Dye-sensitised semiconductors modified with molecular catalysts for light-driven H₂ production

Abstract

The development of synthetic systems for the conversion of solar energy into chemical fuels is a research goal that continues to attract growing interest owing to its potential to provide renewable and storable energy in the form of a 'solar fuel'. Dye-sensitised photocatalysis (DSP) with molecular catalysts is a relatively new approach to convert sunlight into a fuel such as H2 and is based on the self-assembly of a molecular dye and electrocatalyst on a semiconductor nanoparticle. DSP systems combine advantages of both homogenous and heterogeneous photocatalysis, with the molecular components providing an excellent platform for tuning activity and understanding performance at defined catalytic sites, whereas the semiconductor bridge ensures favourable multi-electron transfer kinetics between the dye and the fuel-forming electrocatalyst. In this tutorial review, strategies and challenges for the assembly of functional molecular DSP systems and experimental techniques for their evaluation are explained. Current understanding of the factors governing electron transfer across inorganic-molecular interfaces is described and future directions and challenges for this field are outlined.

Origin and Perspectives of the Photochemical Activity of Nanoporous Carbons

“…Although much progress has been made, photocatalytic reactions still have numerous limitations to achieve satisfactory performance metrics with current photoactive materials based on semiconductors 108, 109…”

Plasmon‐Mediated Solar Energy Conversion via Photocatalysis in Noble Metal/Semiconductor Composites

“…As a potential solution to efficiently convert solar energy to chemical energy, semiconductor photocatalysis has attracted much interest 13. Some semiconductor photocatalysts with high photocatalytic performance and good stability, such as TiO 2 and ZnO, possess wide band gaps and cannot absorb visible light 14.…”

Electrocatalytic and Solar‐Driven CO2 Reduction to CO with a Molecular Manganese Catalyst Immobilized on Mesoporous TiO2

“…Herein, we present a novel Mn I CO 2 reduction electrocatalyst with a phosphonate functionality ( MnP , Scheme 1) that allows anchoring and direct wiring between the catalytic center and a metal oxide surface,15 as has been achieved for an analogous phosphonate‐modified Re complex 16. We employ a mesoporous TiO 2 electrode, because it offers 1) long‐term stability and conductivity under reducing conditions,17 2) a three‐dimensional morphology for high catalyst loading and to facilitate close inter‐molecular interactions, and 3) transparency for spectroelectrochemical characterization of catalytic intermediates 18.…”