As<sub>2</sub>O<sub>3</sub>与Cu-ZSM-5催化剂的相互作用机理

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摘要基于密度泛函理论计算了NO和As₂O₃在Cu-ZSM-5表面的吸附性能.通过确立As₂O₃在Cu-ZSM-5表面的最佳吸附位点,对As³⁺在其活性位点吸附的反应路径进行研究,计算As在催化剂上的吸附反应活化能垒和决速步骤,揭示As₂O₃与活性位点Cu-O-Cu的成键机制和相互作用机理.结果表明,NO和As₂O₃都以非氧端吸附在Cu-ZSM-5活性位点Cu-O-Cu的晶格氧位,吸附能分别为-218.515kJ/mol和-206.422kJ/mol,吸附过程中有电荷转移且发生了强烈的相互作用.As₂O₃在Cu-ZSM-5活性位点Cu-O-Cu的晶格氧上的氧化过程分两步进行,As³⁺作为Lewis碱与Lewis酸中心的Cu-O-Cu发生非均相氧化反应,第一阶段的氧化产物As₂O₄在相邻的活性位点上发生二次氧化反应,生成的As₂O₅成为As³⁺吸附后的主要存在形式.其中,生成As₂O₄的反应阶段需要跨越242.75kJ/mol的能垒,成为整个氧化进程的决速步骤.

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	张欢
	史一林
	刘梁
	王晨星
	孙瑞彬
	贾里
	金燕

关键词 ： Cu-ZSM-5, As₂O₃, 吸附, 氧化反应, 能垒

Abstract：The adsorption properties of NO and As₂O₃ over Cu-ZSM-5surface were calculated based on density functional theory in this paper. By determining the optimum adsorption site of As₂O₃ over Cu-ZSM-5, the reaction pathway of As³⁺ adsorbed on its active site was investigated, and the activation energy barriers and decisive speed steps of As adsorption reaction on the catalyst were calculated, to reveal the bonding and interaction mechanisms of the reaction between As₂O₃ and Cu-O-Cu. The results show that the non-oxygen sites of NO and As₂O₃ are adsorbed on the lattice oxygen sites of active site Cu-O-Cu and the adsorption energies are -218.515kJ/mol and -206.422kJ/mol, respectively. The loss of charge suggests that they interact strongly during adsorption process. The oxidation of As₂O₃ on lattice oxygen of Cu-O-Cu is divided into two steps. As³⁺, as Lewis base, is easy to react with Cu-O-Cu as Lewis acid center, and the oxidation product of the first stage, As₂O₄, undergoes a secondary oxidation reaction at the adjacent active site. As₂O₅ becomes the main form after As³⁺ adsorption. The reaction pathway to produce As₂O₄ has to overcome energy barrier of 242.75kJ/mol, which becomes the decisive speed step of the whole oxidation process.

Key words： Cu-ZSM-5 As₂O₃ adsorption oxidation reaction energy barrier

收稿日期: 2023-09-20

PACS:

X511

基金资助:国家自然科学基金资助项目(U1910214)

通讯作者: 金燕,博士,jinyan@tyut.edu.cn E-mail: jinyan@tyut.edu.cn

引用本文:

张欢, 史一林, 刘梁, 王晨星, 孙瑞彬, 贾里, 金燕. As₂O₃与Cu-ZSM-5催化剂的相互作用机理[J]. 中国环境科学, 2024, 44(4): 2003-2010. ZHANG Huan, SHI Yi-lin, LIU Liang, WANG Chen-xing, SUN Rui-bin, JIA Li, JIN Yan. Adsorption mechanism of As₂O₃ and Cu-ZSM-5catalysts. CHINA ENVIRONMENTAL SCIENCECE, 2024, 44(4): 2003-2010.

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http://www.zghjkx.com.cn/CN/ 或 http://www.zghjkx.com.cn/CN/Y2024/V44/I4/2003

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