The salt ions (typically > 1000 mg/L) present in copper plating wastewater limit the application of ion exchange in the deep treatment of copper complexes (such as copper-pyrophosphate (Cu-PPi)). Metal nanoparticle immobilization is an effective method, and bimetallic nanoparticles have more potential than monometallic ones. In this study, bimetallic nanocomposite Ti-Zr-201 was successfully synthesized by confining Ti-Zr oxide nanoparticles in the pores of anion exchange polymer (D201). The obtained new adsorbent Ti-Zr-201 with bimetallic doped structure had more active sites (7.22 mmol/g), higher hydroxyl content (3.51 × 10²² OH/ nm²) and larger specific surface area (31.65 m²/g) than monometallic nanocomposite adsorbents (Zr-201 and Ti-201). The results showed that Ti-Zr-201 has better Cu-PPi adsorption capacity (24.82 mg Cu/g) than Zr-201 (21.48 mg Cu/g) and Ti-201 (21.71 mg Cu/g) in the high salt water (2000 mg/L NO₃^–). Further mechanistic studies revealed that Cu-PPi removal as a whole was mainly realized via ternary complexation (Ti/Zr-O-Cu-PPi of Type-A, Ti/Zr-O-PPi-Cu of Type-B) and quaternary complexation (Ti/Zr-O-PPi-Cu-PPi of Type-B) both formed during the adsorption. The saturated Ti-Zr-201 can be regenerated more than 90% rapidly and had good stability. Moreover, the novel adsorbent also had a excellent removal effect on several other phosphorous copper complexes (tripolyphosphate, methyl dihydrogen phosphate, etc.). Therefore, the nanocomposite Ti-Zr-201 exhibited promising application on the deep removal of complex-state Cu with phosphorus ligands from high salty wastewater.

中文翻译：

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利用纳米限域 Ti-Zr 二元金属氧化物增强高盐废水焦磷酸铜络合物去除：多元络合机理


镀铜废水中存在的盐离子（通常为 > 1000 mg/L）限制了离子交换在铜络合物（如焦磷酸铜 （Cu-PPi）））的深处理中的应用。金属纳米颗粒固定化是一种有效的方法，双金属纳米颗粒比单金属纳米颗粒具有更大的潜力。在本研究中，通过将 Ti-Zr 氧化物纳米颗粒限制在阴离子交换聚合物 （D201） 的孔隙中，成功合成了双金属纳米复合材料 Ti-Zr-201。与单金属纳米复合吸附剂（Zr-201 和 Ti-201）相比，所得的双金属掺杂结构新型吸附剂 Ti-Zr-201 具有更多的活性位点 （7.22 mmol/g）、更高的羟基含量 （3.51 × 10²² OH/ nm²） 和更大的比表面积 （31.65 m²/g）。结果表明，Ti-Zr-201在高盐水（2000 mg/L NO₃^–）中的吸附容量（24.82 mg Cu/g）优于Zr-201（21.48 mg Cu/g）和Ti-201（21.71 mg Cu/g）。进一步的机理研究表明，Cu-PPi 整体的去除主要通过吸附过程中形成的三元络合 （Ti/Zr-O-Cu-PPi， Ti/Zr-O-PPi-Cu-PPi） 和四元络合 （Ti/Zr-O-PPi-B型的 Cu-PPi） 来实现。饱和的 Ti-Zr-201 可快速再生 90% 以上，稳定性好。此外，这种新型吸附剂对其他几种磷铜络合物（三聚磷酸盐、磷酸二氢甲酯等）也具有极好的去除效果。因此，纳米复合材料 Ti-Zr-201 在从高盐废水中深度去除含磷配体的复杂态 Cu 方面表现出有前途的应用。