毕业论文（设计）HFO-1234ze热解机理的DFT研究.docVIP

HFO-1234ze热解机理的DFT研究 摘 要:通过密度泛函理论（DFT）对1,1,1,3-四氟丙烯（HFO-1234ze，CF3CH=CHF）的热解反应路径进行计算，并对热解可能的产物（CF3H, CF4, HF）进行了研究。结果表明：在均裂反应中，CF3自由基最易生成，其活化能为210.25 kJ mol-1。相比之下，由于较高的活化能，F自由基最难产生。在随后的链式反应中，生成CF3H所需的活化能最低为 64.23 kJ mol-1。而生成CF4和HF所需的活化能。本文从分子尺度研究了HFO-1234ze的热解机理并为研究工质的热稳定性提供了参考。 关键词 Mechanism of Thermal Decomposition of HFO-1234ze by DFT Study Hao Zhang1, Chao Liu1, Yu Cao1, Xiaoxiao Xu1, Qibin Li2 （1. Key Laboratory of Low-grade Energy Utilization Technology System, Ministry of Education, College of Power Engineer, Chongqing University, Chongqing 400030, China; 2. College of Aerospace Engineering, Chongqing University, Chongqing 400030, China） Abstract: Some reaction pathways of thermal decomposition of 1,1,1,3-tetrafluoro-1-propene（HFO-1234ze, CF3CH=CHFwere proposed to investigate the formation mechanism of some possible products(CF3H, CF4, HF) by using density function theory (DFT) simulations. The results point out that CF3 is the most preferred product in homolytic cleavage reactions with the lowest energy barrier of 210.25 kJ/mol. F radical is hard to be generated during thermal decomposition processes because of its higher energy barrier. In subsequent radical attacking chain reactions, a lower energy barrier (64.23 kJ/mol) is required to form CF3H. CF4 and HF will be generated with higher energy barriers. Our work presents the mechanism of thermal decomposition of HFO-1234ze from a molecule level and provides a reference for studying the thermal stability of working fluids. Key word: HFO-1234ze; Thermal decomposition; Density function theory (DFT) 基金项目：国家自然科学基金资助项目（No.和 No.515060131-），男，江苏人，硕士研究生，主要从事工质热稳定性的分子动力学模拟研究。 0前言 近些年来1,1,1,3-四氟丙烯CF3CH=CHF），ODP值为0，GWP值只有6，在大气中的寿命也只有18天，被认为是最有潜力的替代工质之一。HFO-1234ze 在ASHRAE 标准中被列为A1类, 即为低毒不可燃物质，具有良好的物理化学性质。现今，学者对于HFO-1234ze的研究较少而对于其同分异构体HFO-1234yf的研究较多，主要集中在工质的热物理性质和热力性能上。Tanaka等[1]通过实验研究了HFO-1234yf的临界温度临界压力和临界密度等参数发现与4a的性质接近Yamada等[2]比较了[3-6]表明HFO-1234yf与某些工质存在共沸现象。HFO-1234ze作为HFO