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本研究采用水热法制备钙掺杂钛酸钡(Ba_xCa1-xTiO3)压电光催化剂，通过X射线衍射(XRD)和X射线光电子能谱(XPS)表征，证实钙元素已成功掺入钛酸钡晶格。在超声协同磁力搅拌条件下，研究了该催化剂对四环素(TC)的吸附性能及压电催化降解性能。结果表明，相比商业钛酸钡(BaTiO3)，最优掺杂比例为Ba0.8Ca0.2TiO3的样品对TC的吸附量提升59.75%。在10 mg/L的TC溶液中加入100 mg催化剂，经120 min超声压电催化反应后，TC的降解率超过90%。pH效应研究表明，中性条件下吸附效果最佳(中性>碱性>酸性)，而碱性条件下催化降解效果最优(碱性>中性>酸性)。Zeta电位分析表明，酸性和碱性环境中，催化剂分别带正电和负电，且两种情况下均与TC带同种电荷；在暗吸附过程中，因同种电荷相互排斥，吸附效果较差。循环稳定性测试证实，该催化剂具有良好的重复使用性能。自由基猝灭实验进一步明确，h+、·OH和O2~-是催化反应中的主要活性物种。结合表征结果分析，钙掺杂改变了钛酸钡的表面结构和化学组成，既增强了其对TC的吸附能力，又促进了表面活性氧物种的生成，从而显著提升了TC的降解效率。
Abstract：Calcium-doped barium titanate(Ba_xCa1-xTiO3) piezoelectric photocatalysts were prepared by the hydrothermal method. X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS) characterizations confirmed that the Ca element had been successfully incorporated into the barium titanate lattice. Under the condition of ultrasonic-assisted magnetic stirring, the adsorption performance and piezoelectric catalytic degradation performance of the catalyst for tetracycline(TC) were investigated. The results showed that compared with commercial barium titanate(BaTiO3), the sample with the optimal doping ratio of Ba0.8Ca0.2TiO3 increased the adsorption capacity of TC by 59.75%. When 100 mg of the catalyst was added to a 10 mg/L TC solution and subjected to 120 min of ultrasonic piezoelectric catalytic reaction, the degradation rate of TC exceeded 90%. The pH effect study indicated that the adsorption effect was best under neutral conditions(neutral > alkaline > acidic), while the catalytic degradation effect was optimal under alkaline conditions(alkaline > neutral > acidic). Zeta potential analysis showed that the catalyst carried positive and negative charges in acidic and alkaline environments, respectively, and both cases carried the same charge as TC. In the dark adsorption process, due to the mutual repulsion of the same charges, the adsorption effect was poor. The cyclic stability test confirmed that the catalyst had good reusability. The radical scavenging experiment further confirmed that h+, ·OH and O2~- were the main active species in the catalytic reaction. Combined with the characterization results, it was analyzed that the Ca doping changed the surface structure and chemical composition of barium titanate, which not only enhanced its adsorption capacity for TC but also promoted the generation of surface active oxygen species, thereby significantly improving the degradation efficiency of TC.
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基本信息:
DOI：10.16026/j.cnki.iea.2026010009
中图分类号:X703;TQ426
引用信息:
[1]肖六七,张雷,莫倩倩,等.钙掺杂钛酸钡压电催化剂的制备及其四环素降解性能[J].离子交换与吸附,2026,42(01):9-18.DOI:10.16026/j.cnki.iea.2026010009.
基金信息:
天津工业大学沧州研究院项目(项目号TGCYY-F-0206)