具有磁性回收性能的钴纳米颗粒催化剂用于高选择性高性能环氧化合物羰基化制备β-内酯

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

摘要/Abstract

摘要：

环氧化物羰基化制备β-内酯是可持续化学生产的一条有吸引力的途径, 但该过程受[Co(CO)₄]^-的稳定性差的制约, 现有催化剂活性难以满足需求. 本文报道了一种负载在碳上的钴纳米粒子催化剂(Co-NPs-C), 该催化剂与[(TPP)CrCl]结合表现出较好的催化性能, 转化数和生产效率分别达到了230000和11000 mol/(mol-_Cr·h). 量子力学研究结果表明, 钴纳米粒子原位生成[Co(CO)₄]^-, 并与路易斯酸协同活化确保高的β-内酯选择性. 该催化剂具备磁性可回收, 可放大合成至200 g以上的优势, 为工业β-内酯合成提供了一个实用的平台, 并展示了基于纳米粒子钴催化的应用前景.

关键词: 环氧化物羰基化制备β-内酯, [Lewis acid]⁺[Co(CO)₄]^-, [Co(CO)₄]^-稳定性, 钴纳米粒子, 高活性催化剂

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. 具有磁性回收性能的钴纳米颗粒催化剂用于高选择性高性能环氧化合物羰基化制备β-内酯[J]. 催化学报, 2026, 86: 89-98.

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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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65044-9

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

图/表 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].

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