Theoretical Study on Mechanism of CO2 Hydrogenation to Formic Acid Catalyzed by Manganese Complex †

doi:10.7503/cjcu20190292

Abstract

Abstract:

Density functional theory(DFT) was used to study the mechanism of carbon dioxide hydrogenation to formic acid catalyzed by manganese complex. The whole catalytic cycle mainly includes two stages of hydrogen activation and carbon dioxide hydrogenation. The calculation results show that the participation of formic acid significantly reduces the reaction energy barrier of hydrogen activation. The hydrogenation process of carbon dioxide follows the outer-sphere mechanism and hydrogen transfer is a stepwise process, in which the hydride transfer is the rate-determining step, with an energy barrier of 21.0 kJ/mol. In addition, the modulation effect of R group on S atom was explored. The results show that when R is an electron-withdrawing group, it can reduce the activation barriers of hydrogen cracking and proton transfer during carbon dioxide hydrogenation. The transfer of hydride is facilitated when the R group is an electron-donating group. When R=CF₃, the energy span of the whole reaction is the smallest, which is 80.4 kJ/mol.

Key words: Manganese complex, Hydrogen activation, Carbon dioxide hydrogenation, Reaction mechanism, Density functional theory

CLC Number:

O641

TrendMD:

ZHANG Lin, ZHANG Wei, YUE Xin, LI Pengjie, YANG Zuoyin, PU Min, LEI Ming. Theoretical Study on Mechanism of CO₂ Hydrogenation to Formic Acid Catalyzed by Manganese Complex ^†[J]. Chem. J. Chinese Universities, 2019, 40(9): 1911.

Figures/Tables 6

Fig.1 Catalytic reaction mechanism

Fig.2 Gibbs free energy profiles of hydrogen activation process

Fig.3 Geometric parameters of key intermediates and transition states in hydrogen activation Bond lengths are in nm.

Fig.4 Gibbs free energy profiles of carbon dioxide hydrogenation process

Fig.5 Geometric parameters of key intermediates and transition states in the hydrogenation of carbon dioxide Bond lengths are in nm, angles are in degree.

Fig.6 Effect of R group modulation on Gbbis free energy in the whole catalytic cycle(A) and effect of R group modulation on the energy span, the energy barrier of hydride and proton transfer(B)

References 34

[1]	Kennedy J. F., Shimizu J., ,. Carbohyd. Polym. 1995, 26( 1), 81— 82
[2]	Klein H. F., ,. Ber. Bunsen-Ges. Phys. Chem. 1989, 93( 7), 827
[3]	Aresta M., Quaranta E., Tommasi I., Giannoccaro P., Ciccarese A., ,. Gazz. Chim. Ital. 1995, 125( 11), 509— 538
[4]	Baiker A., ,. Appl. Organomet. Chem. 2000, 14( 12), 751— 762
[5]	Schuchmann K., Müller V ., Science 2013, 342( 6164), 1382— 1385
[6]	Wang W., Wang S. P., Ma X. B., Gong J. L., ,. Chem. Soc. Rev. 2011, 40( 7), 3703— 3727
[7]	Mellmann D., Sponholz P., Junge H., Beller M., ,. Chem. Soc. Rev. 2016, 45( 14), 3954— 3988
[8]	Eppinger J., Huang K. W., ,. ACS Energy Lett. 2016, 2( 1), 188— 195
[9]	Moret S., Dyson P. J., Laurenczy G., ,. Nat. Commun. 2014, 5, 4017
[10]	Kayaki Y., Shimokawatoko Y., Ikariya T., ,. Inorg. Chem. 2007, 46( 14), 5791— 5797
[11]	Darensbourg D. J., Yoder J. C., Holtcamp M. W., Klausmeyer K. K., Reibenspies J. H., ,. Inorg. Chem. 1996, 35( 16), 4764— 4769
[12]	Walther D., Ruben M., Rau S., ,. Coord. Chem. Rev. 1999, 182( 1), 67— 100
[13]	Hutschka F., Dedieu A., Eichberger M., Fornika R., Leitner W., ,. J. Am. Chem. Soc. 1997, 119( 19), 4432— 4443
[14]	Munshi P., Main A. D., Linehan J. C., Tai C. C., Jessop P. G., ,. J. Am. Chem. Soc. 2002, 124( 27), 7963— 7971
[15]	Ohnishi Y. Y., Nakao Y., Sato H., Sakaki S ., Organometallics 2006, 25( 14), 3352— 3363
[16]	Arup M., Alexander N., Gregory L., Shimon L. J. W., Yehoshoa B. D., Angel E. J. N., Milstein D., ,. J. Am. Chem. Soc. 2016, 138( 13), 4298— 4301
[17]	Elangovan S., Topf C., Fischer S., Jiao H., Spannenberg A., Baumann W., Ludwig R., Junge K., Beller M., ,. J. Am. Chem. Soc. 2016, 138( 28), 8809— 8814
[18]	Das K., Mondal A., Srimani D., ,. Chem. Commun. 2018, 54( 75), 10582— 10585
[19]	Das K., Mondal A., Pal D., Srivastava H. K., Srimani D ., Organometallics 2019, 38( 8), 1815— 1825
[20]	Chai J. D., Head-Gordon M., ,. Phys. Chem. Chem. Phys. 2008, 10( 44), 6615— 6620
[21]	Frisch M J. . Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Scalmani G., Barone V., Mennucci B., Petersson G. A., Nakatsuji H., Caricato M., Li X., Hratchian H. P., Izmaylov A. F., Bloino J., Zheng G., Sonnenberg J. L., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Vreven T., Montgomery J. A. Jr., Peralta J. E., Ogliaro F., Bearpark M., Heyd J. J., Brothers E., Kudin K. N., Staroverov V. N., Keith T., Kobayashi R., Normand J., Raghavachari K., Rendell A., Burant J. C., Iyengar S. S., Tomasi J., Cossi M., Rega N., Millam J. M., Klene M., Knox J. E., Cross J. B., Bakken V., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochterski J. W., Martin R. L., Morokuma K., Zakrzewski V. G., Voth G. A., Salvador P., Dannenberg J. J., Dapprich S., Daniels A. D., Farkas O., Foresman J. B., Ortiz J. V., Cioslowski J., Fox D. J., Gaussian 09, Revision B, Gaussian Inc., Wallingford, CT, 2010
[22]	Wang M., Zhang X., Chen Z., Tang Y. H., Lei M., ,. Sci. China Chem. 2014, 57( 9), 1264— 1275
[23]	Lei M., Wang Z. D., Du X. J., Zhang X., Tang Y. H., ,. J. Phys. Chem. A 2014, 118( 39), 8960— 8970
[24]	Ma X. L., Tang Y. H., Lei M., ,. Dalton Trans. 2014, 43( 30), 11658— 11666
[25]	Lei M., Ma X. L., Pan Y. H., ,. Eur. J. Inorg. Chem. 2015, 2015( 5), 794— 803
[26]	Ma X. L., Lei M., Liu S. B ., Organometallics 2015, 34( 7), 1255— 1263
[27]	Li H., Ma X. L., Lei M., ,. Dalton Trans. 2016, 45( 20), 8506— 8512
[28]	Li L. F., Pan Y. H., Lei M., ,. Catal. Sci. Technol. 2016, 6( 12), 4450— 4457
[29]	Zhang Y. W., Ma X. L., Zhang X., Lei M., ,Acta Chim. Sinica, 2016,74( 4), 340— 350 doi: 10.6023/A15120781
	(张益伟, 马雪璐, 张欣, 雷鸣.化学学报,2016,74(4), 340— 350) doi: 10.6023/A15120781
[30]	Yue X., Li L. F., Li P. J., Luo C. G., Pu M., Yang Z. Y., Lei M., ,. Chinese J. Chem. 2019, 37( 8), 883— 886
[31]	Xiao M., Yue X., Xu R. R., Tang W. J., Xue D., Li C. Q., Lei M., Xiao J. L., Wang C., ,. Angew. Chem. Int. Ed. 2019, 58( 31), 10528— 10536
[32]	Musashi Y., Sakaki S., ,. J. Am. Chem. Soc. 2002, 124( 25), 7588— 7603
[33]	Filonenko G. A., Hensen E. J. M., Pidko E. A., ,. Catal. Sci. Technol. 2014, 4( 10), 3474— 3485
[34]	Yin C. Q., Xu Z. T., Yang S. Y., Ng S. M., Wong K. Y., Lin Z. Y., Lau C. P ., Organometallics 2001, 20( 6), 1216— 1222

Theoretical Study on Mechanism of CO₂ Hydrogenation to Formic Acid Catalyzed by Manganese Complex ^†

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 6

References 34

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	HE Hongrui, XIA Wensheng, ZHANG Qinghong, WAN Huilin. Density-functional Theoretical Study on the Interaction of Indium Oxyhydroxide Clusters with Carbon Dioxide and Methane [J]. Chem. J. Chinese Universities, 2022, 43(8): 20220196.
[2]	ZHOU Zixuan, YANG Haiyan, SUN Yuhan, GAO Peng. Recent Progress in Heterogeneous Catalysts for the Hydrogenation of Carbon Dioxide to Methanol [J]. Chem. J. Chinese Universities, 2022, 43(7): 20220235.
[3]	YANG Dan, LIU Xu, DAI Yihu, ZHU Yan, YANG Yanhui. Research Progress in Electrocatalytic CO₂ Reduction Reaction over Gold Clusters [J]. Chem. J. Chinese Universities, 2022, 43(7): 20220198.
[4]	WONG Honho, LU Qiuyang, SUN Mingzi, HUANG Bolong. Rational Design of Graphdiyne-based Atomic Electrocatalysts： DFT and Self-validated Machine Learning [J]. Chem. J. Chinese Universities, 2022, 43(5): 20220042.
[5]	SUN Cuihong, LYU Liqiang, LIU Ying, WANG Yan, YANG Jing, ZHANG Shaowen. Mechanism and Kinetics on the Reaction of Isopropyl Nitrate with Cl， OH and NO₃ Radicals [J]. Chem. J. Chinese Universities, 2022, 43(2): 20210591.
[6]	LIU Yang, LI Wangchang, ZHANG Zhuxia, WANG Fang, YANG Wenjing, GUO Zhen, CUI Peng. Theoretical Exploration of Noncovalent Interactions Between Sc₃C₂@C₈₀ and ［12］Cycloparaphenylene Nanoring [J]. Chem. J. Chinese Universities, 2022, 43(11): 20220457.
[7]	CHENG Yuanyuan, XI Biying. Theoretical Study on the Fragmentation Mechanism of CH₃SSCH₃ Radical Cation Initiated by OH Radical [J]. Chem. J. Chinese Universities, 2022, 43(10): 20220271.
[8]	ZHOU Chengsi, ZHAO Yuanjin, HAN Meichen, YANG Xia, LIU Chenguang, HE Aihua. Regulation of Silanes as External Electron Donors on Propylene/butene Sequential Polymerization [J]. Chem. J. Chinese Universities, 2022, 43(10): 20220290.
[9]	WANG Yuanyue, AN Suosuo, ZHENG Xuming, ZHAO Yanying. Spectroscopic and Theoretical Studies on 5-Mercapto-1，3，4-thiadiazole-2-thione Microsolvation Clusters [J]. Chem. J. Chinese Universities, 2022, 43(10): 20220354.
[10]	ZHONG Shengguang, XIA Wensheng, ZHANG Qinghong, WAN Huilin. Theoretical Study on Direct Conversion of CH₄ and CO₂ into Acetic Acid over MCu₂O_x（M = Cu²⁺， Ce⁴⁺， Zr⁴⁺） Clusters [J]. Chem. J. Chinese Universities, 2021, 42(9): 2878.
[11]	MA Lijuan, GAO Shengqi, RONG Yifei, JIA Jianfeng, WU Haishun. Theoretical Investigation of Hydrogen Storage Properties of Sc， Ti， V-decorated and B/N-doped Monovacancy Graphene [J]. Chem. J. Chinese Universities, 2021, 42(9): 2842.
[12]	MENG Fanwei, GAO Qi, YE Qing, LI Chenxi. Potassium Poisoning Mechanism of Cu-SAPO-18 Catalyst for Selective Catalytic Reduction of NO_x by Ammonia [J]. Chem. J. Chinese Universities, 2021, 42(9): 2832.
[13]	HUANG Luoyi, WENG Yueyue, HUANG Xuhui, WANG Chaojie. Theoretical Study on the Structures and Properties of Flavonoids in Plantain [J]. Chem. J. Chinese Universities, 2021, 42(9): 2752.
[14]	WANG Jian, ZHANG Hongxing. Theoretical Study on the Structural-photophysical Relationships of Tetra-Pt Phosphorescent Emitters [J]. Chem. J. Chinese Universities, 2021, 42(7): 2245.
[15]	LI Xinyi, LIU Yongjun. Theoretical Insights into the Cleavage of β-Hydroxy Ketone Catalyzed by Artificial Retro-aldolase RA95.5-8F [J]. Chem. J. Chinese Universities, 2021, 42(7): 2306.