Outlook of Cobalt-Based Catalysts for Heterogeneous Hydroformylation of Olefins: From Nanostructures to Single Atoms

Abstract

Hydroformylation of olefins, as a study of olefinic downstream derivative production, is of great relevance in chemical production. Heterogeneous hydroformylation is beneficial for catalyst separation and recycling compared to homogeneous systems. Cobalt is a cheap metal with excellent catalytic activity in hydroformylation as well as the precious metal rhodium. Therefore, the research on cobalt-based catalysts for heterogeneous hydroformylation has great value and significance. The nano or atomic structures of cobalt-based catalysts have significant impact on the catalytic behaviors of the hydroformylation process. There is rarely the design principles report on how to achieve significant improvement in hydroformylation performance by regulating the structure of the cobalt-based catalyst. Herein, we review the recent research progress on heterogeneous hydroformylation by cobalt-based catalysts with different metal sizes (from nanostructures to single atoms). On the basis of the difference in the catalytic mechanism between homogeneous and heterogeneous hydroformylation, we summarize and propose the regulation principles to enhance the activity and stability of cobalt-based catalysts in hydroformylation, where single-atom engineering is expected to achieve unity of high activity and stability of cobalt-based catalysts for hydroformylation applications. At the end of this review, we present an outlook on the opportunities and challenges in developing cobalt-based catalysts for heterogeneous hydroformylation.

K-promoted cobalt-based catalysts for heterogeneous hydroformylation

“…The as-obtained aldehydes can serve as important intermediates for various bulk chemicals (alcohols, esters, acids, and amines). 1,2 Currently, only cobalt carbonyl and rhodium-based catalysts with phosphine ligands have been used in industry. 3 However, the difficulty in separating the products from homogeneous catalysts poses a significant obstacle to achieve efficient catalyst recovery and recycling for subsequent use.…”

Developing and Understanding Leaching-Resistant Cobalt Nanoparticles Via N/P Incorporation for Liquid Phase Hydroformylation

“…Finally, Hou et al demonstrated that the incorporation of phosphorus helps to stabilize cobalt single atoms in ZrP-supported Co materials. In this regard, a recent review from from Pan et al indicated that many studies have shown that Co-based catalysts suffer from low activity and poor cycling stability, highlighting the importance of exploring new robust cobalt heterogeneous catalysts for this reaction [23].…”