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A Cu/Co tandem catalysis protocol was developed to conduct the hydroformylation of olefins using CO2/H2 and PMHS (polymethylhydrosiloxane) as a readily available and environmentally friendly hydride source. This methodology was performed via a two‐step approach consisting of the copper‐catalyzed reduction of CO2 by hydrosilane and subsequent cobalt‐promoted hydroformylation with H2 and the in situ formed CO. The optimized triphos oxide ligand, which presumably facilitates the migratory insertion of CO gives moderate to excellent yields for both terminal and internal alkenes. This earth‐abundant metal catalysis provides a reliable and efficient way to afford useful aldehydes in industry using silicon by‐product PMHS as hydrogen source and renewable CO2 as carbonyl source. [ABSTRACT FROM AUTHOR]

Designing earth‐abundant metal complexes as efficient molecular photocatalysts for visible light‐driven CO2 reduction is a key challenge in artificial photosynthesis. Here, we demonstrated the first example of a mononuclear iron pyridine‐thiolate complex that functions both as a photosensitizer and catalyst for CO2 reduction. This single‐component bifunctional molecular photocatalyst efficiently reduced CO2 to formate and CO with a total turnover number (TON) of 46 and turnover frequency (TOF) of 11.5 h−1 in 4 h under visible light irradiation. Notably, the quantum yield was determined to be 8.4 % for the generation of formate and CO at 400 nm. Quenching experiments indicate that high photocatalytic activity is mainly attributed to the rapid intramolecular quenching protocol. The mechanism investigation by DFT calculation and electrochemical studies revealed that the protonation of Febpy(pyS)2 is indispensable step for photocatalytic CO2 reduction. [ABSTRACT FROM AUTHOR]

Capturing CO2 and subsequently converting into valuable chemicals has attracted extensive attention. Herein, a series of biomass‐based N‐rich porous carbon materials with high specific surface area and pore volume were prepared using biomass waste soybean dregs as precursors. The nitrogen content was up to 4 % with different forms in the carbon skeleton such as pyridine‐N, pyrrole‐N. The synergistic effect of ultra‐micropore (pore size <0.7 nm) and N‐containing groups endowed the materials with a high CO2 adsorption capacity, reaching 6.3 and 3.6 mmol g−1 at 0 and 25 °C under atmospheric pressure, respectively. In addition, the sufficient interaction between N‐containing groups and CO2 was demonstrated by solid‐state nuclear magnetic resonance spectroscopy, and the captured CO2 was possibly activated in the form of carbamate, which is conducive to subsequent conversion. Therefore, the supported catalyst with the as‐synthetic porous carbon material as the carrier and ZnII as catalytic sites was prepared and successfully applied for carboxylative cyclization of propargylic amine with CO2 to afford the 3‐benzyl‐5‐methyleneoxazolidin‐2‐one. The results showed that CO2 capture and in‐situ conversion work effectively to produce highly value‐added chemicals. In this process, the captured CO2 could be activated and fixed into chemicals in mild conditions. More importantly, the energy consumption in CO2 desorption and adsorbent regeneration could be avoided. The valorization of both solid waste and CO2 to valuable chemicals provides an elegant strategy of killing three birds with one stone. [ABSTRACT FROM AUTHOR]

Designing earth-abundant metal complexes as efficient molecular photocatalysts for visible light-driven CO 2 reduction is a key challenge in artificial photosynthesis. Here, we demonstrated the first example of a mononuclear iron pyridine-thiolate complex that functions both as a photosensitizer and catalyst for CO 2 reduction. This single-component bifunctional molecular photocatalyst efficiently reduced CO 2 to formate and CO with a total turnover number (TON) of 46 and turnover frequency (TOF) of 11.5 h -1 in 4 h under visible light irradiation. Notably, the quantum yield was determined to be 8.4 % for the generation of formate and CO at 400 nm. Quenching experiments indicate that high photocatalytic activity is mainly attributed to the rapid intramolecular quenching protocol. The mechanism investigation by DFT calculation and electrochemical studies revealed that the protonation of Febpy(pyS) 2 is indispensable step for photocatalytic CO 2 reduction., (© 2024 Wiley-VCH GmbH.)

A Cu/Co tandem catalysis protocol was developed to conduct the hydroformylation of olefins using CO 2 /H 2 and PMHS (polymethylhydrosiloxane) as a readily available and environmentally friendly hydride source. This methodology was performed via a two-step approach consisting of the copper-catalyzed reduction of CO 2 by hydrosilane and subsequent cobalt-promoted hydroformylation with H 2 and the in situ formed CO. The optimized triphos oxide ligand, which presumably facilitates the migratory insertion of CO gives moderate to excellent yields for both terminal and internal alkenes. This earth-abundant metal catalysis provides a reliable and efficient way to afford useful aldehydes in industry using silicon by-product PMHS as hydrogen source and renewable CO 2 as carbonyl source., (© 2024 Wiley-VCH GmbH.)