Tian Fuping, Qiao Chenxia, Zheng Renyu, Ru Qiaofeng, Sun Xin, Zhang Yifu, Meng Changgong
School of Chemistry, State Key Laboratory of Fine Chemicals, Dalian University of Technology 2 Linggong Road, P. O. Box 288 Dalian 116024 China
RSC Adv. 2019 May 20;9(27):15642-15647. doi: 10.1039/c9ra02372k. eCollection 2019 May 14.
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.
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。
