Development of a p-n Ni-ZIF/TiO2 Heterojunction for Photoelectrocatalytic Hydrogen Generation from Seawater

IF 2.3 4区化学 Q3 CHEMISTRY, PHYSICAL

Catalysis Letters Pub Date : 2025-07-09 DOI:10.1007/s10562-025-05070-0

Daxiang Jin, Wanggang Zhang, Jian Wang, Xiaohong Li, Yiming Liu

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引用次数: 0

Abstract

Photoelectrochemical (PEC) seawater splitting faces challenges including limited light absorption, rapid charge recombination, and chloride corrosion. This study addresses these issues by constructing a p-n heterojunction composite photoanode (Ni-ZIF/TNTAs) through solvothermal integration of nickel-based zeolitic imidazolate framework (Ni-ZIF) onto anodized TiO₂ nanotube arrays (TNTAs). The synergy between Ni-ZIF (bandgap: 2.23 eV) and TNTAs narrows the composite bandgap to 2.72 eV, extending light absorption to 450 nm. The optimized Ni-ZIF/TNTAs (NT-0.01) achieves a photocurrent density of 2.2 mA/cm² at 1.23 V vs. RHE in simulated seawater (3.5 wt% NaCl), fivefold higher than pristine TNTAs (0.44 mA/cm²), alongside a hydrogen evolution rate of 117.5 µmol/cm². Mott-Schottky and UV-vis analyses confirm a built-in electric field at the p-n junction interface, facilitating charge separation and doubling the incident photon-to-current efficiency (IPCE) to 30% at 365 nm. Remarkably, the composite retains 96% hydrogen yield over four cycles, attributed to dynamically formed surface NiOOH layers that suppress chloride penetration while maintaining 87% oxygen evolution reaction (OER) selectivity. This work pioneers the application of Ni-ZIF/TiO₂ heterojunctions in seawater splitting, offering a scalable strategy to reduce freshwater dependency in solar-driven hydrogen production. The design merges visible-light harvesting, corrosion resistance, and efficient charge transport, advancing sustainable energy solutions.

Graphical Abstract

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海水光电催化制氢用p-n Ni-ZIF/TiO2异质结的研制

光电化学（PEC）海水裂解技术面临着光吸收受限、电荷快速复合和氯化物腐蚀等挑战。本研究通过镍基沸石咪唑盐框架（Ni-ZIF）在阳极氧化的TiO2纳米管阵列（TNTAs）上的溶剂热集成，构建了p-n异质结复合光阳极（Ni-ZIF/TNTAs），解决了这些问题。Ni-ZIF（带隙为2.23 eV）和TNTAs之间的协同作用将复合带隙缩小到2.72 eV，将光吸收扩展到450 nm。优化后的Ni-ZIF/TNTAs （NT-0.01）在模拟海水（3.5 wt% NaCl）中，在1.23 V条件下的光电流密度为2.2 mA/cm²，比原始TNTAs （0.44 mA/cm²）高5倍，析氢率为117.5µmol/cm²。Mott-Schottky和UV-vis分析证实，在p-n结界面处存在内置电场，促进电荷分离，并在365 nm处将入射光子电流效率（IPCE）提高一倍，达到30%。值得注意的是，复合材料在四个循环中保持了96%的产氢率，这归功于动态形成的表面NiOOH层抑制了氯化物的渗透，同时保持了87%的析氧反应（OER）选择性。这项工作开创了Ni-ZIF/TiO2异质结在海水分裂中的应用，为减少太阳能驱动制氢对淡水的依赖提供了一种可扩展的策略。该设计融合了可见光收集、耐腐蚀和高效电荷传输，推进了可持续能源解决方案。图形抽象

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来源期刊

Catalysis Letters 化学-物理化学

CiteScore

5.70

自引率

3.60%

发文量

327

审稿时长

1 months

期刊介绍： Catalysis Letters aim is the rapid publication of outstanding and high-impact original research articles in catalysis. The scope of the journal covers a broad range of topics in all fields of both applied and theoretical catalysis, including heterogeneous, homogeneous and biocatalysis. The high-quality original research articles published in Catalysis Letters are subject to rigorous peer review. Accepted papers are published online first and subsequently in print issues. All contributions must include a graphical abstract. Manuscripts should be written in English and the responsibility lies with the authors to ensure that they are grammatically and linguistically correct. Authors for whom English is not the working language are encouraged to consider using a professional language-editing service before submitting their manuscripts.