近日，中国科学院大连化学物理研究所刘中民院士团队报道了基于空间限域调控的沸石催化烯烃羰基化。这一研究成果发表在2026年10月21日出版的《自然》杂志上。

羰基化是生产醛、羧酸和酯的重要过程，通常由带有配体和碘化物助剂的均相金属配合物催化。Koch曾报道，无机酸中的质子也可以催化羰基化反应。此前研究表明，布朗斯特酸性沸石可作为醇和烯烃羰基化的多相Koch型催化剂，但该情况下产物仅限于叔羧酸。

研究组表明，有针对性地利用沸石中的空间限域并配合高CO/烯烃比，有助于突破这一限制。在使用FER沸石且CO/烯烃比为360时，烯烃羰基化可以以伯羧酸和仲羧酸为主要产物；乙烯羰基化制丙酸在100小时内实现了80%的选择性，丙烯羰基化制异丁酸在750小时内实现了95%的选择性。当CO/烯烃比分别降至24和90时，丙烯和乙烯羰基化的选择性分别降至61%和57%。

实验结合理论计算表明，FER沸石八元环（8-MR）空腔中的T2-O5是乙烯羰基化的主要活性位点，而十元环（10-MR）中的T3-O1是丙烯羰基化的主要活性位点。该发现为烯烃羰基化开辟了新方向，并为开发新型沸石基羰基化过程的先决条件提供了关键见解。

附：英文原文

Title: Zeolite-catalysed olefin carbonylation based on tuning spatial confinement

Author: Qi, Liang, Sheng, Yingying, Zhang, Wenna, Ni, Youming, He, Linhai, Li, Bin, Wang, Anjie, Zhu, Wenliang, Bell, Alexis T., Liu, Zhongmin

Issue&Volume: 2026-10-21

Abstract: Carbonylation is an important process used to produce aldehydes, carboxylic acids and esters1,2,3,4,5 that is usually catalysed by homogeneous metal complexes with ligands and iodide promoters6,7,8,9,10,11,12. Koch has reported that protons of mineral acids can also catalyse carbonylation13. Previous studies have demonstrated that Brnsted acidic zeolites can act as a heterogeneous, Koch-type catalyst for carbonylation of alcohols and olefins, but the products in this case are limited to tertiary carboxylic acids14,15,16,17,18. Here we show that targeted use of spatial confinement in a zeolite together with a high CO/olefin ratio can help break this limitation. We report that, with FER zeolite and a CO/olefin ratio of 360, olefin carbonylation can produce primary and secondary carboxylic acids as the main products; ethylene carbonylation to propanoic acid (PA) is achieved with 80% selectivity over 100h and propylene carbonylation to isobutyric acid (IBA) is achieved with 95% selectivity over 750h. The propylene and ethylene carbonylation selectivities decrease to 61% and 57%, respectively, as the CO/olefin ratio decreases to 24 and 90, respectively. Experiments in combination with theoretical calculations suggest that T2-O5 in eight-membered ring (8-MR) cavities of FER zeolite are the primary active sites for ethylene carbonylation and T3-O1 in ten-membered rings (10-MRs) are the primary active sites for propylene carbonylation. Our findings open new directions for olefin carbonylation and provide critical insights into the prerequisites for developing new zeolite-based carbonylation processes.

DOI: 10.1038/s41586-026-11183-2

Source: https://www.nature.com/articles/s41586-026-11183-2