Hu Chechia, Huang Yu-Chi, Chang Ai-Lun, Nomura Mikihiro
Department of Chemical Engineering, Chung Yuan Christian University, Chungli Dist., Taoyuan City 32023, Taiwan; R&D Center for Membrane Technology and Research Center for Circular Economy, Chung Yuan Christian University, Chungli Dist., Taoyuan City 32023, Taiwan.
Department of Chemical Engineering, Chung Yuan Christian University, Chungli Dist., Taoyuan City 32023, Taiwan.
J Colloid Interface Sci. 2019 Oct 1;553:372-381. doi: 10.1016/j.jcis.2019.06.040. Epub 2019 Jun 13.
Hexavalent chromium (Cr) is one of the most toxic and carcinogenic species known to living beings, the environment, and our eco-system. Thus, it is urgent to develop a facile and effective approach for Cr removal. Zinc-based zeolitic imidazolate frameworks (ZIF-8), a typical metal organic framework, have high porosity, large specific surface area, high chemical stability, and abundant surface grafting sites. These sites can be easily modified with ethylenediamine (EDA) using a solvothermal process to generate a material that can serve as a potential candidate for photocatalytic Cr reduction under visible light irradiation. Various EDA contents and synthetic conditions were adopted in an attempt to investigate the correlation between ZIF-8 amine-functionalization and photocatalytic Cr reduction. The amine functionalization and the grafting sites on ZIF-8 were determined to be located at the -CH site of the 2-methylimidazole chains via X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and nuclear magnetic resonance spectroscopy (NMR). Under optimum conditions, amine-functionalized ZIF-8 exhibited a normalized rate constant (k/specific surface area, k), which was 9.8 times higher than that of unmodified ZIF-8 one for photocatalytic Cr reduction. The increased catalytic activity and range of visible light absorption of amine-functionalized ZIF-8 can be attributed to the increase in electron density due to the lone pairs of the surface grafted amines. In summary, amine-functionalized ZIF-8 could serve as a promising visible-light-active photocatalyst for environmental remediation.
六价铬(Cr)是已知对生物、环境及生态系统毒性最强且具致癌性的物质之一。因此,开发一种简便有效的铬去除方法迫在眉睫。锌基沸石咪唑酯骨架材料(ZIF-8)作为一种典型的金属有机骨架材料,具有高孔隙率、大比表面积、高化学稳定性以及丰富的表面接枝位点。利用溶剂热法可轻松地用乙二胺(EDA)对这些位点进行修饰,从而生成一种有望在可见光照射下用于光催化还原铬的材料。为了研究ZIF-8胺功能化与光催化铬还原之间的相关性,采用了各种EDA含量和合成条件。通过X射线光电子能谱(XPS)、傅里叶变换红外光谱(FTIR)和核磁共振光谱(NMR)确定ZIF-8上的胺功能化及接枝位点位于2-甲基咪唑链的-CH位点。在最佳条件下,胺功能化的ZIF-8表现出的归一化速率常数(k/比表面积,k)比未改性的ZIF-8用于光催化铬还原时高9.8倍。胺功能化的ZIF-8催化活性的提高及可见光吸收范围的扩大可归因于表面接枝胺孤对电子导致的电子密度增加。总之,胺功能化的ZIF-8可作为一种有前景的可见光活性光催化剂用于环境修复。