【作者】 张英男；

【导师】 李吉来；

【作者基本信息】 吉林大学 ， 物理化学， 2015， 硕士

【摘要】 当代社会对能源的需求日益增多,在目前人类的所使用的能源中,占主要地位的仍然是化石能源。然而本着可持续发展的理念,各个国家都在推行低碳经济。由于煤的储量高于其他化石能源,因此如何更高效的利用煤就成了这一方向的关键问题。碳一化学就是这一方面一个重要的研究领域,其中二氧化碳是一种极具潜力的碳一化合物。本文对二氧化碳氢化进行理论计算的研究,采用密度泛函理论B3LYP水平下,使用的def2-svp基组研究了MH~+(M=Fe、Co、Ni)催化二氧化碳氢化反应中的过渡态,反应物和产物几何结构优化,同时为了得到更准确的能量信息,对几何优化的结构进行单点能计算。在单点能的计算中分别采用了B3LYP、BP86、TPSSh、PWPB95、B2PLYP以及耦合簇理论CCSD(T)方法。研究表明氢转移至C上要比转移至O上容易得多。探讨了不同泛函方法对反应的影响,从CCSD(T)的计算结果看出,与CoH+和NiH+相比,FeH+对H转移至C上的活性较高.电子结构分析表明:反应过程中氢转移为氢负离子转移。本文的研究结果能为二氧化碳的氢化及金属氢化物的氢转移反应提供有价值的理论指导更多还原

【Abstract】 In contemporary society, requirement of energy is increasing. At the moment, fossil fuels still play a dominant role in energy used by humans. In line with the concept of sustainable development, most countries around the world want to implement a low-carbon economy. Since coals reserve more than other fossil fuels, how to use coals in an efficient way is a key issue. C1 chemistry is an important aspect of this research area. Among C1 compound, CO2 has a good potential.In this article, density functional theory(DFT) method at B3 LYP level was conducted on the reaction of MH~+(M=Fe、Co、Ni)-catalyzed hydrogenation of carbon dioxide. To have a more accurate energy, we use different methods to do single point energy(SPE) calculation on the optimized geometry structure. In SPE calculation, we use B3 LYP, BP86, TPSSh, PWPB95, B2 PLYP and CCSD(T). Among these calculations, CCSD(T) method. The results show that hydrogen transfer to C is much easier than to O. The effect of DFT methods was also explored. FeH+ has higher reactivity than CoH+ and NiH+ on hydrogen transfer to C according to the coupled cluster theory CCSD(T) calculations. Electronic structure analysis demonstrates hydrogen transfer reaction process is hydride transfer.These studies may provide valuable theoretical guidance for research of hydrogenation of CO2 and hydride transfer of metal hydride.更多还原