Rational design of low‐cost and efficient transition‐metal catalysts for low‐temperature CO₂ activation is significant and poses great challenges. Herein, a strategy via regulating the local electron density of active sites is developed to boost CO₂ methanation that normally requires >350 °C for commercial Ni catalysts. An optimal Ni/ZrO₂ catalyst affords an excellent low‐temperature performance hitherto, with a CO₂ conversion of 84.0 %, CH₄ selectivity of 98.6 % even at 230 °C and GHSV of 12,000 mL g⁻¹ h⁻¹ for 106 h, reflecting one of the best CO₂ methanation performance to date on Ni‐based catalysts. Combined a series of in situ spectroscopic characterization studies reveal that re‐constructing monoclinic‐ZrO₂ supported Ni species with abundant oxygen vacancies can facilitate CO₂ activation, owing to the enhanced local electron density of Ni induced by the strong metal‐support interactions. These findings might be of great aid for construction of robust catalysts with an enhanced performance for CO₂ emission abatement and beyond.

CO₂ hydrogenation to chemicals and fuels is a significant approach for achieving carbon neutrality. It is essential to rationally design the chemical structure and catalytic active sites towards the development of efficient catalysts. Here we show a Ce-CuZn catalyst with enriched Cu/Zn-O_V-Ce active sites fabricated through the atomic-level substitution of Cu and Zn into Ce-MOF precursor. The Ce-CuZn catalyst exhibits a high methanol selectivity of 71.1% and a space-time yield of methanol up to 400.3 g·kg_cat⁻¹·h⁻¹ with excellent stability for 170 h at 260 °C, comparable to that of the state-of-the-art CuZnAl catalysts. Controlled experiments and DFT calculations confirm that the incorporation of Cu and Zn into CeO₂ with abundant oxygen vacancies can facilitate H₂ dissociation energetically and thus improve CO₂ hydrogenation over the Ce-CuZn catalyst via formate intermediates. This work offers an atomic-level design strategy for constructing efficient multi-metal catalysts for methanol synthesis through precise control of active sites.

The quickly increasing demand for sustainable energy and materials requires researchers to develop highly efficient and stable catalytic materials for the hydrogenation of carbon–oxygen bonds into chemicals and fuels. Cu-based catalysts have been attracting tremendous attention in gas-phase catalytic reactions, such as the water-gas shift, CO oxidation and NO_x reduction reactions. In particular, the C–O bond hydrogenation reaction is an economical and environmentally friendly way to produce alcohols. However, the instability of Cu-based catalysts has become a great challenge for industrial application. The majority of publications discuss the instability of Cu-based catalysts for reactions involving the hydrogenation of dimethyl oxalate, methyl acetate, furfural, or CO₂ to alcohols. This review briefly summarizes the roots of Cu-based catalyst deactivation and introduces five strategies for improving their stability, as well as the evolution of copper species during preparation and reaction and a novel Cu-based catalyst technology.