Two Zr-based heterometal–organic frameworks for efficient CO2 reduction under visible light

Abstract

Two new zirconium-based heterometal–organic frameworks, Zr₃CP₃–Mn (1) and Zr₃CP₃–Ni (2), constructed from [Cp₃Zr₃(μ₃-O)(μ₂-OH)₃(IN)₃] secondary building units and transition metal cations, were successfully synthesized through a one-pot method. Single-crystal X-ray diffraction analysis shows that both 1 and 2 have one-dimensional chain structures, in which [Cp₃Zr₃(μ₃-O)(μ₂-OH)₃(IN)₃] SBUs are connected by Mn and Ni ions. Furthermore, photoreduction of CO₂ under visible light irradiation reveals that 1 and 2 have good catalytic activities to reduce CO₂ into carbon monoxide and hydrogen. The CO yields of 1 and 2 were 9.30 and 5.21 mmol g⁻¹ h⁻¹ under one hour irradiation at 293 K, respectively. In addition, the inherent photocatalytic mechanism was studied through photochemical and electrochemical measurements. This work provides a valuable perspective for the design and synthesis of simple, low-cost MOF catalysts for photoreduction of CO₂.