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双金属有机框架Cu/Co-BTC的合成及其对噻吩吸附性能的改善

Synthesis of bimetallic-organic framework Cu/Co-BTC and the improved performance of thiophene adsorption.

作者信息

Tian Fuping, Qiao Chenxia, Zheng Renyu, Ru Qiaofeng, Sun Xin, Zhang Yifu, Meng Changgong

机构信息

School of Chemistry, State Key Laboratory of Fine Chemicals, Dalian University of Technology 2 Linggong Road, P. O. Box 288 Dalian 116024 China

出版信息

RSC Adv. 2019 May 20;9(27):15642-15647. doi: 10.1039/c9ra02372k. eCollection 2019 May 14.

Abstract

A bimetallic-organic porous material (Cu/Co-BTC) with a paddle-wheel structure has been successfully synthesized by a solvothermal approach. The as-synthesized materials were characterized by XRD, SEM, ICP-AES, UV-Vis, TGA and N adsorption at 77 K. The prepared Cu/Co-BTC samples were investigated in thiophene (TP) adsorption from model gasolines by the fixed bed adsorption method at 298 K. The results showed that only a small amount of Co could be successfully introduced into the framework of HKUST-1, and the introduction of Co had little effect on the crystalline structure, morphology, porosity, and thermal stability. The bimetallic Cu/Co-BTC with a Cu/Co ratio of 174 displayed significantly improved adsorption desulfurization performance, showing an increase in breakthrough volume by 30% compared with HKUST-1, implying that the central metal in the MOF plays an important role in adsorption desulfurization. The addition of toluene or cyclohexene (3.20-3.30 vol%) as a competitor in the model gasoline led to a decline in desulfurization performance, especially when cyclohexene was added. The bimetallic Cu/Co-BTC showed a slight loss in breakthrough volume by only 5% after regenerating 7 times, displaying an excellent regeneration property.

摘要

通过溶剂热法成功合成了一种具有桨轮结构的双金属有机多孔材料(Cu/Co-BTC)。采用X射线衍射(XRD)、扫描电子显微镜(SEM)、电感耦合等离子体发射光谱(ICP-AES)、紫外可见光谱(UV-Vis)、热重分析(TGA)和77K下的氮气吸附等方法对合成的材料进行了表征。在298K下,采用固定床吸附法研究了制备的Cu/Co-BTC样品对模型汽油中噻吩(TP)的吸附性能。结果表明,只有少量的Co能够成功引入到HKUST-1的骨架中,且Co的引入对晶体结构、形貌、孔隙率和热稳定性影响较小。Cu/Co比为174的双金属Cu/Co-BTC表现出显著提高的吸附脱硫性能,与HKUST-1相比,穿透体积增加了30%,这意味着金属有机框架(MOF)中的中心金属在吸附脱硫中起重要作用。在模型汽油中加入甲苯或环己烯(3.20 - 3.30体积%)作为竞争剂会导致脱硫性能下降,尤其是加入环己烯时。双金属Cu/Co-BTC在再生7次后穿透体积仅略有损失,仅为5%,表现出优异的再生性能。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/da44/9064320/ed701cce2436/c9ra02372k-f1.jpg

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