Ce掺杂对Ti/Sn _0.918Sb _0.109O ₂电极电催化性能的影响

Effect of Ce doping on the electrochemical performance of Ti/Sn _0.918Sb _0.109O ₂ electrode

摘要

[目的]针对涂料及印染等行业废水中难降解染料污染物的深度处理需求，提高Ti/Sn _0.918Sb _0.109O ₂电极的电催化活性与服役寿命，为电化学法处理涂料废水提供高效、长寿命的阳极材料。[方法]采用热分解法在Ti基体上制备Sn _0.918Sb _0.109O ₂活性层(记为TS电极)，再经脉冲电沉积引入稀土Ce制得Ti/Sn _0.918Sb _0.109O ₂−CeO _{2− x} 电极(记为SC电极)。通过SEM、XRD、循环伏安、电化学阻抗谱、阳极析氧极化曲线和加速寿命试验考察Ce掺杂对电极表面形貌与电化学行为的影响，并辅以密度泛函理论(DFT)计算从原子尺度阐明其电子结构调控机制。[结果]Ce掺杂使涂层晶粒细化、表面致密；与TS电极相比，SC电极的电化学活性面积(ECSA)由186.5 cm ²增至258.5 cm ²，双电层电容 C _dl由7.46 mF/cm ²增至10.34 mF/cm ²，Tafel斜率由456.22 mV/dec降至308.02 mV/dec，电荷转移电阻显著降低，加速寿命由0.575 h延长至9.902 5 h；在10 mA/cm ²下处理100 mg/L罗丹明B(RhB)溶液，SC电极在120 s内即实现完全脱色，伪一级速率常数 k = 0.068 4 s ⁻¹，约为TS电极( k = 5.59 × 10 ⁻⁴ s ⁻¹)的122.4倍。DFT计算表明，Ce的引入使氧空位形成能由3.98 eV降至2.98 eV，进入晶格氧机制(LOM)的活性窗口。[结论]Ce掺杂可显著提升Ti/Sn _0.918Sb _0.109O ₂电极的电催化活性，降低界面电荷转移电阻，并延长服役寿命。

Abstract

[Objective] To meet the demand for advanced treatment of refractory dye pollutants generated from coating and printing-dyeing industrial wastewater, the electrocatalytic activity and service life of Ti/Sn _0.918Sb _0.109O ₂ electrodes need to be further enhanced, so as to provide an efficient and long-lifetime anode material for the electrochemical treatment of coating wastewater. [Method] An Sn _0.918Sb _0.109O ₂ active layer was deposited on a Ti substrate by thermal decomposition (denoted as the TS electrode). Subsequently, rare-earth cerium was introduced via pulse electrodeposition to yield a Ti/Sn _0.918Sb _0.109O ₂–CeO _{2− x} electrode (denoted as the SC electrode). The effects of Ce doping on surface morphology and electrochemical performance of electrodes were systematically investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), anodic oxygen-evolution polarization curves and accelerated life testing. Density functional theory (DFT) calculations were further performed to elucidate the underlying electronic-structure modulation at the atomic scale. [Result] Ce doping refined the grains and densified the coating. Compared with the TS electrode, the SC electrode exhibited an increase in electrochemically active surface area (ECSA) from 186.5 cm ² to 258.5 cm ², an increase in double-layer capacitance ( C _dl) from 7.46 mF/cm ² to 10.34 mF/cm ², a decrease in Tafel slope from 456.22 mV/dec to 308.02 mV/dec, a markedly reduced charge-transfer resistance, and an extension of the accelerated lifetime from 0.575 h to 9.902 5 h. For the degradation of 100 mg/L Rhodamine B (RhB) at a current density of 10 mA/cm ², the SC electrode achieved complete decolorization within 120 s, with a pseudo-first-order rate constant of k = 0.068 4 s ⁻¹, approximately 122.4 times that of the TS electrode ( k = 5.59 × 10 ⁻⁴ s ⁻¹). DFT calculations revealed that Ce incorporation lowered the oxygen-vacancy formation energy from 3.98 eV to 2.98 eV, placing it within the active window of the lattice oxygen mechanism (LOM). [Conclusion] Ce doping significantly enhances the electrocatalytic activity, reduces the interfacial charge-transfer resistance, and prolongs the service life of Ti/Sn _0.918Sb _0.109O ₂ electrodes.

关键词

涂料废水 / 铈掺杂 / 热分解 / 脉冲电沉积 / 晶格氧 / 服役寿命

Key words

paint wastewater / cerium doping / thermal decomposition / pulsed electrodeposition / lattice oxygen / service life

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基金资助

湖南省自然科学基金(2025JJ60080)

湖南省自然科学基金(2025JJ80338)

湖南省自然科学基金(2026JJ90232)

长沙市自然科学基金(KQ2502002)