Abstract:

In this study, the TiO₂ modified graphene composite material (RGO/ TiO₂) was prepared by hydrothermal method, and its morphological structure and electrochemical properties were investigated. Then RGO/TiO₂ material was assembled into electrode, and NH₄⁺ ions electrosorption efficiencies of unmodified graphene (RGO) electrode and the RGO/TiO₂ electrode were compared. The effects of applied voltage, circulating velocity and initial concentration on NH₄⁺ ions electrosorption by RGO/TiO₂ electrode were investigated. The characteristics of NH₄⁺ ions electrosorption and the effect of advanced NH₄⁺ ions removal from simulated actual wastewater containing NH₄⁺ ions were also studied. The results showed that the RGO/TiO₂ composite material had a three-dimensional pore structure with specific surface area of 382.08 m²·g^-1 and specific capacitance of 325.80 F·g^-1 at a scan rate of 0.01 V·s^-1, which were better than those of the RGO material. The initial adsorption capacity of RGO/TiO₂ electrode was 28.3% higher than that of RGO electrode. After 10 cycles of regeneration adsorption, the adsorption capacity of NH₄⁺ ions of RGO/TiO₂ electrode only decreased 5.87%, and its cyclic regeneration adsorption property was better than that of RGO electrode. In addition, the applied voltage 2.0 V, circulating velocity 35 ml·min^-1 and initial concentration 1.0 mmol·L^-1 were the optimal NH₄⁺ ions electrosorption conditions for RGO/TiO₂ electrode. The electrosorption process of NH₄⁺ ions by RGO and RGO/TiO₂ electrodes was in accordance with the quasi-first-order kinetic model and the Freundlich isothermal adsorption model. The electrosorption of NH₄⁺ ions was a multi-layer adsorption behavior on heterogeneous surface and physical adsorption was the dominant. When the RGO/TiO₂ electrode was connected in 4-stage series, the removal efficiency of simulated actual NH₄⁺ refining purified water reached 86.84%.

Key words: graphene, TiO₂, composites, electrosorption, NH₄⁺

摘要：

通过水热法制备得到TiO₂改性石墨烯复合材料（RGO/TiO₂），考察了其形貌结构和电化学性能。将其组装成电极，对比未改性石墨烯（RGO）电极和RGO/TiO₂电极的电吸附NH₄⁺性能。重点考察外加电压、循环流速、初始浓度等工艺参数对RGO/TiO₂电极电吸附NH₄⁺的影响，并对其电吸附NH₄⁺特性和对模拟实际含NH₄⁺废水深度脱NH₄⁺效果进行研究。结果表明：RGO/TiO₂复合材料具有三维孔洞结构，比表面积为382.08 m²·g^-1，比电容量在扫速为0.01 V·s^-1时达到325.80 F·g^-1，优于RGO材料。RGO/TiO₂电极的初次电吸附量较RGO电极提升了28.3%，循环再生吸附10次后，RGO/TiO₂电极的NH₄⁺吸附量仅降低了5.87%，循环再生吸附性能优于RGO电极。外加电压2.0 V、循环流速35 ml·min^-1和NH₄⁺初始浓度1.0 mmol·L^-1为RGO/TiO₂电极的最佳NH₄⁺电吸附条件。RGO和RGO/TiO₂电极电吸附NH₄⁺过程符合准一级动力学模型和Freundlich等温吸附模型，电吸附NH₄⁺为非均匀表面的多层吸附行为，以物理吸附为主。RGO/TiO₂电极4级串联时对模拟实际含NH₄⁺炼油净化水的去除率达到86.84%。

关键词: 石墨烯, TiO₂, 复合材料, 电吸附, NH₄⁺