2026-10-07T02:28:00Z https://api.figshare.com/v2/oai

oai:figshare.com:article/34047261 2026-10-01T17:09:22Z category_1 category_4 category_16 category_873 category_45 category_734 portal_63 item_type_6 month_year_10_2026

Research on Silane-Free CO₂ Hydroformylation: Reaction Mechanisms with Ru₃(CO)₁₂ and Phosphine Catalysts Zhangxinyu Fan (19840088) Yiheng Cui (25157556) Weixiang Wang (402971) Yi Sun (118759) Liqian Lin (17811764) Xinxin Geng (2175290) Guo Tian (1424119) Qin Zhong (566779) Boyang Liu (1894453) Biophysics Biochemistry Physiology Chemical Sciences not elsewhere classified Sociology Biological Sciences not elsewhere classified produce valuable aldehydes different phosphine ligands formic acid alters reaction conditions reveal 2 </ sub 12 </ sub hydroformylation allows olefins acid additives reaction mechanisms profitable reaction two reactions temperature mismatch subsequent high spurred interest rational design olefin carbonylation mechanism understanding experimental evaluations energy barrier competitive relationship carbon fixation also paves activation pathway Global warming has spurred interest in CO₂ utilization. Coupling reverse water–gas shift (RWGS) with hydroformylation allows olefins to react with H₂/CO₂ to produce valuable aldehydes, which is a profitable reaction and helps with carbon fixation. However, temperature mismatch between the two reactions and limited mechanistic understanding hinder the rational design of catalysts. Using density functional theory (DFT) calculations and experimental evaluations, we investigated the effects of different phosphine ligands and acid additives on the performance of silane-free CO₂ hydroformylation. Formic acid alters the CO₂ activation pathway and reduces the energy barrier, thereby improving catalytic activity and chemoselectivity. The effects of reaction conditions reveal a competitive relationship between CO₂ reduction and olefin carbonylation, suggesting that balancing RWGS and hydroformylation rates enhances catalytic performance. Our work not only deepens the mechanism understanding of silane-free CO₂ hydroformylation but also paves the way for the rational design of subsequent high-performance catalysts. 2026-10-01T00:00:00Z Text Journal contribution 10.1021/acs.iecr.6c03873.s001 https://figshare.com/articles/journal_contribution/Research_on_Silane-Free_CO_sub_2_sub_Hydroformylation_Reaction_Mechanisms_with_Ru_sub_3_sub_CO_sub_12_sub_and_Phosphine_Catalysts/34047261 CC BY-NC 4.0