Parasitic Light Absorption, Rate Laws and Heterojunctions in the Photocatalytic Oxidation of Arsenic(III) Using Composite TiO2/Fe2O3

• Published in: Chemistry : a European journal Vol. 28; no. 16
• Main Authors: Bullen, Jay C., Heiba, Hany F., Kafizas, Andreas, Weiss, Dominik J.
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 16.03.2022; John Wiley and Sons Inc
• Subjects: Absorption spectroscopy; Adsorbates; Adsorption; Arsenic; Arsenic removal; Arsenite; Catalysts; Charge transfer; Chemistry; composite; Coupling; Current carriers; Electromagnetic absorption; Ferric oxide; Heterojunctions; Kinetics; Oxidation; Photocatalysis; Photocatalysts; photocatalytic oxidation; Photons; Photooxidation; Pollutant removal; Reaction kinetics; Spectrum analysis; Titanium dioxide; Water pollution; water treatment
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.202104181

Composite photocatalyst‐adsorbents such as TiO2/Fe2O3 are promising materials for the one‐step treatment of arsenite contaminated water. However, no previous study has investigated how coupling TiO2 with Fe2O3 influences the photocatalytic oxidation of arsenic(III). Herein, we develop new hybrid experiment/modelling approaches to study light absorption, charge carrier behaviour and changes in the rate law of the TiO2/Fe2O3 system, using UV‐Vis spectroscopy, transient absorption spectroscopy (TAS), and kinetic analysis. Whilst coupling TiO2 with Fe2O3 improves total arsenic removal by adsorption, oxidation rates significantly decrease (up to a factor of 60), primarily due to the parasitic absorption of light by Fe2O3 (88 % of photons at 368 nm) and secondly due to changes in the rate law from disguised zero‐order kinetics to first‐order kinetics. Charge transfer across this TiO2‐Fe2O3 heterojunction is not observed. Our study demonstrates the first application of a multi‐adsorbate surface complexation model (SCM) towards describing As(III) oxidation kinetics which, unlike Langmuir‐Hinshelwood kinetics, includes the competitive adsorption of As(V). We further highlight the importance of parasitic light absorption and catalyst fouling when designing heterogeneous photocatalysts for As(III) remediation. The mechanisms that control the kinetics of arsenic(III) photocatalytic oxidation when meso‐TiO2 is coupled with an Fe2O3 adsorbent phase are investigated herein. Parasitic light absorption is the primary factor, followed by changes in rate law (from disguised zero‐order to first order). Charge transfer across the heterojunction in our material is negligible.