With the escalating climate crisis caused by uncontrolled CO₂ emissions, technological breakthroughs in CO₂ capture and utilization have become imperative. Among these, photothermal catalysis, which utilizes full-spectrum to deliver necessary thermal input alongside photogenerated charge carriers, stands out by overcoming the high-temperature requirements of thermal catalysis and enhancing reaction kinetics. Composite metal oxides (CMOs) emerge as pivotal catalysts for photothermal CO₂ hydrogenation toward valuable C₁ products, leveraging tunable electronic structures and abundant oxygen vacancies that facilitate CO₂ activation and H₂ dissociation, while multi-phase interfaces promote synergistic electron transfer that refines selective pathways. Despite the rapid development of CMOs in photothermal CO₂ hydrogenation in recent years, the research remains fragmented and lacks a systematic consolidation. This review delineates synthesis strategies for composite metal oxide catalysts, categorically examines recent advancements in application for converting CO₂ into valuable C₁ products, and elaborates on the mechanisms of reverse water–gas shift (RWGS), methanation, and methanol synthesis pathways. Finally, we consolidate these insights to look ahead, addressing persistent challenges and strategic opportunities.

In the context of achieving carbon neutrality, CO₂ catalytic conversion technologies are effective in reducing atmospheric CO₂ concentrations while simultaneously producing renewable products. This approach is seen as a viable method for constructing a new carbon cycle, thereby effectively addressing the issue of global warming. Photothermal CO₂ conversion has recently emerged as a promising research focus due to its high energy utilization efficiency, superior CO₂ conversion, excellent product selectivity, mild operating conditions, low energy consumption and minimal operating costs. Cerium oxide (CeO₂) has been widely used in photothermal catalysis due to its unique chemical properties, particularly when used as a support material with supported metals, creating distinctive interfacial sites for catalytic reactions. As an emerging star support in photothermal CO₂ conversion, its contributions are equally significant and should not be overlooked. However, to our knowledge, there has been no comprehensive review of CeO₂ applications in catalytic hydrogenation of CO₂. In this paper, we summarize and discuss CeO₂-based materials for photothermal CO₂ conversion to value-added products. This research particularly focuses on the synthesis methods of CeO₂-supported catalysts, the history of CeO₂ in photothermal catalysis, types of photothermal catalytic reactors, unique characterization methods for the photothermal catalysts and the photothermal CO₂ hydrogenation reactions by CeO₂-based catalysts. Perspectives related to further challenges and future directions for photothermal CO₂ hydrogenation are also provided.

An effective strategy was proposed to control the formation of the interfacial bonding between Ru and molybdenum oxide support to stabilize the Ru atoms with the aim to enhance the hydrogen evolution reaction (HER) activity of the resultant catalysts in alkaline medium. The different interfacial chemical bonds, including Ru–O, Ru–O–Mo, and mixed Ru–Mo/Ru–O–Mo, were prepared using an induced activation strategy by controlling the composition of reducing agents in the calcination process. And the regulation mechanism of the interfacial chemical bonds in molybdenum oxide supported Ru catalysts for optimizing HER activity was investigated by density functional theory (DFT) and experimental studies. We found that a controlled interfacial chemical Ru–O–Mo bonding in Ru-MoO₂/C manifests a 12-fold activity increase in catalyzing the hydrogen evolution reaction relative to the conventional metal/metal oxide catalyst (Ru-O-MoO₂/C). In a bifunctional effect, the interfacial chemical Ru-O-Mo sites promoted the dissociation of water and the production of hydrogen intermediates that were then adsorbed on the nearby Ru surfaces and recombined into molecular hydrogen. As compared, the nearby Ru surfaces in Ru–Mo bonding have weak adsorption capacity for the generation of these hydrogen intermediates, resulting in a 5-fold increase HER activity for Ru-Mo-MoO₂/C catalyst compared with Ru-O-MoO₂/C.