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Carbon dioxide (CO2) is not only a greenhouse gas but also an abundant carbon resource. CO2 hydrogenation from electrocatalysis and thermocatalysis to high-value-added chemicals has attracted wide attention. The development of a catalyst was critical in the reaction, and the key is the innovation of its synthesis strategy. Carbon materials are widely used in CO2 hydrogenation because of their unique physical and chemical properties. Carbon species could play many roles during catalyst preparation and reaction, not only as bulk catalysts but also as structure modifiers of catalyst, support of catalyst, and electronic regulator of catalyst. In this review, the developmental strategy of catalysts by using a carbon species-assisted method in our research group was summarized, which can be applied to CO2 thermochemical and electrochemical hydrogenation. This review aims to provide insights into CO2 hydrogenation through the design of carbon-based catalysts.

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