CoII-organic ‘soft’ metallo-supramolecular polymer nanofibers for efficient photoreduction of CO2

Abstract

Coordination-driven metallo-supramolecular polymers hold significant potential as highly efficient catalysts for photocatalytic CO₂ reduction, owing to the covalent integration of the light harvesting unit, catalytic center and intrinsic hierarchical nanostructures. In this study, we present the synthesis, characterization, and gelation behaviour of a novel low molecular weight gelator (LMWG) integrating a benzo[1,2-b:4,5-b′]dithiophene core with terpyridine (TPY) units via alkyl amide chains (TPY-BDT). The two TPY ends of the TPY-BDT unit efficiently chelate with metal ions, enabling the formation of a metallo-supramolecular polymer that brings together the catalytic center and a photosensitizer in close proximity, maximizing catalytic efficiency for CO₂ reduction. The self-assembly of TPY-BDT with Co^II ions yields a Co-TPY-BDT coordination polymer gel (CPG) with a 3D interconnected fibrous morphology, facilitating rapid electron transfer and efficient substrate diffusion. The Co-TPY-BDT CPG achieves an outstanding CO₂ to CO conversion, producing 33.74 mmol g⁻¹ of CO in 18 hours with ∼99% selectivity under visible light irradiation, using triethylamine (TEA) as a sacrificial electron donor. Remarkably, the Co-TPY-BDT CPG demonstrates significant catalytic activity even under low-concentration CO₂ atmospheres (5% CO₂, 95% Ar), producing 1.9 mmol g⁻¹ of CO in 10 hours with a selectivity of 94.6%. Moreover, In situ diffuse reflectance Fourier transform (DRIFT) study, femtosecond transient absorption spectroscopy, and DFT calculations were employed to elucidate the CO₂ to CO reaction mechanism.