Transient spectroscopic studies of photocatalysts for CO2 and proton reduction

Abstract

In this thesis, optical and electrochemical techniques are used to study the factors controlling catalytic function in solar-to-fuel conversion systems. Chapter 3, the first results chapter, considers a system for CO2 reduction based on a Re photocatalyst anchored to TiO2. This chapter reports evidence that the immobilisation of the photocatalyst via covalent bonds improves the stability of one of the key reaction intermediates resulting in higher catalytic yields. This chapter also provides insight into the nature and timescale of the steps in the mechanism of CO2 reduction. Chapter 4 considers a proton reduction system based on a Ru absorber, a Ni electrocatalyst and a sacrificial electron donor. This chapter discusses the mechanism behind the strong pH dependence in this system. The results show that whereas the electron transfer between the dye anions and the electrocatalyst is pH independent, the generation of dye anions and the catalytic function of the electrocatalyts have opposite pH-dependencies. Chapter 5 considers a photocathode for proton reduction based on a Cu2O/Al:ZnO buried p-n junction with protection and catalyst layers. The results presented show that the buried junction controls charge separation and the photocurrent onset. Furthermore, the catalyst layer is found to slow down charge recombination and help achieve high reduction yields. This chapter also discuses the mechanism of proton reduction and how the nature of the rate-limiting step has an impact in the recombination kinetics. Chapter 6 discusses the use of transient absorption spectroscopy to study high refractive index materials with high quality interfaces. This chapter investigates light interference effects in TiO2, Cu2O and a CH3NH3PbI3 perovskite device. The results show that interference effects in these materials can dominate their transient spectra, hindering its interpretation. However, it is found that this spectroscopy can also be used to extract information about the changes of the refractive index.