Advancements and Challenges in Reductive Conversion of Carbon Dioxide via Thermo-/Photocatalysis

Abstract

Carbon dioxide (CO2) is the major greenhouse gas and also an abundant and renewable carbon resource. Therefore, its chemical conversion and utilization are of great attraction for sustainable development. Especially, reductive conversion of CO2 with energy input has become a current hotspot due to its ability to access fuels and various important chemicals. Nowadays, the controllable CO2 hydrogenation to formic acid and alcohols using sustainable H2 resources has been regarded as an appealing solution to hydrogen storage and CO2 accumulation. In addition, photocatalytic CO2 reduction to CO also provides a potential way to utilize this greenhouse gas efficiently. Besides direct CO2 hydrogenation, CO2 reductive functionalization integrates CO2 reduction with subsequent C–X (X = N, S, C, O) bond formation and indirect transformation strategies, enlarging the diverse products derived from CO2 and promoting CO2 reductive conversion into a new stage. In this Perspective, the progress and challenges of CO2 reductive conversion, including hydrogenation, reductive functionalization, photocatalytic reduction, and photocatalytic reductive functionalization are summarized and discussed along with the key issues and future trends/directions in this field. We hope this Perspective can evoke intense interest and inspire much innovation in the promise of CO2 valorization.

Activating photocatalytic hydrogen evolution by constructing Ni-based organic layers and tailoring its crystal facets

“…Thus, this study might open new opportunities in the design of more effective cocatalysts (inorganic catalysts, [76][77][78][79] MOFs, 80 covalent organic frameworks, 81,82 phthalocyanine derivatives and so on), which could physically or chemically combine with other semiconductor photocatalysts to achieve outstanding performance for extensive applications. 83,84…”

Incorporating Catalytic Units into Nanomaterials: Rational Design of Multipurpose Catalysts for CO2 Valorization

“…Reductive CO 2 transformation implies a decrease in the CO 2 oxidation state and has gained sustained attention due to its ability to access fuels and various important chemicals, among which the reductive functionalization of CO 2 , i.e., CO 2 reduction accompanied by new C–X bond formation, breaks through the limitation of the CO 2 valence state; therefore, CO 2 can be used as a methylation, methylenation, or formylation reagent for a suitable nucleophile. , …”

“…Reductive CO 2 transformation implies a decrease in the CO 2 oxidation state and has gained sustained attention due to its ability to access fuels and various important chemicals, among which the reductive functionalization of CO 2 , i.e., CO 2 reduction accompanied by new C−X bond formation, breaks through the limitation of the CO 2 valence state; therefore, CO 2 can be used as a methylation, methylenation, or formylation reagent for a suitable nucleophile. 27,28 Our group concentrates on catalyst development and product regulation for the reductive functionalization of CO 2 with amine using hydrosilane as a reductant. It is found that the slightly polar Si−H bond in hydrosilanes can be activated by silicophilic species such as the carboxylate anion by forming a hypervalent silicon intermediate.…”

Photocatalytic Reduction of Carbon Dioxide to Methanol: Carbonaceous Materials, Kinetics, Industrial Feasibility, and Future Directions

“…In the last three decades, numerous research efforts have been made to develop active heterogeneous catalysts for the conversion of CO 2 by three processes to produce methanol. A large number of review articles, publications, and books ,,,− have been published on research topics of CO 2 conversion such as CO 2 utilization by thermal catalysis, , electrocatalytic reduction, , photocatalytic synthesis, ,,− plasma, and other methods. − Recently, the research group of Shanmuga and Ramyashree published a review article on MOF compounds for PCCR of methanol . In 2022, Gawande’s group discussed recent developments in the photocatalytic hydrogenation of CO 2 to methanol.…”