Metal-organic framework-supported palladium(II) single-site as a solid catalyst for the hydroformylation and hydroxycarbonylation of styrene with formic acid
Journal
Applied Catalysis B: Environmental
Journal Volume
382
Start Page
125952
ISSN
09263373
Date Issued
2026-03
Author(s)
Abstract
Although hydroformylation and hydroxycarbonylation of olefin with syngas are two of the most important chemical processes in the industry, with over 10 million tons of chemicals produced annually with the processes, harsh conditions for the reactions remain the major challenge in the industry. To address this issue, formic acid, an eco-friendly and sustainable energy carrier, has been recently introduced as a carbon monoxide and hydrogen source to provide a green alternative for the reactions. However, both hydroformylation and hydroxycarbonylation of olefin with formic acid are so far catalyzed by homogeneous catalysts, which limit the reusability of the catalyst, and the use of heterogeneous catalysts for the reaction has not been reported yet. Herein, heterogeneous catalysts, Pd(II)-MOF-808 and Pd(II)-PPh3-MOF-808, were for the first time applied for the hydroformylation and hydroxycarbonylation of styrene with formic acid, respectively. The open metal sites in MOF-808 not only allowed the immobilization of single-site Pd(II) but also enable functionalization with a phosphorous compound that anchors the Pd(II) complex. Under mild reaction conditions (80 ℃ for 24 h), a 73 % yield of 3-phenylpropanal was achieved with very high selectivity (> 99 %) over Pd(II)-MOF-808, while a 52 % yield of 3-phenylpropanoic acid was maintained over five cycles with Pd(II)-PPh3-MOF-808, hence, highlighting the efficiency of the as-synthesized single-site catalyst. Moreover, DFT calculations showed that the nucleophilicity and structure of ligand play a key role in determining product distribution.
Subjects
Formic acid
Heterogeneous catalysis
Hydroformylation
Hydroxycarbonylation
MOF-808
Palladium single-site
Publisher
Elsevier B.V.
Type
journal article