Abstract
Photothermal catalytic CO(2) 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 Zn(II)-Co(III)PBA into a synergistic architecture. This unique configuration offers dual functional advantages: (1) the abundant heterointerfaces provide highly active sites for enhanced CO(2) and H(2) adsorption/activation, and (2) the engineered energy band structure optimizes charge separation and transport efficiency. The optimized T-C(3)Z(1)-PBA (SC) achieves exceptional photothermal catalytic performance, demonstrating a CO(2) 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 (CO(2)* and CO*) and overall reaction kinetics. This research provides insights for engineering high-performance heterostructured catalysts by controlling interfacial and electronic structures.