丙烯腈的催化燃烧及其量化计算的研究化学工程与技术专业论文.docxVIP

北京化工大学硕士学位论文kcal／m01)远远高于生成N2(0．8 北京化工大学硕士学位论文 kcal／m01)远远高于生成N2(0．8 kcal／m01)的反应能垒，从而也揭示了在 Cu／ZSM．5上AN-SCC高N2选择性的原因。 继而，基于DFT模拟计算，对比了Co／ZSM．5和Cu／ZSM-5两种分子 筛催化剂发现Co／ZSM-5上的每一反应步骤能垒均高Cu／ZSM．5，说明在 Co／ZSM．5上更不容易生成N2；Cu／SSZ．13上的每一反应步骤能垒均高于 Cu／ZSM．5，揭示了丙烯腈在Cu／ZSM．5上活性要好于Cu／SSZ一13的原因。 通过对丙烯腈在Cu／ZSM一5上催化燃烧分解微观动力学参数研究发现： 从反应速率常数的大下比较可以发现AN-SCC分解反应第一个过渡态 (TSl)是速率控制步骤，这与反应能垒对比得出TSl是AN—SCC分解反 应速控步骤的结论是一致的：通过对丙烯腈在CⅣZSM．5上催化燃烧分解 关键步骤的电子转移分析发现在Cu／ZSM-5上AN-SCC反应中对于吸附态 反应，电子转移方向为：吸附态分子一活性位点以及分子筛骨架。对于过 渡态反应，电子转移方向不是非常的明确。 关键词：丙烯腈，选择性催化燃烧，机理，分子筛，Cu／ZSM-5，DFT Ⅱ 万方数据 CATALYTIC CATALYTIC COMBUSTION OF CHeCHCN AND RESEARCH OF REACTION MECHANISM VIA QUANTUM CHEMISTRY CALCULATION METHOD ABSTRACT Cu／ZSM-5 exhibited a superior catalytic performance[1 00％CzH3CN (AN)conversion and～96％N2 yield at T350。C]during selective catalytic combustion(SCC)of AN．The related AN-SCC mechanism was systematically investigated by in situ diffuse reflectance infrared Fourier transform spectra(in—situ DRIFTS)and density functional theory(DFT)．NCO Was found to be one kind of vital intermediate during AN—SCC based on in-situ DRIFTS．Then，the DFT was employed to give a deeper insight into how NCO Was generated and eventually turned into the final product of N2， wherein three kinds of models were constructed during DFT simulations： 20T-O—Cu-Z20，5T-O—Cu．Z5 with【CuO]+acting as the active site；and 5T-Cu-Z5 with[Cu]+acting as the active site．It Was revealed that(i)the AN could be initially oxidized into NCO and C02 over[CuO]十active site after overcoming an energy barrier of 17．0 kcal mol’1(Route I)；(ii)thereafter,three kinds of reaction pathways were proposed for the further reaction of NCO to produce N2，including NCO direct dissociation(NCO_÷N+COof Route II， 万方数据 万方数据 万方数据 北京化工大学硕士学位论文100．9 北京化工大学硕士学位论文 100．9 kcal molJ)，NCO coupling reaction(2NCO—N2+2CO of Route III， 48．7 kcal mol一1)，and NO+NCO reaction(NO+NCO-÷N2+c02 of Routes Iv-V 1 3．9 and O．8 kcal／m01)；the third reaction pathway possessing the lowest energy barri