Interfacial engineering of hematite photoanodes toward high water splitting performance

Author(s)

Thomaz, Kelly T. C. ; Bedin, Karen C. ; Rodriguez-Gutierrez, Ingrid ; Verissimo, Nathalia C. ; Bettini, Jefferson ; Souza, Flavio L.

• Document type: Journal article
• Source: MATERIALS TODAY ENERGY; v. 37, p. 11-pg., 2023-10-01.

Abstract

Efficient and scalable photoelectrochemical water splitting electrode designs are a challenge. This study focuses on hafnium-modified hematite (X%Hf-HEM) photoanodes, prepared via spin-coating polymeric precursor solutions with varying Hf4 thorn /Fe3 thorn (mol) ratios (1.0%, 3.0%, 4.0%, and 5.0%) onto fluorine-doped tin oxide substrates. Structural, morphological, and compositional analyses confirm pure hematite phases in all X%Hf-HEM samples. Increasing Hf4 thorn content correlated with reduced grain size, thickness, and surface roughness due to Hf4 thorn segregation at grain boundaries during thermal treatment. Hafnium segregation at hematite grain boundaries and hematite|fluorine-doped tin oxide interfaces is confirmed using scanning transmission electron microscopy coupled with energy dispersive spectroscopy. Notably, the 4%Hf-HEM photoanode exhibits exceptional efficiency enhancement, outperforming HEM efficiency by 4.5 times. Gas chromatography results highlight O2 and H2 evolution rates of 14.49 +/- 0.09 mmol/cm2/h and 8.1 +/- 0.5 mmol/cm2/h, respectively, for 4%Hf-HEM, with a H2/O2 ratio close to 2:1. The charge dynamics investigated from intensity-modulated photocurrent spectroscopy evidence the main Hf4 thorn effect of improving charge separation, achieving greater efficiency for 4%Hf-HEM. Shifts in valence band maximum from ultraviolet photoelectron spectroscopy measurements indicate surface state presence, supported by htransfer trends calculated from intensity-modulated photocurrent spectroscopy. This research presents a scalable, cost-effective approach to multiinterface photoanode development, holding promise for innovative photoelectrochemical water splitting technologies.(c) 2023 Elsevier Ltd. All rights reserved. (AU)

• FAPESP's process: 17/11986-5 - Generation and storage of New Energy: bringing technological development for the country
• Grantee: Ana Flávia Nogueira
• Support Opportunities: Research Grants - Research Centers in Engineering Program
• FAPESP's process: 17/02317-2 - Interfaces in materials: electronic, magnetic, structural and transport properties
• Grantee: Adalberto Fazzio
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 21/07459-5 - Control of electronic properties of columnar hematite nanostructure by double transition elements insertion for photoelectrocatalitic water splitting
• Grantee: Karen Cristina Bedin
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 19/06654-9 - Incorporation of metallic nanoparticles in hematite photoelectrodes: effect of solid-solid interface on optical and electrical properties
• Grantee: Ingrid Guadalupe Rodriguez Gutierrez
• Support Opportunities: Scholarships in Brazil - Post-Doctoral