Kinetic and mechanistic analysis for the photodegradation of gaseous formaldehyde by core-shell CeO2@LDHs

光降解 甲酸 甲醛 光催化 催化作用 激进的 光化学 反应速率 化学工程 反应机理 过氧化氢 化学 无机化学 有机化学 工程类
作者
Shengjie Xia,Guanhua Zhang,Yue Meng,Chao Yang,Zheming Ni,Jun Hu
出处
期刊:Applied Catalysis B-environmental [Elsevier BV]
卷期号:278: 119266-119266 被引量:121
标识
DOI:10.1016/j.apcatb.2020.119266
摘要

• Core-shell structure composite of CeO 2 and LDHs (CeO 2 @LDHs) was synthesized. • Photodegradation of dynamic formaldehyde was realized in a continuous flow reaction device. • Reaction order, kinetic equation and activation energy during photodegradation were calculated. • Main reactive species of photodegradation are hydroxyl radical and superoxide radical. • Built-in electric field in heterojunction promotes the flow of electrons from CeO 2 to LDHs. While the removal of gaseous formaldehyde in breathing air via photocatalytic oxidation technology (POT) has shown great promise for pratical applications, the search of highly efficient and stable catalysts and mechanistic interpretations are highly desirable. We synthesized a core-shell structured composite of CeO 2 and layered double hydroxides (CeO 2 @LDHs). The degradation of gaseous formaldehyde was realized with high efficiency under visible light irradiation using a home-built continuous flow reaction device at an industrial reaction scale. It was confirmed that the catalytic activity of LDHs after CeO 2 complexation was significantly improved. Under optimum reaction conditions, a formaldehyde conversion of 86.9 % was achieved by CeO 2 @LDHs after 300 min equilibrium (3.73 μg g –1 h –1 ). Kinetic study showed that the flow rate of gaseous formaldehyde had the largest influence on the degradation rate of formaldehyde, followed by the relative humidity and the light intensity with a descending order. The rate equation and activation energy of photocatalytic degradation of formaldehyde were also obtained and discussed. The catalytically active radicals and the reaction intermediates were detected on CeO 2 @LDHs, shedding light on the intepretation of the reaction mechanism. Under the oxidation of hydroxyl and superoxide radicals and hot holes, gaseous formaldehyde was eventually degraded into carbon dioxide and water, as a result of the generation of formic acid, carbon hydrogen oxygen radicals ( CHO) and CO 2 – radicals. The present study demonstrates a systematic logical flow from design, preparation and mechanistic understanding of efficient LDHs-based photocatalyst for the degradataion of gaseous formaldehyde under practical conditions.
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