents（e.g., triethanolamine, triethylamine, and methanol） are mostly necessary, which produce useless chemicals, and thus cause costs/environmental concerns. Therefore,utilizing oxidation ability of holes to develop an alternative photooxidation reaction to produce value-added chemicals, especially coupled with CO2 photoreduction, is highly desirable. Here, an in situ partial phosphating method of In2O3 is reported for synthesizing In P–In2O3 p-n junction. A highly selective photooxidation of tetrahydroisoquinoline（THIQ） into value-added dihydroisoquinoline（DHIQ） is to replace the hole driven oxidation of typical sacrificial agents. Meanwhile, the photoelectrons of In P–In2O3 p-n junction can induce the efficient photoreduction of CO2 to CO with high selectivity and stability. The evolution rates of DHIQ and CO are 2 and 3.8 times higher than those of the corresponding In2O3 n-type precursor, respectively. In situ irradiated X-ray photoelectron spectroscopy and electron spin resonance are utilized to confirm that the direct Z-scheme mechanism of In P–In2O3 p-n junction accelerate the efficient separation of photocarriers.

关 键 词：CO2 reduction DEHYDROGENATION photocatalysis Z-scheme TETRAHYDROISOQUINOLINE 

分 类 号：O643.36[理学—物理化学] O644.1[理学—化学]