Selective placement of modifiers on hematite thin films for solar water splitting

Author(s)

Pires, Fabio A. ; dos Santos, Gabriel T. ; Bettini, Jefferson ; Costa, Carlos A. R. ; Goncalves, Renato V. ; Castro, Ricardo H. R. ; Souza, Flavio L.

• Document type: Journal article
• Source: SUSTAINABLE ENERGY & FUELS; v. 7, n. 20, p. 14-pg., 2023-10-10.

Abstract

The design of nanostructured materials for photoelectrochemical water splitting relies on a detailed understanding of the reactional bottlenecks. For hematite, a model system for photoanodes, the challenges concern poor charge transfer and separation, carrier recombination rate, and sluggish water oxidation kinetics. Several methods have been proposed to address each individually, with complex multi-step processes offered as solutions to improve overall performance. Here, we introduce a single polymeric precursor solution that enables the design of hematite (alpha-Fe2O3) with synergistic bulk and interfacial engineering using Ga3+, Hf4+ and NiFeOx. The solution causes Ga3+ to dope hematite lattice to reduce polaronic effects, while simultaneously induces Hf4+ enrichment at both surface and grain boundaries, improving charge separation and reducing recombination. Hf4+ also led to a refined microstructure derived from interface stabilization, which associated with Ga3+ bulk doping and NiFeOx electrodeposition resulted in a thin film with 65% of overall photoelectrode efficiency. As a consequence, the modified hematite photoanode (176 nm-thick) delivered a water oxidation photocurrent of 2.30 mA cm-2 in contrast to 0.37 mA cm-2 for the pristine system measured at 1.23 V against hydrogen reversible electrode (RHE). The results suggest the simplicity of this new polymeric solution may offer a cost-effective, scalable and versatile alternative for multiple chemical modifications in oxides beyond hematite. A dual-modification strategy enabling the design of hematite with synergistic bulk and interfacial engineering for improved performance as photoanode. (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: 22/04150-6 - Study of nanoceramics for energy application: sintering and interface
• Grantee: Flavio Leandro de Souza
• Support Opportunities: Research Grants - Visiting Researcher Grant - International
• FAPESP's process: 21/04967-0 - Designing hematite photoelectrode via chemical routes for sunlight-induced water splitting
• Grantee: Fabio Augusto Pires
• Support Opportunities: Scholarships in Brazil - Doctorate (Direct)