Recent Progress in Materials Exploration for Thermocatalytic, Photocatalytic, and Integrated Photothermocatalytic CO₂‐to‐Fuel Conversion

The excess depletion of carbon‐rich fossil fuels and agroforest biomass resources has aggravated the energy crisis and environmental pollution, causing increased CO 2 emissions. Accordingly, the goal of “peak CO 2 emissions and carbon neutrality” is proposed to alleviate global warming. CO 2 ‐to‐fuel conversion is considered as a preferable move for reducing the atmospheric CO 2 concentration and further upgrading to chemical feedstocks. However, the highly efficient CO 2 conversion remains challenging due to the thermodynamic limits and kinetic barriers, which require high energy input through conventional thermocatalysis. Inspired by “artificial photosynthesis,” photocatalytic CO 2 transformation has received tremendous attention and makes remarkable progress over the past decades, although it is still far from practical application. Recently, the integrated photothermocatalysis has emerged as an intelligent strategy to utilize solar energy to induce local heating and energetic hot carriers, which synergistically promote CO 2 ‐to‐fuel conversion. The key to the success of CO 2 upgradation is catalysts’ development with improved activity, selectivity, and stability. This review highlights the recent advancements in materials designing for practical CO 2 conversion through thermocatalysis, photocatalysis, and photothermocatalysis during the past five years, emphasizing the reaction pathways and mechanism on the CO bond activation and intermediates formation. Finally, the current challenges and future opportunities are described.