采用原位生长法,在紫铜网表面构筑氢氧化铜微米级粗糙结构,在均苯三甲酸的作用下,氢氧化铜微米级粗糙结构进一步转化为铜基-金属有机框架(HKUST-1)晶体层,制备了具有超亲水水下超疏油特性的HKUST-1复合网(HCM网)。通过扫描电子显微镜、傅里叶变换红外光谱仪、X射线多晶粉末衍射仪对网表面的微观形貌、化学官能团及晶体结构进行了表征,评价了HCM网的润湿性、油水分离性能、重复利用性及化学稳定性。结果表明:由于HKUST-1晶体固有的亲水性及网膜表面微纳米晶体堆积的粗糙结构,HCM网在空气中的水接触角为0°,在水下二氯甲烷的接触角为152.6°;对汽油、煤油、柴油、正己烷、二氯甲烷与水混合物的分离效率均大于99.5%,通量最高可达78526L/(m2·h),经过30次重复实验后,油水分离效率仍高于98.6%,通量衰减小于3%,表现出优异的油水分离性能及可重复使用性。经过-10～250℃温度变化、2～22h紫外线照射、pH=2～12强酸碱浸泡、质量分数 1%～5%氯化钠溶液浸泡后HCM网的分离性能没有受到显著影响,油水分离效率高于98.3%,通量衰减小于2%,具有良好的热稳定性和化学稳定性。
The Cu-based metal-organic framework (HKUST-1) composite mesh (HCM) with superhydrophilic and underwater superoleophobic properties was successfully fabricated by using an in-situ growth method to build a rough micron-scale structure of copper hydroxide on the surface of the copper mesh,which was further converted into the crystal layer made of HKUST-1 under the action of trimesic acid.SEM,FTIR and XRD were used to characterize the micromorphology,chemical functional groups and crystal structure of the mesh surface.The wettability,oil-water separation performance,reusability and chemical stability of the HCM mesh were evaluated.The results showed that the HCM mesh had a water contact angle of 0° in air and a under water dichloromethane contact angle of 152.6° due to the inherent hydrophilicity of HKUST-1 crystals and the rough structure of micro and nano crystal stacking on the surface of the mesh.The separation efficiencies of the mixtures of gasoline,kerosene,diesel fuel,hexane,methylene chloride and water all exceeded 99.5%,and the flow rate was up to 78526L/(m2·h).After 30 repeated experiments,the separation efficiencies were still over 98.6% and the flow attenuation was less than 5%,showing excellent oil-water separation performance and reusability.The separation performance of the mesh was not significantly affected by the temperature change of -10～250℃,2～22h UV irradiation,2～12pH acid and alkali,and 1wt%～5wt% NaCl solution immersion,and the separation efficiency was higher than 98.3%,the flux attenuation was less than 2%,indicating good thermal and chemical stability.
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基金资助
国家自然科学基金面上项目(52478237);黑龙江省自然科学基金(LH2020E14);河北省自然科学基金(E2024107006)
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