氧化锰与氧化铈协同等离子体催化氧化甲醇的活性差异研究  

Exploration on the difference in performance of manganese oxide and cerium oxide in synergistic plasma-catalytic oxidation of methanol

作　　者：毛梦绮 王子琨 王雪青 苏春景 黎欢毅 石雪风 黄皓旻 付名利 胡芸 叶代启 吴军良 MAO Mengqi;WANG Zikun;WANG Xueqing;SU Chunjing;LI Huanyi;SHI Xuefeng;HUANG Haomin;FU Mingli;HU Yun;YE Daiqi;WU Junliang(School of Environment and Energy,South China University of Technology,Guangzhou 510006;National Engineering Laboratory for VOCs Pollution Control Technology and Equipment,Guangzhou 510006;Guangdong Provincial Key Laboratory of Atmospheric Environment and Pollution Control(SCUT),Guangzhou 510006)

机构地区：[1]华南理工大学环境与能源学院,广州510006 [2]挥发性有机物污染治理技术与装备国家工程实验室,广州510006 [3]广东省大气环境与污染控制重点实验室,广州510006

出　　处：《环境科学学报》2021年第7期2607-2616,共10页Acta Scientiae Circumstantiae

基　　金：国家重点研发计划(No.2016YFC0204200);国家自然科学基金(No.51678245,51578245);广东省自然科学基金(No.2020A1515010929);广州市科技计划项目(No.201804020026)。

摘　　要：在等离子体催化系统中,不同催化剂常表现出显著的性能差异.本文通过表面氧物种表征及臭氧氧化原位反应,探究了α-MnO_(2)与CeO_(2)两种常用催化剂在等离子体催化系统中催化氧化甲醇性能差异的本质原因.等离子体催化氧化甲醇的性能评价结果显示,在相同输入功率下CeO_(2)对甲醇的转化率和CO_(2)选择性均高于α-MnO_(2).氧气程序升温脱附(O_(2)-TPD)和X射线光电子能谱(XPS)等表征手段及甲醇常温催化、O_(3)分解和O_(3)催化氧化实验结果表明,CeO_(2)比α-MnO_(2)拥有更多的表面活性氧,能吸附活化更多的甲醇分子;同时,CeO_(2)能更有效地利用臭氧分解产生的活性氧物种对甲醇进行深度氧化.进一步通过原位DRIFTS实验研究两种催化剂协同臭氧催化氧化甲醇反应中间产物的变化,结果表明,CeO_(2)催化剂氧化甲醇的表面副产物较少,而α-MnO_(2)表面则会累积大量的副产物碳酸盐,从而影响其催化性能.Different types of catalysts usually exhibit significant activity differences in plasma-catalytic systems.In this paper,the performance ofα-MnO_(2) and CeO_(2) in the plasma-catalytic oxidation of methanol was explored by characterizing the surface oxygen species and investigating the in-situ ozone oxidation.At the same input power,CeO_(2) demonstrated higher methanol conversion and CO_(2) selectivity thanα-MnO_(2).By characterizing the catalysts with temperature-programmed desorption of oxygen(O_(2)-TPD)and X-ray photoelectron spectroscopy(XPS),and performing catalytic methanol oxidation,O_(3) decomposition and methanol ozonation experiments at ambient temperature,we revealed that CeO_(2),as compared toα-MnO_(2),possessed more surface oxygen species that are highly beneficial for activating methanol molecules.Besides,CeO_(2) might utilize more effectively the active oxygen species generated by ozone decomposition for complete methanol degradation.In-situ DRIFTS was performed to track the formation of intermediates in catalytic methanol oxidation by ozone over the two catalysts,and suggests that,while a large amount of carbonate by-products accumulate on the surface ofα-MnO_(2),CeO_(2) generated less surface by-products.

关 键 词：等离子体催化 α-MnO_(2) CeO_(2) 挥发性有机物 表面氧物种 

分 类 号：X701[环境科学与工程—环境工程] O643.3[理学—物理化学]