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Functional Inorganic Materials and Devices
Enhanced Breakthrough Efficiency by a Chemically Stable Porous Coordination Polymer with Optimized Nanochannel Haifei Cao, Zhiyong Lu, Kim Hyeon-Deuk, I-Ya Chang, Yang Wang, Zhifeng Xin, Jingui Duan, and Wanqin Jin ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b12728 • Publication Date (Web): 22 Oct 2018 Downloaded from http://pubs.acs.org on October 23, 2018
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ACS Applied Materials & Interfaces
Enhanced Breakthrough Efficiency by a Chemically Stable Porous Coordination Polymer with Optimized Nanochannel Haifei Cao†#, Zhiyong Lu‡#, Kim Hyeon-Deuk§, I-Ya Chang§, Yang Wang†, Zhifeng Xin ∥ , Jingui Duan†*, and Wanqin Jin† †State
Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical
Engineering, Nanjing Tech University, Nanjing 210009, China ‡College
of Mechanics and Materials, Hohai University, Nanjing, 210098, China
§Department
∥Institute
of Chemistry, Kyoto University, Yoshida, Sakyo-ku, Kyoto, 606-8502, Japan
of Molecule Engineering & Applied Chemistry, Anhui University of Technology,
Maanshan 243002, China Keywords: Chemically stable porous coordination polymer, Inserted/shifted methyl group, Optimized nanochannel, Breakthrough efficiency, Methane purification
Abstract: High separation efficiency is very important for process of pressure swing adsorption (PSA) in the industry. Herein, we propose a fine design of chemically stable porous coordination polymers (PCPs) with optimized nanochannel by strategy of inserting and shifting shortest alkyl
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group on T-shaped ligand. Remarkably, the synergistic effect of optimized nanochannel, unique crystal morphology and fitted channel enable sharply enhanced breakthrough efficiency of C2H6/4/CH4, 1.17 or 0.77 g CH4 can be separated from corresponding dual mixtures (2/8, v/v) by 1 g NTU-25 at 273K, and which was further validated and understood by controlled experiments and density functional theory (DFT) computations.
Introduction The relative abundance of CH4 in our world makes it as a most crucial starting material and energy source for modern industry and social life. Converting CH4 to C2H4 would offer enormous economic benefits, while the wide usage of CH4 could alleviate the environment pollution by nearly 100% on SO2 and dust emission. However, the geochemical streams commonly contain high concentration of CO2 and C2 hydrocarbons1, which may hinder the value-added conversion or lead pipeline corrosion2-3. Thus, selective removal of CO2 and C2 hydrocarbons is an important process for natural gas upgrading. To date, worldwide efforts focused on developing suitable material for PSA technology, as conventional and current alternatives (compression/cryogenic distillation) carry high risks with higher energy cost4. PCPs5-8 that assembled from organic ligands and inorganic clusters were believed as the most promising candidate for CH4 purification because their pore environment can be facilely designed and prepared7, 9-10. With rapid development in the last two decades, a few of them with functional pore surface showed high gas selectivity of C2H6/4 and CO2 toward CH46, 11-15 based on their single adsorption isotherms, or the possible separation from breakthrough experiments. However, as the crucial factors for PSA process, breakthrough efficiency, a newly defined concept for identifying how much amount gas can be purified by per unit adsorbent in a single
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ACS Applied Materials & Interfaces
breakthrough operation, was not well investigated. For improving the breakthrough efficiency, higher gas adsorption and rational molecular diffusion within the framework are considered as the most important factors. Ideally, the pore with a large inner diameter can hold enhanced capacity, while the most suitable channel will broaden the significant gap during gas diffusion. In addition, the robustness of the framework under chemical environment is also highly required1618.
Therefore, the challenges we now face became more practical in nature, i.e., how to integrate
those factors in a single domain. We are interested in design and synthesis of functional porous materials for energy gas separation16,
18-24.
Herein, a new PCP (NTU-23) with T-shaped ligand and Cu dimers was
prepared, as well as its -CH3 inserted derivative (NTU-24) and -CH3 shifted analogue (NTU-25) (Scheme 1). By integrating the characters of high porosity and good chemical stabilities (2
