A chronological review of photochemical reactions of ferrioxalate at the molecular level:New insights into an old story  

作　　者：Xiaodie Li Meiru Hou Yu Fu Lingli Wang Yifan Wang Dagang Lin Qingchao Li Dongdong Hu Zhaohui Wang 

机构地区：[1]Shanghai Key Lab for Urban Ecological Processes and Eco-Restoration,School of Ecological and Environmental Sciences,East China Normal University,Shanghai 200241,China [2]Technology Innovation Center for Land Spatial Eco-Restoration in Metropolitan Area,Ministry of Natural Resources,Shanghai 200062,China [3]Shanghai Engineering Research Center of Biotransformation of Organic Solid Waste,Shanghai 200241,China

出　　处：《Chinese Chemical Letters》2023年第5期38-45,共8页中国化学快报（英文版）

基　　金：supported by the National Natural Science Foundation of China(No.41977313);the support from the Foundation of Key Laboratory of Yangtze River Water Environment,Ministry of Education(Tongji University),China(No.YRWEF202003);Key Laboratory of Eco-geochemistry,Ministry of Natural Resources(No.ZSDHJJ202006)。

摘　　要：Owing to its outstanding photoactivity,ferrioxalate is originally used as an actinometer and subsequent work has discovered that photochemistry of ferrioxalate is also fundamentally or technically important in atmospheric chemistry and water treatment.While the overall products generated from photolysis of ferrioxalate are known to include Fe(Ⅱ),a series of oxidizing(e.g.,·OH,O_(2)^(·-)/HO_(2)^(·-))or reducing(C_(2)O_(4)^(·-)/CO_(2)^(·-))radicals and H_(2)O_(2),however,at the molecular level,the primary step of the photoreaction of ferrioxalate remains as an unsolved mystery due to the difficulty in examining such ultrafast processes.Benefiting from the development of time-resolved spectroscopy,this old question has been studied with increasing vigor recently,by means of such ever-more-sophisticated techniques(e.g.,flash photolysis,time-resolved X-ray absorption spectroscopy(XAS),femtosecond infrared(IR)absorption spectroscopy,ultrafast photoelectron spectroscopy(PES)).There are two contrary views on the primary reaction mechanism:(1)Intramolecular electron transfer(ET)precedes the cleavage of the metal-ligand bond;(2)The dissociation of C-C or Fe-O bond occurs before intramolecular ET.Thus,this review presents a comprehensive summary about the overall reaction mechanism and molecular level mechanism of ferrioxalates.In chronological order,we have elaborated two predominant but controversial views from the perspectives of different experimental approaches.Some challenges and research opportunities in this active field are also briefly discussed.

关 键 词：FERRIOXALATE PHOTOLYSIS Ligand-to-metal charge transfer(LMCT) Time-resolved spectroscopy 

分 类 号：O644.1[理学—物理化学]