Co-doped Metal-Organic Framework as a Heterogeneous Catalyst for Ethylene Dimerization

doi:10.1007/s40242-025-5014-z

Abstract

Abstract: The Co-MOF-5 catalyst was synthesized by substituting Zn²⁺ ions with Co²⁺ ions within the Zn₄O metal clusters of MOF-5, achieved via direct agitation at room temperature. The removal of solvent molecules that exhibit additional coordination with Co²⁺ can be accomplished through high-temperature treatment, thereby enabling the catalyst to function effectively in ethylene dimerization reactions. At 10 atm (1 atm=101325 Pa) and 25 °C, with Et₂AlCl as a cocatalyst, it showed significant activity and 1-C4 selectivity. At a Co/(Co+Zn) molar ratio of 20%, the oligomerization activity of ethylene was observed to be 5.38×10⁵ g·mol^-1·h^-1. Additionally, the selectivity for C4 products was recorded at 97.11%, with 1-butene constituting 88.06% of the resultant product. Density functional theory (DFT) calculations corroborated that the ethylene oligomerization process catalyzed by Co-MOF-5 adheres to the Cossee-Arlman mechanism. Co-MOF-5 not only facilitates the dimerization process effectively but also directs the reaction pathway to preferentially yield 1-C4. Consequently, Co-MOF-5 presents significant potential for applications in industrial catalysis and organic synthesis, particularly in processes that necessitate highly selective products. By further optimizing and modifying the structure and reaction conditions of Co-MOF-5, it is anticipated that its catalytic performance can be enhanced, thereby advancing the development and application of ethylene dimerization reaction technologies.

Key words: Metal-organic framework, Ethylene dimerization, Heterogeneous, Catalysis, Density functional theory (DFT)

NING Yao, ZHAO Bo, MIN Wenpeng, LI Changlian, LIU Pengxiao, JIA Yan, LI Xinyuan, ZHANG Ying. Co-doped Metal-Organic Framework as a Heterogeneous Catalyst for Ethylene Dimerization[J]. Chemical Research in Chinese Universities, 2025, 41(3): 601-610.

References

[1] Breuil P. A. R., Magna L., Olivier-Bourbigou H., Catal. Lett., 2015, 145, 173.
[2] Kissin Y. V.; Ed.: Kirk-Othmer, Kirk-Othmer Encyclopedia of Chemical Technology, 1st ed., Wiley, New York, 2015.
[3] Bender M., ChemBioEng Rev., 2014, 1, 136.
[4] Chau N. T. K., Kim S., Lee H.-J., Lee M., Chung Y. M., Chem. Commun., 2024, 60, 168.
[5] Belov G. P., Matkovsky P. E., Pet. Chem., 2010, 50, 283.
[6] Sydora O. L., Organometallics, 2019, 38, 997.
[7] McGuinness D. S., Chem. Rev., 2011, 111, 2321.
[8] Petit J., Magna L., Coord. Chem. Rev., 2022, 450, 214227.
[9] Alenezi H., Alwi S. R. W., Manan Z. A., Zaidel D. N. A., International Journal of Innovative Technology and Exploring Engineering, 2019, 8, 3969.
[10] Al-Sa’doun A.W., Appl. Catal. A: Gen., 1993, 105, 1.
[11] Rajapaksha R., Samanta P., Quadrelli E. A., Canivet J., Chem. Soc. Rev., 2023, 52, 8059.
[12] Olivier-Bourbigou H., Breuil P. A. R., Magna L., Michel T., Espada Pastor M. F., Delcroix D., Chem. Rev., 2020, 120, 7919.
[13] Canivet J., Aguado S., Schuurman Y., Farrusseng D., J. Am. Chem. Soc., 2013, 135, 4195.
[14] Joubert J., Delbecq F., Sautet P., Le Roux E., Taoufik M., Thieuleux C., Blanc F., Cope ́ret C., Thivolle-Cazat J., Basset J. M., J. Am. Chem. Soc., 2006, 128, 9157.
[15] Corriu R. J. P., Mehdi A., Reyé C., Thieuleux C., Frenkel A., Gibaud A., New J. Chem., 2004, 28, 156.
[16] Yaghi O. M., O’Keeffe M., Ockwig N. W., Chae H. K., Eddaoudi M., Kim J., Nature, 2003, 423, 705.
[17] Furukawa H., Cordova K. E., O’Keeffe M., Yaghi O. M., Science, 2013, 341, 1230444.
[18] Yuan S., Feng L., Wang K., Pang J., Bosch M., Lollar C., Sun Y. J., Qin J. S., Yang X. Y., Zhang P., Wang Q., Zou L. F., Zhang Y. M., Zhang L. L., Fang Y., Li J. L., Zhou H.C., Adv. Mater., 2018, 30, 1704303.
[19] Wang C., Liu D., Lin W., J. Am. Chem. Soc., 2013, 135, 13222.
[20] Metzger E. D., Brozek C. K., Comito R. J., Dincă M., ACS Cent. Sci., 2016, 2, 148.
[21] Metzger E. D., Comito R. J., Wu Z., Zhang G., Dubey R. C., Xu W., Miller J. T., Dinca M., ACS Sustain. Chem. Eng., 2019, 7, 6654.
[22] Madrahimov S. T., Gallagher J. R., Zhang G., Meinhart Z., Garibay S. J., Delferro M., Miller J. T., Farha O. K., Hupp J. T., Nguyen S. T., ACS Catal., 2015, 5, 6713.
[23] Chen C., Alalouni M. R., Dong X., Cao Z., Cheng Q., Zheng L., Meng L., Guan C., Liu L., Abou-Hamad E., Wang J., Shi Z., Huang K., Cavallo L., Han Y., J. Am. Chem. Soc., 2021, 143, 7144.
[24] Chen W., Elumalai P., Mamlouk H., Rentería‐Gómez Á., Veeranna Y., Shetty S., Kumar D., Al-Rawashdeh M., Gupta S. S., Gutierrez O., Zhou H., Madrahimov S. T., Adv. Sci., 2024, 11, 2309540.
[25] Tranchemontagne D. J., Hunt J. R., Yaghi O. M., Tetrahedron, 2008, 64, 8553.
[26] Frisch M. J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Scalmani G., Barone V., Petersson G. A., Nakatsuji H., Li X., Caricato M., Marenich A. V., Bloino J., Janesko B. G., Gomperts R., Mennucci B., Hratchian H. P., Ortiz J. V., Izmaylov A. F., Sonnenberg J. L., Williams-Young D., Ding F., Lipparini F., Egidi F., Goings J., Peng B., Petrone A., Henderson T., Ranasinghe D., Zakrzewski V. G., Gao J., Rega N., Zheng G., Liang W., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Vreven T., Throssell K., Montgomery Jr. J. A., Peralta J.E., Ogliaro F., Bearpark M. J., Heyd J. J., Brothers E. N., Kudin K. N., Staroverov V. N., Keith T. A., Kobayashi R., Normand J., Raghavachari K., Rendell A. P., Burant J. C., Iyengar S. S., Tomasi J., Cossi M., Millam J. M., Klene M., Adamo C., Cammi R., Ochterski J. W., Martin R. L., Morokuma K., Farkas O., Foresman J. B., Fox D. J., Gaussian˜09 Revision D.01, 2009.
[27] Lee C., Yang W., Parr R. G., Phys. Rev. B, 1988, 37, 785.
[28] Becke A. D., J. Chem. Phys., 1993, 98, 5648.
[29] Becke A. D., Phys. Rev. A, 1988, 38, 3098.
[30] Grimme S., Chem.: Eur. J., 2012, 18, 9955.
[31] Liu L., Liu Z., Tang S., Cheng R., He X., Liu B., ACS Catal., 2019, 9, 10519.
[32] Lu T., Chen Q., Comput. Theor. Chem., 2021, 1200, 113249.
[33] Caskey S. R., Matzger A. J., Inorg. Chem., 2008, 47, 7942.
[34] Chen C., Meng L., Alalouni M. R., Dong X., Wu Z., Zuo S., Zhang H., Small, 2023, 19, 2301235.
[35] Li H., Shi W., Zhao K., Li H., Bing Y., Cheng P., Inorg. Chem., 2012, 51, 9200.
[36] Botas J. A., Calleja G., Sánchez-Sánchez M., Orcajo M. G., Langmuir, 2010, 26, 5300.
[37] Ravel B., Newville M., J. Synchrot. Radiat., 2005, 12, 537.
[38] Zabinsky S. I., Rehr J. J., Ankudinov A., Albers R. C., Eller M. J., Phys. Rev. B, 1995, 52, 2995.
[39] Hu Y., Zhang Y., Han Y., Sheng D., Shan D., Liu X., Cheng A., ACS Appl. Nano Mater., 2019, 2, 136.
[40] Bernales V., League A. B., Li Z., Schweitzer N. M., Peters A. W., Carlson R. K., Hupp J. T., Cramer C. J., Farha O. K., Gagliardi L., J. Phys. Chem. C, 2016, 120, 23576.
[41] Wang C., Li G., Guo H., Catalysts, 2023, 13, 640.
[42] Andrei R. D., Popa M. I., Fajula F., Hulea V., J. Catal., 2015, 323, 76.
[43] Liu B., Jie S., Bu Z., Li B.-G., RSC Adv., 2014, 4, 62343.
[44] Löbbert L., Chheda S., Zheng J., Khetrapal N., Schmid J., Zhao R., Gaggioli C. A., Camaioni D. M., Bermejo-Deval R., Gutiérrez O. Y., Liu Y., Siepmann J. I., Neurock M., Gagliardi L., Lercher J. A., J. Am. Chem. Soc., 2023, 145, 1407.