文献类型：期刊文献

英文题名：Manipulating Oxidation States of Copper within Cu-BTC Using Na2S2O3 as a New Strategy for Enhanced Adsorption of Sulfide

作者：Wang, Dan[1];Jiang, Hao[1];Tan, Jialun[1];Chen, Yuxiang[1];An, Yang[1];Chen, Yonghao[1];Wu, Yuan[1];Liu, Chuanlei[1];Sun, Hui[1,2];Liu, Jichang[1,2];Wu, Di[3,4,5,6];Shen, Benxian[1]

机构：[1]East China Univ Sci & Technol, Petr Proc Res Ctr, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Int Joint Res Ctr Green Energy Chem Engn, Shanghai 200237, Peoples R China;[3]Washington State Univ, Alexandra Navrotsky Inst Expt Thermodynam, Pullman, WA 99163 USA;[4]Washington State Univ, Gene & Linda Voiland Sch Chem Engn & Bioengn, Pullman, WA 99163 USA;[5]Washington State Univ, Mat Sci & Engn, Pullman, WA 99163 USA;[6]Washington State Univ, Dept Chem, Pullman, WA 99163 USA

年份：2019

卷号：58

期号：42

起止页码：19503

外文期刊名：INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH

收录：;EI(收录号：20194207535279);WOS:【SCI-EXPANDED(收录号:WOS:000500349200017)】；

基金：This work is financially supported by the National Natural Science Foundation of China (grant 91634112 and 21878097), the Natural Science Foundation of Shanghai (grant 16ZR1408100), and the Open Project of State Key Laboratory of Chemical Engineering (SKL-ChE-16C01). Di Wu acknowledges the fund of Alexandra Navrotsky Institute for Experimental Thermodynamics, and the institutional funds from the Gene and Linda Voiland School of Chemical Engineering and Bioengineering at Washington State University.

语种：英文

外文关键词：Organometallics - Copper compounds - Sodium compounds - Adsorption - Oxidation - Crystalline materials - Density functional theory - Molar ratio

摘要：Manipulation of the oxidation states of the metal species within metal-organic frameworks leads to compositional, structural, and surface property evolutions, which will impact their performance as sorbents in adsorptive separation processes. In this study, we propose a new low-cost postsynthesis strategy to modify the oxidation states of copper species within the copper-1,3,5-benzenetricarboxylic acid (Cu-BTC) structure employing Na2S2O3 as the reducing agent. The compositional and structural evolutions of the modified samples were thoroughly characterized by a series of methods, and the dimethyl disulfide (DMDS) adsorption performance was evaluated. Accurately controlled reduction of Cu(II) to Cu(I) and formation of nanopores in the modified Cu(I)/Cu(II)-BTC samples have been observed and confirmed experimentally. Specifically, the sample 0.46/Cu-BTC/24h with a Cu(I)/Cu(II) molar ratio of 1.79 exhibits both the highest DMDS adsorption capacity (146.66 mg-S/g) and fastest diffusion with D of 7.59 x 10(-13) cm(2)/s at 298 K. Further density functional theory calculations reveal that the modified Cu(I)/Cu(II)-BTC structures exhibit much higher interaction energy, E-in, with DMDS (70.65 kJ/mol) than the parent Cu(II)-BTC (20.28 kJ/mol). Controllable reduction of Cu(II) to Cu(I) in Cu-BTC leads to significantly enhanced guest-host interactions as well as the formation of uniform nanoscale porosity leading to effect enhancement for the adsorption of DMDS using modified Cu-BTC materials.