Yu Guangli, Ni Fei, Niu Wenyue, Chen Yu, Zhang Feng, Li Guo-Dong, Song Xingfei, Zhang Yajing, Wang Kangjun
College of Chemical Engineering, Shenyang University of Chemical Technology, Shenyang, 110142, PR China.
Key Laboratory of Photochemical Biomaterials and Energy Storage Materials, Heilongjiang Province and College of Chemistry and Chemical Engineering, Harbin Normal University, Harbin, 150025, PR China.
Chemosphere. 2024 Dec;369:143816. doi: 10.1016/j.chemosphere.2024.143816. Epub 2024 Nov 30.
Metal-organic frameworks (MOFs) recently gained immense popularity for the adsorption of organic impurities. In this work, the adsorptive separation of bisphenol A (BPA) from aqueous mixtures was explored utilizing three types of zirconium-based MOFs, namely MOF-808, UiO-66, and hierarchically porous UiO-66 (HP-UiO-66). The HP-UiO-66, which was etched by sodium acetate as the terminal ligand, generated large mesopores ranging from 40 to 300 Å due to the departure of partial linkers and metallic clusters. The adsorption ability for BPA increased significantly with the introduction of numerous mesopores onto the HP-UiO-66 framework, even though the surface area of HP-UiO-66 was lower compared to that of the pristine UiO-66 and MOF-808. The study revealed that the maximum adsorption capacities (q) for BPA by HP-UiO-66 reached up to 295.04 mg g, which was about 88.5% and 17.4% higher in comparison to UiO-66 and MOF-808, respectively. Furthermore, the q value of HP-UiO-66 was also better than many other previously reported MOF adsorbents. The analysis of possible adsorption mechanisms indicated that physical pore-filling was anticipated as the principal mechanism, attributed to the larger window size and high mesopore surface area of HP-UiO-66. Furthermore, X-ray photoelectron and Fourier transform infrared spectroscopic measurements inferred that the synergetic effects of H-bonding and π-π interactions played crucial roles in BPA capture as well. Overall, this study revealed a structure-property relationship in the Zr-MOFs-based adsorbents and opened up a new avenue to exploit unique MOF platforms for the efficient removal of emerging contaminations in the future.
金属有机框架材料（MOFs）最近在有机杂质吸附方面受到了极大关注。在本研究中，利用三种锆基金属有机框架材料，即MOF-808、UiO-66和分级多孔UiO-66（HP-UiO-66），探索了从水性混合物中吸附分离双酚A（BPA）的方法。以醋酸钠作为端基配体对HP-UiO-66进行蚀刻，由于部分连接体和金属簇的脱离，产生了范围为40至300 Å的大孔。尽管HP-UiO-66的表面积低于原始UiO-66和MOF-808，但随着大量介孔引入到HP-UiO-66骨架上，其对BPA的吸附能力显著提高。研究表明，HP-UiO-66对BPA的最大吸附容量（q）高达295.04 mg/g，分别比UiO-66和MOF-808高出约88.5%和17.4%。此外，HP-UiO-66的q值也优于许多先前报道的MOF吸附剂。对可能的吸附机制分析表明，物理孔填充被认为是主要机制，这归因于HP-UiO-66较大的窗口尺寸和高介孔表面积。此外，X射线光电子能谱和傅里叶变换红外光谱测量推断，氢键和π-π相互作用的协同效应在BPA捕获中也起着关键作用。总体而言，本研究揭示了基于Zr-MOFs吸附剂的结构-性能关系，并为未来开发用于高效去除新出现污染物的独特MOF平台开辟了一条新途径。
