A Robust Microporous Porphyrin-based Hydrogen-bonded Organic

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A Robust Microporous Porphyrin-based Hydrogenbonded Organic Framework for Highly Selective Separation of C2 Hydrocarbons versus Methane Qi Yin, Jian Lü, Hong-Fang Li, Tian-Fu Liu, and Rong Cao Cryst. Growth Des., Just Accepted Manuscript • Publication Date (Web): 22 May 2019 Downloaded from http://pubs.acs.org on May 30, 2019

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Crystal Growth & Design

A Robust Microporous Porphyrin-based Hydrogen-bonded Organic Framework for Highly Selective Separation of C2 Hydrocarbons versus Methane Qi Yin,†,‡ Jian Lü,ξ,§ Hong-Fang Li,‡ Tian-Fu Liu,*,‡ and Rong Cao*,†,‡ † Department of Chemistry, University of Science and Technology of China, Hefei, Anhui, 230026, P. R. China. ‡ State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, P. R. China. ξ Fujian Provincial Key Laboratory of Soil Environmental Health and Regulation, College of Resources and Environment, Fujian Agriculture and Forestry University, Fuzhou 350002, P.R. China § Samara Center for Theoretical Materials Science (SCTMS), Samara State Technical University, Samara 443100, Russia. KEYWORDS: hydrogen-bonded organic framework, light hydrocarbons, selective adsorption

ABSTRACT

A microporous porphyrin-based hydrogen-bonded organic framework (HOF), named PFC-5, was precisely designed and successfully constructed. Because of the 1 ACS Paragon Plus Environment

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present of multiple hydrogen-bondings and π-π interactions between porphyrinic ligands, PFC-5 possesses robust framework with excellent water, thermal and chemical stability. CO2 sorption isotherm demonstrated that PFC-5 possesses permanent microporosity after activation. The obtained material has been explored for highly C2 light hydrocarbons/CH4 separations at room temperature and normal pressure. Introduction C2 light hydrocarbons are of important industrial resources.1 Thermal conversion of natural gas to C2H4 (or C2H2) with the yield of acetylene about 50% is a most cost-effective process and the resulted production with a part of methane is harmful for the efficient use of natural gas.2 Therefore, it is highly important to separate methane from C2 light hydrocarbons to achieve the maximize utilization of natural gas. Solid adsorbent separation is a kind of alternative technology to effectively separate C2 light hydrocarbons at ambient atmosphere for lower energy cost.3 With deepening the research on separation technologies, various porous materials, such as activated carbons4, zeolites5, metal-organic frameworks (MOFs)6-11, and covalent organic frameworks (COFs)12, have been used as candidates to work out the difficulty of highly effective separation of gas mixture. Hydrogen-bonded organic frameworks (HOFs), as a new type of pure organic periodic materials with high porosity, has tremendous potential application in gas separation.13-16

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HOFs are assembled by only organic components connected through hydrogen bondings and π-system interactions. Just like other periodic frameworks, for example MOFs and COFs, HOFs seized of the merits of permanent porosity17-20, designable structure and tunable pore size/shape21, 22. Besides, the nature of hydrogen bonding endows HOFs with some unique characteristics, such as solution processability18, easy purification and recovery.23 Despite great attention was paid to HOFs field, due to the limit of structural stability, only a few HOFs have been demonstrated to survive in harsh conditions.18,

23

The low stability seriously hampers the development of

HOFs for practical applications. Although some progress has been made for the separation of mixture gas of HOFs, construction of HOFs with stability and highly separation selectivity, is still very important while highly challenging. In previous work, it is testified that π-π stacking interactions play an important role in construction of robust HOFs.18,

24

Given the fact that porphyrinic moieties are a

kind of planar molecules with large π-conjugated system and highly important components, constructing a variety of functional materials25, herein, we chose tetrakis (4-carboxyphenyl) porphyrin (H4TCPP) as a tetra-topic building block for HOF construction. As expected, the ligand assembled into a robust HOF, named PFC-5. The activated PFC-5 has moderate surface area of 256 m2/g and high performance for water, thermal and chemical stability. The activated material emerges the potential application for highly C2 light hydrocarbons/CH4 separations at normal pressure and room temperature.



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Scheme 1. The chemical structure of the organic ligand H4TCPP used to construct PFC-5. Materials and Methods All chemicals were received from supplier without further purification before used. H4TCPP ligand was prepared according to the reported method26 (Supporting Information 2). The calculation methods of isosteric heats of adsorption (Qst) and ideal adsorbed solution theory (IAST) were recorded in Supporting Information 5.2-5.3. Preparation of PFC-5. H4TCPP (50 mg, 0.063 mmol) was dissolved in 22 mL methanol to which 3.1 mL methanol solution of hexamethylenetetramine (0.02 mmol/mL) was added and stirred for 10 seconds. The mixture stands at 60 oC for 5 days to afford purple rod-like crystals of PFC-5 (28.9 mg, Yield: 57.8 %). Chemical Stability Test. The samples of PFC-5 were immersed in 0.1 M HCl aqueous solution, deionized water and various organic solvents (methanol, 4 ACS Paragon Plus Environment

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acetonitrile, acetic ether and chloroform) for 24 hours and then filtered and dried at room temperature. PXRD data were used to confirm their crystallinity and phase purity. Gas Adsorption Measurements. The N2, CO2, CH4, C2H2, C2H4, C2H6 gas isotherms of the samples were measured using ASAP 2020 from Micromeritics Co. Ltd. The temperatures of 77 K, 195 K, 273 K, and 298 K were provided by liquid nitrogen, liquid mixture of acetone and solid carbon dioxide, ice-water mixture, and water baths, respectively. The samples were activated at 363 K for 6 hours by using the “degas” function in instrument and then transferred to the analysis port for the measurements. Results and discussion Crystal Structure of PFC-5. Crystallographic data reveals that PFC-5 crystallizes in the triclinic system and P-1 space group, exhibiting a distinctive two-dimensional (2D) framework. There are six O‒H···O hydrogen bonds for each H4TCPP molecule to interact with four neighboring ones, extending into a layer (Figure 1a). There are three kind of hydrogen bonds with the O-H···O distance between 2.4823 Å and 2.6054 Å and the O‒H···O angle between 169.976 o and 174.182 o (Figure 1b, Table 1). Those hydrogen bonds are in the strong hydrogen bonding interactions range through the comparison of bond distances and literature reports.27 Each 2D square layer (sql) stacks as ABAB mode through intermolecular π-π interactions, leaving an one-dimensional channel of 5.2 Å x 4.0 Å along [101] direction (Figure 1b and 1c). 5 ACS Paragon Plus Environment


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PLATON analysis reveals that the simulated solvent accessible void space is 719.8 Å3, which occupy about 30.3 % of unit cell volume.28 The relative low accessible void space is caused by the staggered structure of ABAB stacking.

Figure 1. Crystal structure of PFC-5 indicating a) Three kind of hydrogen bonding interactions between organic building block and four neighboring ones; b) The ABAB packing mode of 2D layers; c) Representation of one-dimensional (1D) channels of 5.2 Å x 4.0 Å.

D-H···A Type

distance of D···A (Å)

angle of D−H···A (deg)

HA

2.4823

174.182 6

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HB

2.6054

169.976

HC

2.5520

172.241

Table 1. The hydrogen bond length and angle in the crystal structures of PFC-5. Water, Chemical and Thermal stability Properties. The as-synthesized PFC-5 has similar PXRD pattern as simulated one, indicating successful preparation of PFC-5 in bulky amount (Figure 2).

Activated PFC-5 sample was prepared through

soaked in acetone to remove residual H4TCPP ligands and followed by vacuuming activation at 90 oC for 6 hours.

Figure 2. PXRD patterns for PFC-5 (red, experimental; black, calculated). Considering the practical requirement of applications, we investigate the stability of PFC-5. The TGA and VT-PXRD patterns reveal the PFC-5 remains the crystallinity in the range from 25 to 150 oC (Figure S1-S2). After soaking PFC-5 in water, 0.1 M HCl solution and some organic solvents, such as MeOH, CHCl3, CH3CN and acetic ether for 24 h, respectively, the frameworks well maintain the crystallinity, which are 7 ACS Paragon Plus Environment


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confirmed by the PXRD measurements (Figure S3-S4). The above results reveal that PFC-5 has excellent water, thermal and chemical stability. Gas Adsorption and Separation Properties. The existence of available void space and stable framework prompt us to evaluate the porosity of PFC-5. The material does not adsorb N2 at 77 K, likely due to the narrow channel windows and nitrogen emerge the strong interactions, hindering gas diffusion into the material29, which is a common phenomenon in HOF field.14,

30, 31

Alternatively, we choose CO2 to evaluate the

porosity of the material (Figure 3). The result shows that PFC-5 has a CO2 uptake of 121 cm3/g (STP) at 195 K with the Brunauer-Emmett-Teller (BET) surface area of 256 m2/g, being moderate value among HOFs with permanent porosity (Table S5). The calculated theoretic surface area (222 m2/g) through Zeo++ software package32 has a similar value.

The sorption isotherms show a type I isotherm with a very sharp

uptake at low pressure, indicative of a microporous material. As showing in Figure 3, sorption isotherm has a small sorption hysteresis, probably caused by the framework flexibility.


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Figure 3. CO2 sorption isotherms (195 K) of activated PFC-5. It has been verified that microporosity can enhance the adsorption selectivities for porous materials, such as MOFs6 and molecular sieves33. With the establishment of intrinsic permanent microporosity, structural robustness, moderate pore size and functional sites located on pore surface, the potential application of PFC-5 for gas storage and selective adsorption are further investigated. Figure 4a and 4b show the sorption isotherms of PFC-5 for N2, CH4, CO2, C2H2, C2H4, and C2H6 at 273 K and 298 K, respectively. PFC-5 adsorb 40.3 cm3/g of C2H2, 32.2 cm3/g of C2H4 and 32.5 cm3/g of C2H6 at 273 K. While at 298 K and 1 bar, PFC-5 shows lower uptake for C2H2 (30.7 cm3/g), C2H4 (26.2 cm3/g) and C2H6 (25.9 cm3/g). In contrast to the high C2 hydrocarbons uptakes, PFC-5 shows much less amount of CH4 (273 K, 13.7 cm3/g; 298 K, 8.0 cm3/g), N2 (273 K, 4.0 cm3/g; 298 K, 2.0 cm3/g) and CO2 (273 K, 32.8 cm3/g; 298 K, 23.9 cm3/g) at 1 atm and 273 K.



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Figure. 4 N2, CO2, CH4, C2H2, C2H4 and C2H6 sorption isotherms of PFC-5 at a) 273 K and b) 298 K; c) IAST-predicted separation selectivities for PFC-5 at 298 K. In order to evaluate the affinity of PFC-5 toward these gas molecules, the isosteric heats of adsorption (Qst), a parameter indicating the affinity of adsorbate toward adsorbents and closely concerning the adsorptive selectivity2, 34, were calculated by 10 ACS Paragon Plus Environment

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the virial method35 (Supporting Information 5.2). The near zero-coverage Qst of PFC-5 are 26.6 KJ/mol for C2H2, 24.5 KJ/mol for C2H4, 25.0 KJ/mol for C2H6, 17.5 KJ/mol for CH4, and 26.9 KJ/mol for CO2 (Figure S5). To analysis the separation capacities of PFC-5, ideal adsorbed solution theory (IAST) was applied to predict the gas separation selectivity36 (Supporting Information 5.3). As display in Figure 4c, the adsorption selectivities of PFC-5 at 298K were determined to be 20, 24, 84 for C2H2/CH4 (v:v = 50:50), C2H4/CH4 (v:v = 50:50), and C2H6/CH4 (v:v = 50:50) at pressure of 1 kPa, respectively, predicting excellent separation behavior toward binary gas mixtures. Those results show that PFC-5 is a candidate for highly separating mixture gas of C2 light hydrocarbons and CH4. Conclusions In summary, a robust microporous HOF material PFC-5 has been successfully constructed by a porphyrin-based organic building block. Permanent porosity, robust framework, micropore , and functional sites located on pore surface enable this HOF with highly effective adsorptive selectivity for C2 light hydrocarbons versus methane, which has been clearly testified by the experimental sorption isotherms and IAST-predicted selectivities. This work facilitates the research on construction of multifunctional HOFs based on -COOH moieties and is expected to provide insight about rational design of HOFs material for gas separation and other important applications. AUTHOR INFORMATION 11 ACS Paragon Plus Environment


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Supporting Information The Supporting Information is available free of charge on the ACS Publications website. Experimental details, TGA curve of PFC-5, PXRD patterns of PFC-5, calculations of Qst and IAST selectivities. CCDC 1883913 contains the supplementary crystallographic data for this paper. Corresponding Author *[email protected], *[email protected]. Author Contributions The manuscript was written through contributions of all authors. Funding Sources The authors thank National Key Research and Development Program of China, (Grant No. 2018YFA020860), the National Natural Science Foundation of China (NSFC, Grant No. 21520102001, 21571177, 21871267), Key Research Program of Frontier Science, CAS (QYZDJ-SSW-SLH045), “Strategic Priority Research Program” of the Chinese Academy of Sciences (Grant No. XDB20000000), the Key Research Program of the Chinese Academy of Sciences, (Grant NO. ZDRW-CN-2016-1). Notes The authors declare no competing financial interests. 12 ACS Paragon Plus Environment

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ABBREVIATIONS HOFs, Hydrogen-bonded organic frameworks; H4TCPP, tetrakis(4-carboxyphenyl) porphyrin; PFC, Porous materials from Fjirsm, CAS; PXRD, powder X-ray diffraction; VT-PXRD, various temperature powder X-ray diffraction; TGA, thermogravimetric analysis; Qst, isosteric heats of adsorption; IAST, ideal adsorbed solution theory; sql, two-dimensional square layers; BET, Brunauer-Emmett-Teller.

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For Table of Contents Use Only, A Robust Microporous Porphyrin-based Hydrogen-bonded Organic Framework for Highly Selective Separation of C2 Hydrocarbons versus Methane Qi Yin, Jian Lü, Hong-Fang Li, Tian-Fu Liu,* and Rong Cao*

A

microporous

porphyrin-based

two-dimensional

hydrogen-bonded

organic

framework (PFC-5) was constructed which exhibits excellent water, thermal and chemical stability. Beyond that, the material shows highly selective separation performance toward C2 light hydrocarbons versus methane.



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SYNOPSIS TOC A microporous porphyrin-based two-dimensional hydrogen-bonded organic framework (PFC-5) was constructed and exhibits excellent water, thermal and chemical stability. Beyond that, activated material possesses highly selective separation of C2 light hydrocarbons versus methane.

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A Robust Microporous Porphyrin-based Hydrogen-bonded Organic

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