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

Direct hydrogenation of CO 2 to liquid hydrocarbons (C 5+ ) 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 ZrO 2 /Co catalyst that enables direct CO 2 hydrogenation to C 5+ hydrocarbons at a low temperature of 200 ° C. Under optimal conditions, the catalyst achieves a high CO 2 hydrogenation activity of 26.0 mmol CO2 ·g Co –1 ·h –1 with 58.9 C-mol % selectivity toward C 5+ liquid hydrocarbons and negligible CO formation. The inverse architecture of ZrO 2 /Co, wherein ZrO 2 nanoislands are dispersed over metallic Co 0 particles, concurrently not only enhances CO 2 adsorption and suppresses H 2 adsorption but also delivers a surface C/H ratio approximately 31 times higher than that of pristine Co 0 , thereby promoting chain growth. In situ DRIFTS reveals that the inverse catalyst generates abundant oxygen-containing intermediates (HCOO–, HCO 3 –, CH 3 O–, and CH 3 COO–), which are subsequently hydrogenated to CH x for chain growth over Co 0 sites. This work not only provides a low-temperature catalyst for direct CO 2 -to-C 5+ conversion but also establishes inverse oxide/metal interfaces as a general platform for tuning C–C bond coupling in CO 2 hydrogenation.