The existing literature survey reports rare and conflicting studies on the effect of the preparation method of metal-based semiconductor photocatalysts on structural/morphological features, electronic properties, and kinetics regulating the photocatalytic H-2 generation reaction. In this investigation, we compare the different copper/titania-based photocatalysts for H-2 generation synthesized via distinct methods (i.e., photodeposition and impregnation). Our study aims to establish a stringent correlation between physicochemical/electronic properties and photocatalytic performances for H-2 generation based on material characterization and kinetic modeling of the experimental outcomes. Estimating unknown kinetic parameters, such as charge recombination rate and quantum yield, suggests a mechanism regulating charge carrier lifetime depending on copper distribution on the TiO2 surface. We demonstrate that H-2 generation photoefficiency recorded over impregnated CuxOy/TiO2 is related to an even distribution of Cu(0)/Cu(I) on TiO2, and the formation of an Ohmic junction concertedly extended charge carrier lifetime and separation. The outcomes of the kinetic analysis and the related modeling investigation underpin photocatalyst physicochemical and electronic properties. Overall, the present study lays the groundwork for the future design of metal-based semiconductor photocatalysts with high photoefficiencies for H-2 evolution.

Effect of Synthesis Method on Reaction Mechanism for Hydrogen Evolution over CuxOy/TiO2 Photocatalysts: A Kinetic Analysis

Di Somma Ilaria;
2023

Abstract

The existing literature survey reports rare and conflicting studies on the effect of the preparation method of metal-based semiconductor photocatalysts on structural/morphological features, electronic properties, and kinetics regulating the photocatalytic H-2 generation reaction. In this investigation, we compare the different copper/titania-based photocatalysts for H-2 generation synthesized via distinct methods (i.e., photodeposition and impregnation). Our study aims to establish a stringent correlation between physicochemical/electronic properties and photocatalytic performances for H-2 generation based on material characterization and kinetic modeling of the experimental outcomes. Estimating unknown kinetic parameters, such as charge recombination rate and quantum yield, suggests a mechanism regulating charge carrier lifetime depending on copper distribution on the TiO2 surface. We demonstrate that H-2 generation photoefficiency recorded over impregnated CuxOy/TiO2 is related to an even distribution of Cu(0)/Cu(I) on TiO2, and the formation of an Ohmic junction concertedly extended charge carrier lifetime and separation. The outcomes of the kinetic analysis and the related modeling investigation underpin photocatalyst physicochemical and electronic properties. Overall, the present study lays the groundwork for the future design of metal-based semiconductor photocatalysts with high photoefficiencies for H-2 evolution.
2023
Istituto di Scienze e Tecnologie per l'Energia e la Mobilità Sostenibili - STEMS
photocatalysis
hydrogen production
kinetic modeling
CuxOy
TiO2
Ohmic junction
long-lived charge-separated state
charge carrier recombination
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/20.500.14243/456657
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