The role of structural disorder in increasing the activity of cobalt oxide and manganese oxide water oxidation catalysts

This dataset consists of 36 spreadsheets containing raw data and charts for the figures included in the research chapters of the author's thesis.
Chapter 2 of the thesis examines disorder in heterogenite-like cobalt oxides. It presents a structure versus function study for a series of phosphate doped heterogenite-like cobalt oxides with the aim of explaining the mechanistic importance of disorder in Kanan and Nocera’s highly efficient 'Co-Pi'(heterogenite-like cobalt oxide with phosphate) electrocatalyst. The phosphate doped heterogenite-like cobalt oxide series was synthesised ex situ to allow an in-depth structural characterisation of the materials by X-ray absorption spectroscopy (XAS) and transmission electron microscopy (TEM). The relationship between thermodynamic stability and catalytic activity was examined by measuring the oxidative strength of each material in a reaction with hydrogen peroxide (H2O2).  
Chapter 3 examines disorder in birnessite-like manganese oxides. It presents a structure versus function study for disordered and ordered birnessite-like manganese (III,IV) oxides with the aim of explaining why disordered birnessite phases are more catalytically active than ordered birnessite phases. The two disordered birnessite-like phases (one with 2D stacking disorder and one with no crystalline order) and an ordered birnessite-like phase were comprehensively structurally characterised by X-ray diffraction (XRD), XAS and TEM. The thermodynamic stability of each material was quantified by examining how each material functioned in the competitive 'direct oxidation' / 'catalytic disproportionation' reaction with H2O2. 
Chapter 4 examines heterogenite-like cobalt oxides in an in situ XAS-electrochemical study. It presents the design and utilisation of a new spectroelectrochemical cell for the investigation of electrochemical and photoelectrochemical reaction mechanisms during in situ XAS-electrochemical experiments. Specifically, the cell was used to study the reaction mechanisms of two heterogenite-like cobalt oxides and to quantify X-ray beam-induced phenomenon associated with the in situ characterisation of these samples. 
The relevant figures/files are listed below and in the thesis:

Figure 2.1: Powder XRD spectra collected on bulk heterogenite, CoOx (0 %P), and CoOx (9 %P)
Figure 2.2: XRD simulations of single crystal heterogenite
Figure 2.4 a, b: Co K-edge XAS spectra collected on the CoOx (x %P) series in transmission mode
Figure 2.10: FTIR data collected on the CoOx (x %P) series
Figure 2.15: Cyclic voltammetry of the CoOx (x %P) series (analysed in 0.1 M, pH 7 phosphate buffer)
Figure 2.17: Cyclic voltammetry analysis of CoOx (0 %P) (analysed in 0.1 M, pH 7 phosphate buffer) for 50 cycles
Figure 2.18: Tafel plot containing the Tafel slopes for the CoOx (x %P) series and bulk heterogenite
Figure 2.19: Ex situ measure of water oxidation catalysis using hypochlorite as a sacrificial oxidant. Gas evolution is presented as a total after 5 mins of reaction

Figure 3.5: Mn K-edge XAS data collected on the manganese oxide samples
Figure 3.6: Visual representation of the EXAFS fits for the manganese oxides
Figure 3.7: Oxidation state calculation for the manganese oxide materials
Figure 3.9: XRD spectra for the manganese oxides and a biogenic manganese
oxide sample
Figure 3.13: Activity of the manganese oxide samples for the ex situ water
oxidation reaction using CeIV as a chemical oxidant
Figure 3.14: Mn K-edge XAS data of screen-printed 0%Pi-MnOx
Figure 3.16: CV data collected on the manganese oxide samples
Figure 3.21 a, b: Ce L1-edge data collected on Ce3+ and Ce4+ in the Mn K-edge region
Figure 3.22: Mn K–edge XANES spectra collected on samples manganese oxide with CeIV samples

Figure 4.3: Cyclic voltammetry (v = 0.020 V s-1; quasi-stabilized fifth cycle shown) of a nickel (Ni0)-modified gold electrode in contact with an Ar-saturated 0.1 M NaOH
Figure 4.4: Cyclic voltammetry of each CoOx  and CoOx NTA modified electrode
Figure 4.5: Single Co K-edge X-ray absorption spectra collected in situ for cobalt oxides on 1 mm thick glassy carbon and CoOxNTA on 0.5 mm thick ITO/PET
Figure 4.6: Electrochemical and spectroscopic data collected on nickel-based materials
Figure 4.7 a, b, c, d: Electrochemical and in situ Co K-edge XAS data collected on CoOx /ITO/PET and CoOx NTA/ITO/PET
Figure 4.8: Chronoamperomograms recorded on CoOx /ITO/PET and CoOxNTA/ITO/PET during spectroscopic data collection
Figure 4.9: In situ Co K-edge XANES data collected on a very low loading of CoOx NTA. CoOx NTA (Γ = 0.4 mC cm-2 ≈ 4 nmol cm-2) was electrodeposited onto ITO/PET in contact with 0.1 M borate buffer (pH 9.2)