Photothermal catalytic CO2 conversion into chemicals that provide added value represents a promising strategy for sustainable energy utilization, yet the development of highly efficient, stable, and selective catalysts remains a significant challenge. Herein, we report a rationally designed p-n junction heterostructure, T-CZ-PBA (SC), synthesized via controlled pyrolysis of high crystalline Prussian blue analogues (PBA) precursor, which integrates CuCo alloy, ZnO, N-doped carbon (NC), and ZnII-CoIIIPBA into a synergistic architecture. This unique configuration offers dual functional advantages: (1) the abundant heterointerfaces provide highly active sites for enhanced CO2 and H2 adsorption/activation, and (2) the engineered energy band structure optimizes charge separation and transport efficiency. The optimized T-C3Z1-PBA (SC) achieves exceptional photothermal catalytic performance, demonstrating a CO2 conversion rate of 126.0 mmol gcat⁻1 h⁻1 with 98.8% CO selectivity under 350 °C light irradiation, while maintaining robust stability over 50 h of continuous operation. In situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS) investigations have identified COOH* as a critical reaction intermediate and elucidated that photoexcitation accelerates charge carrier dynamics, thereby substantially promoting the conversion of key intermediates (CO2* and CO*) and overall reaction kinetics. This research provides insights for engineering high-performance heterostructured catalysts by controlling interfacial and electronic structures.
Keywords: CO production; CO2 hydrogenation; Prussian blue analogues-based catalyst; heterostructure; photothermal catalysis.