Sulfonic Acid Group Docking Synthesis of Platinum Clusters in MOFs Cavity Enables Low-Temperature Stable Selective CO2 Hydrogenation to Methanol.

Platinum (Pt) nanoparticles favor the hydrogenation of CO2 to CO, presenting a significant challenge for value-added methanol synthesis. Herein we report a sulfonic acid group docking strategy for the gram-scale synthesis of monodispersed Pt clusters within the cavities of double sulfonated zirconium terephthalate UiO-66. The resulting catalyst enables the efficient hydrogenation of CO2 to methanol, achieving nearly 100% methanol selectivity at 60 °C and sustaining stable performance for 500 h of continuous operation. Computational and experimental investigations reveal that sulfonic acid groups facilitate the modulation of the electronic structures of adjacent Pt clusters and defective zirconium sites, thereby promoting the adsorption and activation of H2 and CO2. Consequently, the interfaces between Pt edges and defective zirconium sites efficiently promote the hydrogenation of CO2 to methanol at low temperatures. Our developed sulfonic acid group docking strategy can be extended to synthesize a wide range of highly active and stable metal clusters in porous supports, opening new possibilities for important catalytic applications.