Cobalt nanoparticle catalyst with magnetic recoverability for high-performance epoxide carbonylation to β-lactones with high selectivity

doi:10.1016/S1872-2067(26)65044-9

Abstract

Abstract:

The carbonylation of epoxides to β-lactones is an attractive route for sustainable chemical production but remains constrained by the instability of [Co(CO)₄]^- and the limited activity of current catalysts. We report a cobalt nanoparticle catalyst supported on carbon (Co NPs-C) that, with [(TPP)CrCl], delivers unprecedented performance, achieving a turnover number (TON) of 230000 and a productivity of 11000 mol/(mol-_Cr·h). Mechanistic studies reveal in-situ generation of [Co(CO)₄]^- from Co NPs, with synergistic Lewis acid activation ensuring high β-lactone selectivity. The catalyst is recyclable and scalable to > 200 g, offering a practical platform for industrial β-lactone synthesis and highlighting the promise of nanoparticle-based cobalt catalysis.

Key words: Carbonylation of epoxide to β-lactone, [Lewis acid]⁺[Co(CO)₄]^-, [Co(CO)₄]^- stability, Cobalt nanoparticles, Highly active catalyst

Jianwei Jiang, Minji Kang, Jeongcheol Shin, Kiyoung Park, Sungho Yoon. Cobalt nanoparticle catalyst with magnetic recoverability for high-performance epoxide carbonylation to β-lactones with high selectivity[J]. Chinese Journal of Catalysis, 2026, 86: 89-98.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65044-9

https://www.cjcatal.com/EN/Y2026/V86/I7/89

Figures/Tables 6

Fig. 1. Characterization of Co NPs-C with XRD (a), TEM (b), and XPS (c-e).

Table 1 The results of the HO carbonylation reaction using Co NPs-C / [(TPP)CrCl] catalyst system.

Entry	HO:Cr:Co^a	T (°C)	Time (h)	Conv. ^b (%)	Selectivity^c (%)					β-lactone yield ^d (%)	β-lactone TON ^e
Entry	HO:Cr:Co^a	T (°C)	Time (h)	Conv. ^b (%)	lac.	ket.	ald.	iso.	hex.	β-lactone yield ^d (%)	β-lactone TON ^e
1 ^f	10000:1:1	60	24	>99	>98	<1	—	<1	—	97	9700
2	10000:1:33	80	12	>99	>97	<1	<1	<1	—	96	9600
3	100000:1:132	80	48	>99	>97	<1	—	<1	<1	96	96000
4	100000:1:66	80	48	>99	>97	<1	—	<1	<1	95	95000
5	200000:1:20	100	30	>99	>91	<1	<1	<1	6	90	180000
6	200000:1:20	100	10	>57	>96	<1	<1	<1	<1	55	110000
7 ^g	250000:1:66	80	120	>99	>93	<1	<1	<2	<3	92	230000
8 ^g	250000:1:20	80	120	>99	>93	<1	<1	<2	<3	92	230000
9 ^h	10000:1:33	80	12	>99	>97	<1	<1	<1	—	96	9600

Fig. 2. Comparative analysis of the TON based on reaction time between [(TPP)Cr(THF)2]+[Co(CO)4]- with additional 4 equivalent of NaCo(CO)4 (■) and Co NPs-C/[(TPP)CrCl] catalyst system (○) at 80 °C (HO:Cr:Co = 50000:1:5).

Fig. 3. (a) Recyclability test. Cycle 1-8: PO:Cr:Co = 10,000:1:33, 80 °C, 4 h in DME. Cycle 9: 16 h. (b) TEM characterization of Co NPs-C after 9 cycles.

Fig. 4. DFT-caculated reaction profiles for the PO carbonylation catalyzed by the [(TPP)Cr(THF)2]+[Co(CO)4]- catalyst (Lactone formation vs. ketone formation).

Scheme 1. A plausible pathway for epoxide carbonylation with Co NPs-C and [TPP)CrCl].

References

[1]	J. T. Lee, P. J. Thomas, H. Alper, J. Org. Chem., 2001, 66, 5424-5426.
[2]	H. D. Park, M. Dincă, Y. Román-Leshkov, ACS Cent. Sci., 2017, 3, 444-448.
[3]	A. W. Peters, Z. Li, O. K. Farha, ACS Cent. Sci., 2017, 3, 367-368.
[4]	T. L. Church, Y. D. Y. L. Getzler, C. M. Byrne, G. W. Coates, Chem. Commun., 2007, 657-674.
[5]	J. W. Kramer, J. M. Rowley, G. W. Coates, in: Organic Reactions, John Wiley & Sons, Inc., 2015.
[6]	S. Yoon, S. Rajendiran, J. Jiang, K. H. Park, US Patent 11,648,545 B2, 2023.
[7]	J. A. R. Schmidt, E. B. Lobkovsky, G. W. Coates, J. Am. Chem. Soc., 2005, 127, 11426-11435.
[8]	T. M. Bockman, J. K. Kochi, J. Am. Chem. Soc., 1989, 111, 4669-4683.
[9]	K. Y. Lee, J. K. Kochi, Inorg. Chem., 1989, 28, 567-578.
[10]	L. A. Lucia, K. Abboud, K. S. Schanze, Inorg. Chem., 1997, 36, 6224-6234.
[11]	H. van Rensburg, R. P. Tooze, D. F. Foster, S. Otto, Inorg. Chem., 2007, 46, 1963-1965.
[12]	F. Hebrard, P. Kalck, Chem. Rev., 2009, 109, 4272-4282.
[13]	Y. D. Y. L. Getzler, V. Mahadevan, E. B. Lobkovsky, G. W. Coates, J. Am. Chem. Soc., 2002, 124, 1174-1175.
[14]	T. L. Church, Y. D. Y. L. Getzler, G. W. Coates, J. Am. Chem. Soc., 2006, 128, 10125-10133.
[15]	J. M. Rowley, E. B. Lobkovsky, G. W. Coates, J. Am. Chem. Soc., 2007, 129, 4948-4960.
[16]	S. Rajendiran, P. Natarajan, S. Yoon, RSC Adv., 2017, 7, 4635-4638.
[17]	J. Jiang, S. Rajendiran, S. Yoon, Asian J. Org. Chem., 2019, 8, 151-154.
[18]	J. Jiang, S. Yoon, J. Mater. Chem. A, 2019, 7, 6120-6125.
[19]	H. Li, Y. Tang, Z. Li, Y. Li, B. Chen, C. Shen, Z. Huang, K. Dong, Mol. Catal., 2022, 533, 112779.
[20]	J. A. R. Schmidt, V. Mahadevan, Y. D. Y. L. Getzler, G. W. Coates, Org. Lett., 2004, 6, 373-376.
[21]	J. W. Kramer, E. B. Lobkovsky, G. W. Coates, Org. Lett., 2006, 8, 3709-3712.
[22]	V. Ganesan, S. Yoon, Catalysts, 2020, 10, 905.
[23]	L. He, J.-C. Yang, T.-T. Song, Y. Liu, X.-B. Lu, Eur. J. Inorg. Chem., 2022, 2022, e202200496.
[24]	X. Chen, Z. Ren, Y. Wang, J. Huang, Appl. Surf. Sci., 2025, 686, 162184.
[25]	S. Li, S. Liu, R. Yan, R. Xie, Q. Xue, B. Li, G.-P. Wu, Chem. Eur. J., 2025, 31, e202500571.
[26]	V. Mahadevan, Y. D. Y. L. Getzler, G. W. Coates, Angew. Chem. Int. Ed., 2002, 41, 2781-2784.
[27]	V. Ganesan, S. Yoon, Chin. J. Chem., 2023, 41, 3560-3566.
[28]	E. Baral, D. Kim, S. Lee, M. Park, J. Kim, Catalysts, 2019, 9, 311.
[29]	Y.-Y. Zhang, L. Yang, R. Xie, G.-W. Yang, G.-P. Wu, Macromolecules, 2021, 54, 9427-9436.
[30]	J. R. Lamb, A. K. Hubbell, S. N. MacMillan, G. W. Coates, J. Am. Chem. Soc., 2020, 142, 8029-8035.
[31]	L. Jens, L. Matthias, G. Christoph, R. Suresh, US 20220204465 A1, 2022.
[32]	J. Jiang, V. Ganesan, I. Choi, J. Shin, S. Yoon, K. Park, Chin. J. Catal., 2025, 68, 336-344.
[33]	V. Ganesan, S. Rajendiran, J. Jiang, S. Yoon, J. Catal., 2025, 451, 116381.
[34]	J. Jiang, S. Rajendiran, L. Piao, S. Yoon, Top. Catal., 2017, 60, 750-754.
[35]	V. Ganesan, S. Yoon, Inorg. Chem., 2020, 59, 2881-2889.
[36]	B. Liu, J.-G. Guan, Q. Wang, Q.-J. Zhang, Mater. Trans., 2005, 46, 1865-1867.
[37]	A. Das, S. Mondal, K. M. Hansda, M. K. Adak, D. Dhak, Appl. Catal. A, 2023, 649, 118955.
[38]	M. D. L. Balela, S. Yagi, Z. Lockman, A. Aziz, A. V. Amorsolo, E. Matsubara, J. Electrochem. Soc., 2009, 156, E139.
[39]	T. Fu, J. Lv, Z. Li, Ind. Eng. Chem. Res., 2014, 53, 1342-1350.
[40]	P. Xiao, Y. Wang, H. Du, Z. Yan, B. Xu, G. Li, Nanomaterials, 2023, 13, 2724.
[41]	R. Qiao, X.-L. Zhang, R. Qiu, Y. Li, Y. S. Kang, J. Phys. Chem. C, 2007, 111, 2426-2429.
[42]	N. Wu, L. Fu, M. Su, M. Aslam, K. C. Wong, V. P. Dravid, Nano Lett., 2004, 4, 383-386.
[43]	Q. Jia, Y. Gao, Y. Li, X. Fan, F. Zhang, G. Zhang, W. Peng, S. Wang, Carbon, 2019, 155, 287-297.
[44]	P.-C. Poon, Y. Wang, W. Li, D. W. Suen, W. W. Y. Lam, D. Z. J. Yap, B. L. Mehdi, J. Qi, X.-Y. Lu, E. Y. C. Wong, C. Yang, C.-W. Tsang, J. Mater. Chem. A, 2022, 10, 5580-5592.
[45]	C. Bock, C. Paquet, M. Couillard, G. A. Botton, B. R. MacDougall, J. Am. Chem. Soc., 2004, 126, 8028-8037.
[46]	Z. C. Orel, E. Matijević, D. V. Goia, J. Mater. Res., 2003, 18, 1017-1022.
[47]	Y. Holade, N. Sahin, K. Servat, T. Napporn, K. Kokoh, Catalysts, 2015, 5, 310-348.
[48]	J. Jiang, Y. Soo Lim, S. Park, S.-H. Kim, S. Yoon, L. Piao, Nanoscale, 2017, 9, 3873-3880.
[49]	J. Jiang, S. Yoon, L. Piao, CrystEngComm, 2020, 22, 4386-4392.
[50]	J. Jiang, J. Choi, S. Yoon, RSC Adv., 2023, 13, 10379-10383.
[51]	W. Gao, S. Liu, Z. Wang, J. Peng, Y. Zhang, X. Yuan, X. Zhang, Y. Li, Y. Pan, Energy Fuels, 2024, 38, 2526-2547.
[52]	J. Liu, J. Chen, J. Zhang, H. Lei, M. Dong, Catal. Lett., 2025, 155, 213.
[53]	C.-A. Liang, B. Zeng, B. Feng, H. Shi, F. Zhang, J. Liu, L. He, Y. Ding, C. Xia, Chin. J. Catal., 2025, 70, 115-141.
[54]	B. Zeng, L. Chen, G. Zhu, B. Yang, C. Xia, L. He, Mol. Catal., 2020, 494, 111109.
[55]	J. Luo, P. Liu, W. Yang, H. Niu, S. Li, C. Liang, Front. Chem., 2022, 10, 945028.
[56]	P. Zhang, L. An, C. Zhao, Q. Chang, F. Wang, C. Zhang, Y. Zhu, Y. Yang, Y. Li, Catal. Sci. Technol., 2024, 14, 2235-2243.
[57]	Z. Zheng, H. Zhou, L. Deng, X. Jia, Y. Li, J. Catal., 2024, 430, 115349.
[58]	P. Chini, V. Albano, J. Organomet. Chem., 1968, 15, 433-440.
[59]	P. Chini, V. Albano, S. Martinengo, J. Organomet. Chem., 1969, 16, 471-477.
[60]	K. M. Rao, G. Spoto, A. Zecchina, J. Catal., 1988, 113, 466-474.
[61]	P. Chini, Chem. Commun., 1967, 440-441.
[62]	K. M. Rao, G. Spoto, E. Guglielminotti, A. Zecchina, J. Chem. Soc., araday Trans. 1, 1988, 84, 2195.
[63]	C. Cesari, J.-H. Shon, S. Zacchini, L. A. Berben, Chem. Soc. Rev., 2021, 50, 9503-9539.
[64]	P. Ganji, D. J. Doyle, H. Ibrahim, Org. Lett., 2011, 13, 3142-3145.