A triblock amphiphilic polymer derived from the copolymerization of CO2 and epoxides containing a bipyridine rhenium complex in its backbone is shown to effectively catalyze the visible‐light‐driven reduction of CO2 to CO. This polymer provides uniformly spherical micelles in aqueous solution, where the metal catalyst is sequestered in the hydrophobic portion of the nanostructured micelle. CO2 to CO reduction occurs in an efficient visible‐light‐driven process in aqueous media with turnover numbers up to 110 (>99 % selectivity) in the absence of a photosensitizer, which is a 37‐fold enhancement over the corresponding molecular rhenium catalyst in organic solvent. Notably, the amphiphilic polycarbonate micelle rhenium catalyst suppresses H2 generation, presumably by preventing deactivation of the active catalytic center by water.

Compounds bearing organophosphorus motifs and 2-oxazolidinone have found numerous applications in pharmaceutical chemistry, homogeneous catalysis, and organic materials. Here, we describe an efficient and selective protocol for straightforward access to a series of 5-((diarylphosphoryl)­methyl)­oxazolidin-2-ones via the copper-catalyzed difunctionalization of the CC bond of propargylic amines with CO2 and phosphine oxide. Notably, copper catalysis is a sustainable and benign catalytic mode. This reaction proceeds under mild reaction conditions, which is operationally simple and scalable with a broad scope, exclusive selectivity, and good functional group compatibility. Mechanistic studies suggest a one-pot tandem cyclization/radical addition sequence, along with the phosphorylation/cyclization scheme.

Thermocatalysis of CO2 into high valuable products is an efficient and green method for mitigating global warming and other environmental problems, of which Noble‐metal‐free metal–organic frameworks (MOFs) are one of the most promising heterogeneous catalysts for CO2 thermocatalysis, and many excellent researches have been published. Hence, this review focuses on the valuable products obtained from various CO2 conversion reactions catalyzed by noble‐metal‐free MOFs, such as cyclic carbonates, oxazolidinones, carboxylic acids, N‐phenylformamide, methanol, ethanol, and methane. We classified these published references according to the types of products, and analyzed the methods for improving the catalytic efficiency of MOFs in CO2 reaction. The advantages of using noble‐metal‐free MOF catalysts for CO2 conversion were also discussed along the text. This review concludes with future perspectives on the challenges to be addressed and potential research directions. We believe that this review will be helpful to readers and attract more scientists to join the topic of CO2 conversion.

A triblock amphiphilic polymer derived from the copolymerization of CO2 and epoxides containing a bipyridine rhenium complex in its backbone is shown to effectively catalyze the visible‐light‐driven reduction of CO2 to CO. This polymer provides uniformly spherical micelles in aqueous solution, where the metal catalyst is sequestered in the hydrophobic portion of the nanostructured micelle. CO2 to CO reduction occurs in an efficient visible‐light‐driven process in aqueous media with turnover numbers up to 110 (>99 % selectivity) in the absence of a photosensitizer, which is a 37‐fold enhancement over the corresponding molecular rhenium catalyst in organic solvent. Notably, the amphiphilic polycarbonate micelle rhenium catalyst suppresses H2 generation, presumably by preventing deactivation of the active catalytic center by water.

The photocatalytic reduction of CO 2 into fuels offers the prospect for creating a new CO 2 economy. Harnessing visible light-driven CO 2 -to-CO reduction mediated by the long-lived triplet excited state of rhenium(I) tricarbonyl complexes is a challenging approach. We here develop a series of new mononuclear rhenium(I) tricarbonyl complexes (Re-1À Re-4) based on the imidazole-pyridine skeleton for photo-driven CO 2 reduction. These catalysts are featured by combining pyridyl-imidazole with the aromatic ring and different pendant organic groups onto the N1 position of 1,3imidazole unit, which display phosphorescence under Arsaturated solution even at ambient conditions. By contrast, {Re[9-(pyren-1-yl)-10-(pyridin-2-yl)-9H-pyreno[4,5-d] imidazole)](CO) 3 Cl} (Re-4) by introducing pyrene ring at the N1 position of pyrene-fused imidazole unit exhibits superior catalytic performance with a higher turnover number for CO (TON CO = 124) and > 99.9 % selectivity, primarily ascribed to the strong visible light-harvesting ability, long-lived triplet lifetimes (164.2 μs) and large reductive quenching constant. Moreover, the rhenium(I) tricarbonyl complexes derived from π-extended pyrene chromophore exhibit a long lifetime corresponding to its ligand-localized triplet state ( 3 IL) evidenced from spectroscopic investigations and DFT calculations.