Hierarchical flower-like zinc ferrite photoanode for enhanced photoelectrocatalytic water splitting effect of ammonium fluoride-assisted morphological control

IF 3.6 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Solid State Sciences Pub Date : 2025-12-01 Epub Date: 2025-10-28 DOI:10.1016/j.solidstatesciences.2025.108115

R.A. Kadam , S.B. Madake , M.A. Yewale , A.A. Jadhawar , S.A. Alshehri , R. Venkatesan , D.K. Shin , Minjae Kim

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Abstract

In this study, hierarchical ZnFe₂O₄ nanostructures were synthesized via a hydrothermal method using ammonium fluoride (NH₄F) as a morphology-directing agent. By varying NH₄F concentrations (30–120 mM), we successfully modulated the material morphology from agglomerated nanoparticles to highly ordered flower-like architectures. Comprehensive structural and morphological analyses confirmed the formation of phase-pure spinel ZnFe₂O₄ with tailored crystal orientation and reduced lattice strain. Among the samples, the ZF-AF-120mM nanostructure, composed of radially assembled nanosheets, exhibited outstanding photoelectrochemical (PEC) performance for solar water splitting. It delivered a peak photocurrent density of 6.25 mA cm⁻² at 1.3 V vs. Ag/AgCl and an applied bias photon-to-current efficiency (ABPE) of 0.45 %, along with excellent stability (61.1 % retention over 2h). Electrochemical impedance spectroscopy revealed the lowest charge transfer resistance (R_ct = 16.09 Ω) for ZF-AF-120mM, indicating enhanced charge transport and reduced recombination. The exceptional PEC activity is attributed to the hierarchical nanoflower morphology, which promotes superior light harvesting, increased surface area, and efficient charge carrier dynamics. These results underscore the crucial role of NH₄F-mediated morphology engineering in optimizing spinel ferrite photoanodes for efficient and durable solar-driven hydrogen generation.

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层次化花状铁酸锌光阳极对增强氟化铵光电催化水裂解效果的辅助形态控制

本研究以氟化铵（NH4F）为形态导向剂，通过水热法制备了具有层次结构的ZnFe2O4纳米结构。通过改变NH4F浓度（30-120 mM），我们成功地将材料形态从凝聚的纳米颗粒调节为高度有序的花状结构。综合结构和形态分析证实，形成了取向定制、晶格应变减小的相纯尖晶石ZnFe2O4。其中，由径向组装纳米片组成的ZF-AF-120mM纳米结构在太阳能水分解中表现出优异的光电化学（PEC）性能。在1.3 V vs. Ag/AgCl下，它的峰值光电流密度为6.25 mA cm−2，应用偏压光子电流效率（ABPE）为0.45%，具有优异的稳定性（2h内保持率为61.1%）。电化学阻抗谱显示ZF-AF-120mM的电荷转移电阻最低（Rct = 16.09 Ω），表明电荷传输增强，复合减少。特殊的PEC活性归因于分层纳米花的形态，它促进了优越的光收集，增加了表面积，以及有效的载流子动力学。这些结果强调了nh4f介导的形态学工程在优化尖晶石铁氧体光阳极以实现高效耐用的太阳能制氢方面的关键作用。

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来源期刊

Solid State Sciences 化学-无机化学与核化学

CiteScore

6.60

自引率

2.90%

发文量

214

审稿时长

27 days

期刊介绍： Solid State Sciences is the journal for researchers from the broad solid state chemistry and physics community. It publishes key articles on all aspects of solid state synthesis, structure-property relationships, theory and functionalities, in relation with experiments. Key topics for stand-alone papers and special issues: -Novel ways of synthesis, inorganic functional materials, including porous and glassy materials, hybrid organic-inorganic compounds and nanomaterials -Physical properties, emphasizing but not limited to the electrical, magnetical and optical features -Materials related to information technology and energy and environmental sciences. The journal publishes feature articles from experts in the field upon invitation. Solid State Sciences - your gateway to energy-related materials.