Inverse ZrO2/Co Enables Low-Temperature Direct CO2 Hydrogenation to Liquid Hydrocarbons

Abstract Direct hydrogenation of CO2 to liquid hydrocarbons (C5+) at low temperature is a highly desirable but challenging transformation, as conventional catalysts typically operate at high temperatures via indirect pathways by producing and using a CO intermediate. In this work, we report an inverse ZrO2/Co catalyst that enables direct CO2 hydrogenation to C5+ hydrocarbons at a low temperature of 200 °C. Under optimal conditions, the catalyst achieves a high CO2 hydrogenation activity of 26.0 mmolCO2·gCo–1·h–1 with 58.9 C-mol % selectivity toward C5+ liquid hydrocarbons and negligible CO formation. The inverse architecture of ZrO2/Co, wherein ZrO2 nanoislands are dispersed over metallic Co0 particles, concurrently not only enhances CO2 adsorption and suppresses H2 adsorption but also delivers a surface C/H ratio approximately 31 times higher than that of pristine Co0, thereby promoting chain growth. In situ DRIFTS reveals that the inverse catalyst generates abundant oxygen-containing intermediates (HCOO–, HCO3–, CH3O–, and CH3COO–), which are subsequently hydrogenated to CHx for chain growth over Co0 sites. This work not only provides a low-temperature catalyst for direct CO2-to-C5+ conversion but also establishes inverse oxide/metal interfaces as a general platform for tuning C–C bond coupling in CO2 hydrogenation.