The UIO-66 type of metal–organic frameworks (MOFs) showed excellent performance in water purification, however, the recovery difficulty for powdered UIO-66 remains challenging for the practical applications. Herein, we prepared granular adsorbents (gGO-U-N) derived from a UIO-66/GO composite and granulated them using polyacrylamide (PAM) and polyvinyl alcohol (PVA) polymers to improve F removal capacity. The gGO-U-N resulted in COZr lattice contraction, improving the Coulomb interactions in Zr for better F interaction. Consequently, gGO-U-50 with 50 % (w/w) of UIO-66 mass ratio showed a higher F adsorption capacity (102 mg g) than powdered UIO-66 (67 mg g), exhibiting high synergistic factor (f = 2.1) for F adsorption. Additionally, gGO-U-50 exhibited stable adsorption capability over a wide pH range and higher F adsorption selectivity than gGO. Based on time-lapse Fourier transform infrared attenuated total reflection, X-ray photoelectron spectroscopy, and Raman spectroscopic analysis, the Zr-O-C bond on gGO-U-50 was found to serve as the dominant F sorption site, while the carbon–oxygen and amine groups contributed a minor portion for F removal. Notably, the gGO-U-50 exhibited the F water treatment cost of 1621.6 mg-F $, which is approximately 3 times cost-effective than the UIO-66 (632.07 mg-F $). Fixed-bed column experiments demonstrated that gGO-U-50 exhibited a higher F adsorption capability (6.34 mg g) than other reported granular adsorbents, revealing that gGO-U-50 has the potential for F remediation.

中文翻译：

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使用聚丙烯酰胺/聚乙烯醇制备颗粒状 UIO-66/氧化石墨烯以选择性去除氟化物：通过原位表面增强拉曼光谱分析和连续流柱操作进行机理研究

UIO-66型金属有机框架（MOF）在水净化方面表现出优异的性能，然而，粉末状UIO-66的回收难度对于实际应用仍然具有挑战性。在此，我们制备了由 UIO-66/GO 复合材料衍生的颗粒吸附剂 (gGO-UN)，并使用聚丙烯酰胺 (PAM) 和聚乙烯醇 (PVA) 聚合物将其造粒，以提高除氟能力。 gGO-UN 导致 COZr 晶格收缩，改善 Zr 中的库仑相互作用，从而获得更好的 F 相互作用。因此，含有 50% (w/w) UIO-66 质量比的 gGO-U-50 显示出比粉末状 UIO-66 (67 mg g) 更高的 F 吸附容量 (102 mg g)，表现出高协同因子 (f = 2.1) F吸附。此外，gGO-U-50在较宽的pH范围内表现出稳定的吸附能力，并且比gGO具有更高的F吸附选择性。基于延时傅里叶变换红外衰减全反射、X射线光电子能谱和拉曼光谱分析，发现gGO-U-50上的Zr-OC键是主要的F吸附位点，而碳-氧键是主要的F吸附位点。胺基团对 F 的去除贡献了一小部分。值得注意的是，gGO-U-50 的 F 水处理成本为 1621.6 mg-F $，其成本效益约为 UIO-66（632.07 mg-F $）的 3 倍。固定床柱实验表明，gGO-U-50 比其他报道的颗粒吸附剂表现出更高的 F 吸附能力（6.34 mg g），表明 gGO-U-50 具有 F 修复潜力。