气相中ZrO~+和CS_2、NbS~+和H_2O、Ir~+循环催化N_2O、H_2的反应动力学理论研究
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摘要
目前,“过渡金属化学”一直是实验和理论研究中非常活跃的领域。在工业上,过渡金属氧化物在很多方面被用做多用途的催化剂,但对有些反应其活性太高得不到预期的产品。相反,过渡金属硫化物作为催化剂反应活性低、不容易中毒显示了很高的选择性。过渡金属硫化物在生物化学上也起到了特殊的作用,因为不同的金属硫化物在一些金属酶里面形成了活性中心。另外,在过渡金属离子参与的反应中经常涉及势能面交叉的两态反应,理论化学家们对这类反应也做了大量的理论研究。本文以分子轨道理论、过渡态理论和量子力学理论为基础,利用密度泛函理论DFT和耦合簇理论CCSD(T)详细研究了三个反应体系的反应机理。
在第一个反应体系中,我们利用B3LYP/6-311+G*和CCSD(T)/ SDD+6-311+G*两种方法研究了过渡金属氧化物阳离子ZrO~+与小分子CS_2的反应机理.根据理论计算,我们提出了关于三种产物ZrS~+, ZrS_2~+和ZrOS~+可能的反应通道和反应机理。研究发现,生成ZrS~+, ZrS_2~+的反应都经历了同一个四元环过渡态的O/S交换反应步骤,即通过过渡态TS12形成中间体IM2。IM2除了能直接解离生成ZrS~+产物外,还存在一个分子重排反应而生成产物ZrS_2~+。提出的分子重排反应机理合理地解释了反应没有经过ZrS~+中间体而生成产物ZrS_2~+的实验现象。对于生成ZrOS~+的产物找到了两个平行的反应通道( Path A和B)。Path B是一个插入—消去的反应机理,此通道需要克服25.0 kJ/mol的反应能垒。Path A是一个硫原子的转移反应,但反应能垒很高(174.5 kJ/mol),只有在高能量反应条件下Path A才对生成产物ZrOS~+会有贡献。
在第二个反应体系中,我们利用B3LYP/6-311++G**方法对NbS~+ ( 3∑-, 1Γ)和H_2O的反应进行了理论计算研究,我们发现反应是通过两种反应机理进行的:一个是氧硫交换反应:NbS~+中的S原子与H_2O中的O原子相互交换而得到产物NbO~+;另一个是脱H_2分子(伴随着解离出一个H原子而生成NbOSH+的副反应)而得到产物NbOS~+。对于脱H_2分子的过程,反应进行的最有利的途径是3NbS~+ ( 3∑- ) + H_2O→1NbOS~+-2 ( 1A’) + H_2。反应涉及两态,存在势能面交叉的现象。计算结果合理解释了实验上所观察到的现象。
在第三个反应体系中,我们在CCSD(T)/ [ SDD + 6-311+G** // B3LYP / [ SDD+ TZVP ]理论水平上研究了过渡金属离子Ir~+循环催化反应N_2O + H_2→N_2 + H_2O((1)N_2O + Ir~+→IrO~+ + N_2 (2)IrO~+ + H_2→Ir~++ H_2O)。计算结果表明:整个反应经过了两步过程,第一步是Ir~+从N_2O中夺取O原子生成IrO~+和H_2的过程,是整个反应的速率决定步骤,需要克服一个42.8kJ/mol的能垒;第二步是生成的IrO~+和H_2还原生成Ir~+和H_2O的过程,此过程不需要能垒。这两步反应都是自旋允许的反应,不存在势能面交叉。两个反应都是放热的过程。
Nowadays, the transition-metal-ion chemistry has been an active area for both experimental and theoretical studies. In industry, transition-metal oxides are used as versatile catalysts in many applications, however, for some processes their reactivity is too high and non-specific product formation occurs. In contrast, transition-metal sulfides are less reactive and susceptible to poisoning and can show higher selectivity. Transition metal sulfides also play a particular role in biochemistry in that heterometallic sulfur complexes form the active sites in several metalloenzymes. Besides, theoretical approaches to gas-phase transition-metal chemistry which involve two-state reactivity along reaction path have also been studied by many chemists. In this paper, on the basis of the molecular orbital theory, the transition state theory as well as quantum chemistry theory, three systems choosed have been studied using DFT method and coupled cluster CCSD (T) methods.
For the ~2△ground state of ZrO~+ with CS_2 system, the mechanisms for three products ZrS~+, ZrS_2~+ and ZrOS~+ have been studied by using B3LYP/6-311+G* and CCSD(T)/SDD+6-311+G* methods. It is found that both ZrS~+ and ZrS_2~+ formations involve the same O/S exchange process via a four-center transition state TS12 to form an intermediate IM2. Exception of that IM2 can dissociate into the ZrS~+ product, a favorable intramolecular rearrangement mechanism associated with the ZrS_2~+ formation has been identified, which explains why ZrS~+ was excluded as a precusor for the ZrS_2~+ formation and why the lower efficiency of the ZrS~+ formation was observed in experiment. For the formation of ZrOS~+, two parallel channels (path A and B) yielding their corresponding product isomer have been identified. Path B involving an insertion-elimination mechanism with a calculated barrier underestimated by ca. 25.0 kJ/mol should be attributed to the threshold of 114.8±12.5 kJ/mol assigned in the experiment. But path A is a S-shift reaction (the barrier is 174.5 kJ/mol )and should make some contributions to the formation of ZrOS~+ at elevated energy.
For the NbS~+ (~3∑-, ~1Γ) with H_2O system, two possible reaction mechanisms have been studied by using B3LYP/6-311++G** method: the S/O exchange reaction which involves two hydrogen atoms migration from the O atom to the S atom (NbS~++H_2O→NbO~++H_2S) and the dehydrogenation reaction which involve the elimination of molecular hydrogen from the transition metal niobium center (NbS~++H_2O→NbOS~++H_2). According to the identified reaction mechanisms, a triplet–singlet surface crossing for the dehydrogenation is suggested. The triplet–single intersystem crossing is shown to play a crucial role for the reaction. The crossing point (CP) has been localized with the approach suggested by Yoshizawa et al. The spin-forbidden reaction 3NbS~+ (~3∑~- ) + H_2O→1NbOS~+-2 (1A’) + H_2 was found to be energetically much more favorable than the spin-allowed reaction ~3NbS~+ (~3∑~- ) + H_2O→~3NbO~+ (~3∑~- ) + H_2S. Besides, two possible H_2-elimination pathways and one possible H-elimination pathway have been identified on the two different surfaces. All theoretical results are in reasonable agreement with the experimental observations.
The reaction mechanism of N_2O + H_2→N_2 + H_2O cyclically catalyzed by the late third-row transition metal cation Ir~+ has been investigated on quintet and triplet potential energy surfaces ( PES ) at the CCSD(T)/ [ SDD + 6-311+G** // B3LYP / [ SDD + TZVP ] level of theory. The calculated potential energy surfaces indicate that the activation energy of the first oxidation reaction step of Ir~+ by N_2O is 42.8kJ/mol, which is the rate-determining step. However, the second reduction reaction step of IrO~+ by H_2 on the two surfaces are both kinetically and thermochemically barrierless. The identified reaction mechanisms and the potential energy surfaces indicate that the crossings between the quintet and triplet surfaces are unlikely to occur. Furthermore, both steps of the reaction are exothermic. The experimental observations are well explained.
在第一个反应体系中,我们利用B3LYP/6-311+G*和CCSD(T)/ SDD+6-311+G*两种方法研究了过渡金属氧化物阳离子ZrO~+与小分子CS_2的反应机理.根据理论计算,我们提出了关于三种产物ZrS~+, ZrS_2~+和ZrOS~+可能的反应通道和反应机理。研究发现,生成ZrS~+, ZrS_2~+的反应都经历了同一个四元环过渡态的O/S交换反应步骤,即通过过渡态TS12形成中间体IM2。IM2除了能直接解离生成ZrS~+产物外,还存在一个分子重排反应而生成产物ZrS_2~+。提出的分子重排反应机理合理地解释了反应没有经过ZrS~+中间体而生成产物ZrS_2~+的实验现象。对于生成ZrOS~+的产物找到了两个平行的反应通道( Path A和B)。Path B是一个插入—消去的反应机理,此通道需要克服25.0 kJ/mol的反应能垒。Path A是一个硫原子的转移反应,但反应能垒很高(174.5 kJ/mol),只有在高能量反应条件下Path A才对生成产物ZrOS~+会有贡献。
在第二个反应体系中,我们利用B3LYP/6-311++G**方法对NbS~+ ( 3∑-, 1Γ)和H_2O的反应进行了理论计算研究,我们发现反应是通过两种反应机理进行的:一个是氧硫交换反应:NbS~+中的S原子与H_2O中的O原子相互交换而得到产物NbO~+;另一个是脱H_2分子(伴随着解离出一个H原子而生成NbOSH+的副反应)而得到产物NbOS~+。对于脱H_2分子的过程,反应进行的最有利的途径是3NbS~+ ( 3∑- ) + H_2O→1NbOS~+-2 ( 1A’) + H_2。反应涉及两态,存在势能面交叉的现象。计算结果合理解释了实验上所观察到的现象。
在第三个反应体系中,我们在CCSD(T)/ [ SDD + 6-311+G** // B3LYP / [ SDD+ TZVP ]理论水平上研究了过渡金属离子Ir~+循环催化反应N_2O + H_2→N_2 + H_2O((1)N_2O + Ir~+→IrO~+ + N_2 (2)IrO~+ + H_2→Ir~++ H_2O)。计算结果表明:整个反应经过了两步过程,第一步是Ir~+从N_2O中夺取O原子生成IrO~+和H_2的过程,是整个反应的速率决定步骤,需要克服一个42.8kJ/mol的能垒;第二步是生成的IrO~+和H_2还原生成Ir~+和H_2O的过程,此过程不需要能垒。这两步反应都是自旋允许的反应,不存在势能面交叉。两个反应都是放热的过程。
Nowadays, the transition-metal-ion chemistry has been an active area for both experimental and theoretical studies. In industry, transition-metal oxides are used as versatile catalysts in many applications, however, for some processes their reactivity is too high and non-specific product formation occurs. In contrast, transition-metal sulfides are less reactive and susceptible to poisoning and can show higher selectivity. Transition metal sulfides also play a particular role in biochemistry in that heterometallic sulfur complexes form the active sites in several metalloenzymes. Besides, theoretical approaches to gas-phase transition-metal chemistry which involve two-state reactivity along reaction path have also been studied by many chemists. In this paper, on the basis of the molecular orbital theory, the transition state theory as well as quantum chemistry theory, three systems choosed have been studied using DFT method and coupled cluster CCSD (T) methods.
For the ~2△ground state of ZrO~+ with CS_2 system, the mechanisms for three products ZrS~+, ZrS_2~+ and ZrOS~+ have been studied by using B3LYP/6-311+G* and CCSD(T)/SDD+6-311+G* methods. It is found that both ZrS~+ and ZrS_2~+ formations involve the same O/S exchange process via a four-center transition state TS12 to form an intermediate IM2. Exception of that IM2 can dissociate into the ZrS~+ product, a favorable intramolecular rearrangement mechanism associated with the ZrS_2~+ formation has been identified, which explains why ZrS~+ was excluded as a precusor for the ZrS_2~+ formation and why the lower efficiency of the ZrS~+ formation was observed in experiment. For the formation of ZrOS~+, two parallel channels (path A and B) yielding their corresponding product isomer have been identified. Path B involving an insertion-elimination mechanism with a calculated barrier underestimated by ca. 25.0 kJ/mol should be attributed to the threshold of 114.8±12.5 kJ/mol assigned in the experiment. But path A is a S-shift reaction (the barrier is 174.5 kJ/mol )and should make some contributions to the formation of ZrOS~+ at elevated energy.
For the NbS~+ (~3∑-, ~1Γ) with H_2O system, two possible reaction mechanisms have been studied by using B3LYP/6-311++G** method: the S/O exchange reaction which involves two hydrogen atoms migration from the O atom to the S atom (NbS~++H_2O→NbO~++H_2S) and the dehydrogenation reaction which involve the elimination of molecular hydrogen from the transition metal niobium center (NbS~++H_2O→NbOS~++H_2). According to the identified reaction mechanisms, a triplet–singlet surface crossing for the dehydrogenation is suggested. The triplet–single intersystem crossing is shown to play a crucial role for the reaction. The crossing point (CP) has been localized with the approach suggested by Yoshizawa et al. The spin-forbidden reaction 3NbS~+ (~3∑~- ) + H_2O→1NbOS~+-2 (1A’) + H_2 was found to be energetically much more favorable than the spin-allowed reaction ~3NbS~+ (~3∑~- ) + H_2O→~3NbO~+ (~3∑~- ) + H_2S. Besides, two possible H_2-elimination pathways and one possible H-elimination pathway have been identified on the two different surfaces. All theoretical results are in reasonable agreement with the experimental observations.
The reaction mechanism of N_2O + H_2→N_2 + H_2O cyclically catalyzed by the late third-row transition metal cation Ir~+ has been investigated on quintet and triplet potential energy surfaces ( PES ) at the CCSD(T)/ [ SDD + 6-311+G** // B3LYP / [ SDD + TZVP ] level of theory. The calculated potential energy surfaces indicate that the activation energy of the first oxidation reaction step of Ir~+ by N_2O is 42.8kJ/mol, which is the rate-determining step. However, the second reduction reaction step of IrO~+ by H_2 on the two surfaces are both kinetically and thermochemically barrierless. The identified reaction mechanisms and the potential energy surfaces indicate that the crossings between the quintet and triplet surfaces are unlikely to occur. Furthermore, both steps of the reaction are exothermic. The experimental observations are well explained.
引文
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