Controlling Reaction Pathways of Ethylene Hydroformylation Using Isolated Bimetallic Rhodium–Cobalt Sites

Yuan, Yong; Mou, Tianyou; Hwang, Sooyeon; Porter, William N.; Liu, Ping; Chen, Jingguang G.

doi:10.1021/jacs.5c01105

Controlling Reaction Pathways of Ethylene Hydroformylation Using Isolated Bimetallic Rhodium–Cobalt Sites

Journal Article · Sat Mar 29 00:00:00 EDT 2025 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.5c01105· OSTI ID:2560705

Yuan, Yong ^[1]; Mou, Tianyou ^[1]; ^[2]; ^[3]; ^[1]; ^[4]

Brookhaven National Laboratory (BNL), Upton, NY (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Columbia Univ., New York, NY (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States); Columbia Univ., New York, NY (United States)

Designing efficient ligand-free heterogeneous catalysts for ethylene hydroformylation to produce C₃ oxygenates is of importance for both fundamental research and practical applications, but it is often hindered by insufficient catalytic activity and selectivity. Here, this work designs isolated rhodium–cobalt (Rh–Co) sites confined within a ZSM-5 zeolite to enhance ethylene hydroformylation rates and selectivity while maintaining catalyst stability. By adjusting the Co/Al ratio in Co-ZSM-5, different sizes of Co are formed; subsequent Rh introduction produces isolated Rh₁Co_x clusters with different Rh–Co coordination numbers (CNs). In-situ characterizations and density functional theory calculations reveal that a Rh–Co CN of 3, corresponding to an isolated Rh₁Co₃ site, provides optimal bindings to reaction intermediates and thus achieves the highest hydroformylation rates among supported Rh-based catalysts. This study demonstrates the role of coordination-tuning via a secondary metal in effectively controlling the reaction pathway over single Rh atom catalysts.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012704; SC0012653; AC02-05CH11231

OSTI ID:: 2560705

Report Number(s):: BNL--228015-2025-JAAM

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 14 Vol. 147; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Controlling Reaction Pathways of Ethylene Hydroformylation Using Isolated Bimetallic Rhodium–Cobalt Sites

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