目的 制备TiO2纳米管填充Cu2O纳米棒的芯鞘结构,并讨论其影响因素。方法 通过精准的阴极极化和优化的脉冲沉积工艺在TiO2纳米管内部填充Cu2O,实现Cu2O在TiO2纳米管内部的填充率为100%。通过控制变量法分析电化学沉积方法、脉冲电位沉积工艺参数和电镀液配比对TiO2纳米管填充Cu2O的影响规律。结果 对TiO2纳米管进行精准的阴极极化,选择性地提高内部阻挡层的导电性,促使电沉积过程中Cu2O在TiO2纳米管底部形核析出并沿着底部至顶部的方向定向沉积,形成TiO2纳米管包裹Cu2O纳米棒的芯鞘结构。电化学沉积方法、脉冲电位沉积工艺参数和电镀液配比对Cu2O在TiO2纳米管内的填充率有重要影响。脉冲电位沉积法产生更大的沉积电流密度,提高Cu2O形核速率,减小Cu2O晶核临界半径,是最佳的电化学填充方法。随着阴极脉冲电位负移、脉冲循环数增加和阴阳极脉冲宽度比增大,Cu2O的形核速率和沉积时间增大,TiO2纳米管填充Cu2O的微观形貌从完全不填充转变为部分填充,再转变为完全填充,最后转变为过度填充。随着电镀液的主盐浓度增大、pH值减小、温度升高,Cu2O的形核速率增大,TiO2纳米管填充Cu2O的微观形貌从部分填充转变为完全填充再转变为过度填充。结论 TiO2纳米管填充Cu2O受TiO2纳米管一维导电特性和沉积工艺参数的共同影响,前者为主要因素,后者为次要因素。对于不同长径比的TiO2纳米管填充Cu2O,应注意电化学阴极极化、电化学沉积方法、电化学沉积工艺参数和电镀液配比对Cu2O在TiO2纳米管内部填充率的综合影响。
Abstract
The work aims to fabricate a well-defined core-shell nanostructure consisting of TiO2 nanotube arrays filled with Cu2O nanorods and to comprehensively investigate the multiple factors that affect the filling process. Through the application of a carefully controlled cathodic polarization treatment combined with an optimized pulse electrodeposition technique, Cu2O was successfully deposited into the interior of the TiO2 nanotube arrays, ultimately achieving a 100% filling rate throughout the entire nanotube length. A systematic analysis was conducted to elucidate the effects of several critical variables, including the choice of electrochemical deposition method, the specific pulse potential deposition parameters, and the composition of the electroplating solution, on the efficiency and completeness of Cu2O incorporation within the TiO2 nanotube channels.
By implementing a precise cathodic polarization step prior to deposition, the intrinsic electrical conductivity of the internal barrier layer of the TiO2 nanotube arrays was selectively enhanced. This polarization treatment created a distinct conductivity gradient between the inner barrier layer and the outer nanotube wall, which in turn promoted preferential nucleation of Cu2O at the closed bottom of the nanotube arrays. Following nucleation, Cu2O progressively deposited along the axial direction of the TiO2 nanotube arrays, propagating from the bottom toward the open top and ultimately forming a continuous core-shell architecture with a complete 100% filling rate. It was observed that the electrochemical deposition method, the fine-tuned pulse deposition parameters, and the electrolyte formulation collectively exerted significant effects on the final filling morphology of Cu2O within the TiO2 nanotube arrays. Among these, the pulse potential deposition method proved to be the most effective, as the intermittent potential application generated a higher instantaneous deposition current density, accelerated the nucleation kinetics of Cu2O, and decreased the critical nucleus radius, thereby ensuring dense and uniform filling.
Furthermore, as the cathodic pulse potential shifted toward more negative values, the number of deposition pulse cycles increased, and the ratio of cathodic to anodic pulse widths was adjusted upward, both the nucleation rate and the overall deposition time of Cu2O within the TiO2 nanotube arrays were substantially enhanced. These variations induced a clear microstructural evolution of the filled arrays, which underwent distinct transitional stages, including an initial no-filling state, partial filling, complete filling, and eventually overfilling when deposition exceeded the nanotube capacity. In addition, the characteristics of the electroplating solution played a vital role: increasing the main salt concentration, lowering the pH, and elevating the electrolyte temperature all promoted a higher nucleation rate of Cu2O, which drove the microstructure through the same sequence of partial to complete and overfilling states.
The overall results demonstrate that the successful filling of Cu2O nanorods into TiO2 nanotube arrays is primarily governed by the one-dimensional electrical conductive properties of the TiO2 nanotube arrays, while the deposition process parameters serve as secondary critical affecting factors. For the TiO2 nanotube arrays with different aspect ratios, the combined effects of cathodic polarization, the selected electrochemical deposition approach, the optimized pulse deposition parameters, and the electrolyte composition must be carefully balanced to achieve a high and uniform filling rate of Cu2O within the TiO2 nanotube arrays. These findings provide valuable insights into the rational design of core-shell nanostructures for functional applications in energy conversion, photocatalysis, and sensing technologies.
关键词
TiO2纳米管 /
Cu2O /
填充率 /
芯鞘结构 /
电化学沉积 /
影响因素
Key words
TiO2 nanotube arrays /
Cu2O /
filling rate /
core-sheath structure /
electrochemical deposition /
affecting factors
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基金
国家自然科学基金（42276216,52301087）; 福建省高校产学合作项目（2023H6028）; 福建省中青年教师教育科研项目（科技类）（JAT231049）; 福建省自然科学基金（2023J01783）
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