MH+(M=Fe,Co,Ni)催化二氧化碳的氢化反应

doi:10.7503/cjcu20150680

摘要/Abstract

摘要：

在密度泛函理论的B3LYP 水平下计算了MH⁺(M=Fe, Co, Ni)催化二氧化碳的氢化反应. 研究表明, 氢转移至C上要比转移至O上容易得多. 探讨不同泛函方法对反应的影响, 从CCSD(T)的计算结果可见, 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.

关键词: MH+, 二氧化碳, 氢化, 密度泛函理论

Abstract:

Density functional theory(DFT) method at B3LYP level was conducted on the reaction of MH⁺(M=Fe, Co, Ni)-catalyzed hydrogenation of carbon dioxide. 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.

Key words: MH+, Carbon dioxide, Hydrogenation, Density functional theory

中图分类号:

O641

TrendMD:

张英男, 李吉来, 黄旭日. MH⁺(M=Fe,Co,Ni)催化二氧化碳的氢化反应. 高等学校化学学报, 2016, 37(3): 534.

ZHANG Yingnan, LI Jilai, HUANG Xuri. MH⁺(M=Fe, Co, Ni)-catalyzed Hydrogenation of Carbon Dioxide^†. Chem. J. Chinese Universities, 2016, 37(3): 534.

图/表 7

参考文献 21

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Species	d(M—H)/nm	d(X—H)/nm	d(M—O)/nm	d(C—O)/nm
MH⁺+CO₂	0.156/0.151/0.148			0.116
RC	0.155/0.150/0.147		0.209/0.207/0.203	0.118/0.118/0.118
TSC	0.173/0.196/0.212	0.150/0.123/0.118	0.193/0.184/0.179	0.126/0.131/0.133
IC		0.110/0.110/0.110	0.198/0.198/0.192	0.127/0.127/0.127
TSO	0.235/0.245/0.226	0.104/0.103/0.104		0.124/0.124/0.124
IO		0.097/0.097/0.097		0.129/0.129/0.129

Species	d(M—H)/nm	d(X—H)/nm	d(M—O)/nm	d(C—O)/nm
MH⁺+CO₂	0.156/0.151/0.148			0.116
RC	0.155/0.150/0.147		0.209/0.207/0.203	0.118/0.118/0.118
TSC	0.173/0.196/0.212	0.150/0.123/0.118	0.193/0.184/0.179	0.126/0.131/0.133
IC		0.110/0.110/0.110	0.198/0.198/0.192	0.127/0.127/0.127
TSO	0.235/0.245/0.226	0.104/0.103/0.104		0.124/0.124/0.124
IO		0.097/0.097/0.097		0.129/0.129/0.129

Species	ΔE/(kJ·mol^-1)
Species	BP86	TPSSh	B3LYP	PWPB95	B2PLYP	CCSD(T)	D3(B3LYP)
⁵FeH⁺+CO₂	0	0	0	0	0	0	0
⁵RC	-119.2	-126.4	-123.4	-123.8	-124.7	-102.9	-1.5
⁵TSO	107.1	141.0	138.9	151.0	147.3	238.9	-0.1
Species	ΔE/(kJ·mol^-1)
Species	BP86	TPSSh	B3LYP	PWPB95	B2PLYP	CCSD(T)	D3(B3LYP)
⁵IO	-65.7	-59.0	-37.2	-36.4	-25.9	-21.8	-0.4
⁵TSC	-11.7	-10.0	13.4	8.4	15.5	17.2	0
⁵IC	-149.0	-164.8	-143.1	-156.9	-147.3	-158.6	-0.2
MAD	42.3	38.4	24.9	26.1	21.6	0
⁴CoH⁺+CO₂	0	0	0	0	0	0	0
⁴RC	-95.4	-99.2	-97.5	-101.7	-102.1	-103.8	-1.4
⁴TSO	59.0	86.6	87.4	107.9	106.7	154.8	-0.1
⁴IO	-100.8	-99.2	-71.5	-72.0	-66.9	-33.9	-0.3
⁴TSC	-36.0	-38.5	-4.6	-2.5	1.7	18.8	0
⁴IC	-178.2	-203.3	-166.5	-177.8	-168.2	-165.7	-0.2
MAD	44.4	44.8	24.6	23.3	19.8	0
³NiH⁺+CO₂	0	0	0	0	0	0	0
³RC	-103.8	-105.4	-104.6	-105.9	-106.3	-109.6	-1.3
³TSO	80.3	119.7	110.0	110.5	87.4	144.8	0
³IO	-62.8	-46.0	-30.5	-41.0	-50.6	-5.0	-0.3
³TSC	3.3	28.9	52.7	69.5	67.4	76.1	-0.1
³IC	-113.8	-125.5	-97.5	-107.1	-96.7	-109.2	-0.2
MAD	38.7	25.1	13.4	14.2	19.2	0

Species	ΔE/(kJ·mol^-1)
Species	BP86	TPSSh	B3LYP	PWPB95	B2PLYP	CCSD(T)	D3(B3LYP)
⁵FeH⁺+CO₂	0	0	0	0	0	0	0
⁵RC	-119.2	-126.4	-123.4	-123.8	-124.7	-102.9	-1.5
⁵TSO	107.1	141.0	138.9	151.0	147.3	238.9	-0.1
Species	ΔE/(kJ·mol^-1)
Species	BP86	TPSSh	B3LYP	PWPB95	B2PLYP	CCSD(T)	D3(B3LYP)
⁵IO	-65.7	-59.0	-37.2	-36.4	-25.9	-21.8	-0.4
⁵TSC	-11.7	-10.0	13.4	8.4	15.5	17.2	0
⁵IC	-149.0	-164.8	-143.1	-156.9	-147.3	-158.6	-0.2
MAD	42.3	38.4	24.9	26.1	21.6	0
⁴CoH⁺+CO₂	0	0	0	0	0	0	0
⁴RC	-95.4	-99.2	-97.5	-101.7	-102.1	-103.8	-1.4
⁴TSO	59.0	86.6	87.4	107.9	106.7	154.8	-0.1
⁴IO	-100.8	-99.2	-71.5	-72.0	-66.9	-33.9	-0.3
⁴TSC	-36.0	-38.5	-4.6	-2.5	1.7	18.8	0
⁴IC	-178.2	-203.3	-166.5	-177.8	-168.2	-165.7	-0.2
MAD	44.4	44.8	24.6	23.3	19.8	0
³NiH⁺+CO₂	0	0	0	0	0	0	0
³RC	-103.8	-105.4	-104.6	-105.9	-106.3	-109.6	-1.3
³TSO	80.3	119.7	110.0	110.5	87.4	144.8	0
³IO	-62.8	-46.0	-30.5	-41.0	-50.6	-5.0	-0.3
³TSC	3.3	28.9	52.7	69.5	67.4	76.1	-0.1
³IC	-113.8	-125.5	-97.5	-107.1	-96.7	-109.2	-0.2
MAD	38.7	25.1	13.4	14.2	19.2	0