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POM促进的非晶态MnCeOx催化剂上NO与氯苯的协同催化作用:晶格氧的活化、酸位点的作用及催化机理

POM-promoted synergistic catalysis of NO and chlorobenzene over amorphous MnCeOx catalysts: Activation of lattice oxygen, role of acid site, catalytic mechanism.

作者信息

Lu Shengyong, Guo Xuanhao, Xu Xinlei, Han Zhengdong, Chen Min, Lin Beilong, Peng Yaqi, Wang Guanjie

机构信息

Zhejiang Key Laboratory of Advanced Solid State Energy Storage Technology and Applications, Taizhou Institute of Zhejiang University, Taizhou 318000, China.

State Key Laboratory of Clean Energy Utilization, Institute for Thermal Power Engineering, Zhejiang University, Hangzhou 310027, China.

出版信息

J Hazard Mater. 2025 Sep 5;495:138873. doi: 10.1016/j.jhazmat.2025.138873. Epub 2025 Jun 8.

DOI:10.1016/j.jhazmat.2025.138873
PMID:40516461
Abstract

The release rate of lattice oxygen and surface acidic sites are key factors for the multi-pollutant synergistic catalysis such as nitrogen oxides (NOx) and chlorine-containing volatile organic compounds (Cl-VOCs). In this study, a polyoxometalate (POM)-assisted strategy was employed to optimize the synergistic catalytic performance of MnCeOx for NO and chlorobenzene. The strong proton conductivity of the surface POM structure effectively suppresses the deposition of chlorinated species, preventing the poisoning of active sites. Specifically, POM-SiW structure can act as a dechlorination site in place of MnO and exhibits the highest density of acidic sites and oxygen vacancies, leading to a reduction of the T for chlorobenzene to 167 ℃ and an expansion. The assistance of POM-SiW structure facilitates the electron transfer from POM-SiW to lattice oxygen (O), resulting in reduced orbital overlap between Mn and O atoms, thereby weakening the Mn-O bond and activating O. Furthermore, in-situ DRIFTs, TOF-SIMS and DFT results confirmed that POM-SiW structure can inhibit the competitive adsorption of NO, NH and chlorobenzene, NO and NH act as additional oxidants and dechlorinating agents, effectively promoting the catalytic decomposition of chlorobenzene and its intermediate products. This work provides a novel strategy for catalyst design in low-temperature multi-pollutant synergistic catalysis.

摘要

晶格氧的释放速率和表面酸性位点是氮氧化物(NOx)和含氯挥发性有机化合物(Cl-VOCs)等多污染物协同催化的关键因素。在本研究中,采用多金属氧酸盐(POM)辅助策略优化MnCeOx对NO和氯苯的协同催化性能。表面POM结构的强质子传导性有效抑制了氯化物种的沉积,防止活性位点中毒。具体而言,POM-SiW结构可替代MnO作为脱氯位点,表现出最高密度的酸性位点和氧空位,使氯苯的T降低至167℃并拓宽。POM-SiW结构的辅助促进了电子从POM-SiW向晶格氧(O)的转移,导致Mn与O原子之间的轨道重叠减少,从而削弱了Mn-O键并活化了O。此外,原位DRIFTs、TOF-SIMS和DFT结果证实,POM-SiW结构可抑制NO、NH和氯苯的竞争吸附,NO和NH作为额外的氧化剂和脱氯剂,有效促进氯苯及其中间产物的催化分解。这项工作为低温多污染物协同催化中的催化剂设计提供了一种新策略。

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