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光催化分解水的产氢体系往往采用小分子醇作为电子供体,本工作以纯金红石相与混晶结构P25(80%锐钛矿与20%金红石相)二氧化钛为光催化剂,研究光解水过程中牺牲剂乙醇的氧化路径与反应机理.研究结果表明,无论是金红石相还是锐钛矿相为主的P25二氧化钛,其无氧条件下光催化氧化乙醇的主要终端产物均为乙醛,而不是2,3-丁二醇,2,3-丁二醇产物主要由醇醛特定波长范围内的有机光化学反应偶联产生.另外,不同晶相二氧化钛氧化乙醇至2,3-丁二醇的选择性差异可能主要由非均相固-液界面所产生羟基自由基迁移至溶液体系的距离不同所致,进而与有机光化学反应产生的·CH(OH)CH3自由基发生不同路径与频率的猝灭反应.本研究对乙醇无氧光催化反应步骤的探索与解析可为小分子醇参与的醇类重整反应提供机理借鉴与设计思路.
Photocatalytic decomposition of water hydrogen production system often uses small molecules of alcohol as an electron donor, the work of pure rutile and mixed crystal structure P25 (80% anatase and 20% rutile phase) titanium dioxide photocatalyst water-photolysis process Oxidation Path and Reaction Mechanism of Ethanol as Sacrificial Sacrificial Agent The results show that the main end products of both photocatalytic oxidation of ethanol under anaerobic conditions are acetaldehyde, 2,3-butanediol and 2,3-butanediol are mainly produced by the coupling of organic photochemical reactions in the specific wavelength range of alcoholates.In addition, the selection of 2,3-butanediol from different crystalline phases of titanium dioxide oxidizes ethanol The differences in sex may be mainly caused by the different distance of hydroxyl radical migration from the heterogeneous solid-liquid interface to the solution system, and then the quenching of different pathways and frequencies with CH (OH) CH3 radicals generated by organic photochemical reactions Reaction.In this study, we explored and analyzed the steps of anaerobic photocatalytic reaction of ethanol to provide the mechanism and design ideas for the alcohol reforming reaction involving small molecule alcohols.