Intermetallic Nanocatalyst for Highly Active Heterogeneous Hydroformylation

Abstract

Hydroformylation is an imperative chemical process traditionally catalyzed by homogeneous catalysts. Designing a heterogeneous catalyst with high activity and selectivity in hydroformylation is challenging but essential to allow the convenient separation and recycling of precious catalysts. Here, we report the development of an outstanding catalyst for efficient heterogeneous hydroformylation, RhZn intermetallic nanoparticles. In the hydroformylation of styrene, it shows three times higher turnover frequency (3090 h −1 ) compared to the benchmark homogeneous Wilkinson's catalyst (966 h −1 ), as well as a high chemoselectivity toward aldehyde products. RhZn is active for a variety of olefin substrates and can be recycled without a significant loss of activity. Density functional theory calculations show that the RhZn surfaces reduce the binding strength of reaction intermediates and have lower hydroformylation activation energy barriers compared to pure Rh(111), leading to more favorable reaction energetics on RhZn. The calculations also predict potential catalyst design strategies to achieve high regioselectivity.

In Situ Fabrication of the Al2O3@NiMo Core–Shell Catalyst from LDH for Low-Pressure Hydrodeoxygenation of Fatty Acid Methyl Ester

“…With the increase of temperature, CO that adsorbed on the surface of the catalysts gradually desorbed, in which Ni 1 Mo 2 /Al 2 O 3 -IM completely desorbed at 60 °C and Al 2 O 3 @Ni 1 Mo 2 -LDO completely desorbed at 180 °C. A temperature-programmed desorption study using DRIFTS further revealed that the CO peaks shifted to a lower wavenumber with an increase in temperature on the metal surface, indicating that CO dipole–dipole coupling was eliminated with the decrease of CO coverage . It can be concluded that the core–shell catalyst was more capable of adsorption of CO, which can enable the ability to increase binding to the active site.…”

“…In addition, it was found that the chemical state of Ni species in Al to a lower wavenumber with an increase in temperature on the metal surface, indicating that CO dipole−dipole coupling was eliminated with the decrease of CO coverage. 37 It can be concluded that the core−shell catalyst was more capable of adsorption of CO, which can enable the ability to increase binding to the active site. It was favorable for the deoxygenation reaction of oxygen-containing compounds.…”

Fabrication of the Microenvironment and Active Structure of Single-Rh-Site Catalysts for Efficient Hydroformylation of Olefins

“…The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acssuschemeng.2c04674. More details about the experiments, including characterization conditions of m-3vPAr 3 -POLs and corresponding supported catalysts; 1 H, 13 C, and 31…”

“…For example, Zhang’s group prepared a series of Rh/ZnO-nw catalysts employing the strong metal–support interaction (SMSI) between ZnO and Rh species, and the afforded catalysts exhibited good activity in the hydroformylation of styrene . Huang’s group used Zn species and Rh species to synthesize the intermetallic compounds and loaded them on SBA-15 to prepare an efficient hydroformylation catalyst, which exhibited 3 times more activity than the homogeneous Wilkinson catalyst in the hydroformylation of styrene . However, Rh–P complex catalysts are still the best choice for heterogeneous hydroformylation reactions due to their superior catalytic performance.…”

“…30 Huang's group used Zn species and Rh species to synthesize the intermetallic compounds and loaded them on SBA-15 to prepare an efficient hydroformylation catalyst, which exhibited 3 times more activity than the homogeneous Wilkinson catalyst in the hydroformylation of styrene. 31 However, Rh−P complex catalysts are still the best choice for heterogeneous hydroformylation reactions due to their superior catalytic performance. Many studies certified that Rh ions were anchored by P species in the POP framework and the coordination state between Rh and P has a great impact on the catalytic performance of Rh-based SMSCs in our laboratory.…”