Ultralow‐Content PdCu Disordered Nanoalloys on Carbon Nitrides for Unity‐Selective CO 2 Hydrogenation to Methanol

Abstract Catalytic CO 2 hydrogenation to methanol offers a dual benefit of mitigating CO 2 emissions and producing liquid fuel. Herein, we demonstrate an efficient CO 2 ‐to‐methanol catalyst (PdCu/PCN), consisting of ultrafine PdCu disordered nanoalloys anchored on polymeric carbon nitride (PCN) nanosheets. Prepared via a facile one‐pot co‐polymerization recipe, this strategy permits the in situ formation and integration of PdCu alloys during PCN synthesis, which ensures strong interfacial confinement and prevents the generation of oxide‐derived encapsulation overlayers, maximizing the exposure of active metal sites. Despite its ultralow metal loading (Pd: 0.18%, Cu: 0.16%), the catalyst achieves a high methanol production rate of 21.24 mmol g metal −1 h −1 with 100% selectivity at 160 °C, together with outstanding reusability. Alloying Cu with Pd in a disordered nanoalloy structure modulates the CO 2 hydrogenation pathway toward methanol while lowering the energy barrier of the rate‐determining step. This work highlights the potential of PCN as a flexible metal‐free support for constructing active and durable catalysts for selective CO 2 conversion through in situ alloy engineering.