Nitrogen Coordination to Dramatically Enhance the Stability of

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Nitrogen Coordination to Dramatically Enhance the Stability of In-MOF for Selectively Capturing CO2 from CO2/N2 mixture Ye-Wang Peng, Rui-Juan Wu, Meng Liu, Shuang Yao, Ai-Fang Geng, and Zhi-Ming Zhang Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01709 • Publication Date (Web): 09 Jan 2019 Downloaded from http://pubs.acs.org on January 10, 2019

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Crystal Growth & Design

Nitrogen Coordination to Dramatically Enhance the Stability of In-MOF for Selectively Capturing CO2 from CO2/N2 mixture Ye-Wang Peng,†,‡ Rui-Juan Wu,†,‡ Meng Liu,§ Shuang Yao,*,†,‡ Ai-Fang Geng † and Zhi-Ming Zhang*,§ †College

of Chemistry and Environmental Engineering, Changchun University of Science and

Technology, Changchun, 130022, P.R. China. E-mail: [email protected] (S. Yao) ‡Tianjin

Key Laboratory of Organic Solar Cells and Photochemical Conversion, School of

Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin, 300384, P.R. China. §Institute

for New Energy Materials and Low Carbon Technologies, School of Materials

Science and Engineering, Tianjin University of Technology, Tianjin 300384, P.R. China. E-mail: [email protected] (Z. Zhang)

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ABSTRACT: Two In-based metal-organic frameworks (MOFs) are design and synthesized by

reaction

of

In3L14·(CH3NH2CH3)3

3-phenylpyridine (H3L1

=

polycarboxylic

ligands

5-(3’,5’-dicarboxylphenyl)

In2L22(CH3COO)2·(CH3)2NH2·(CH3)3NH·H2O

(H3L2

=

and

nicotic

In3+ acid,

cations, 1)

and

3-(2,4-dicarboxylphenyl)-6-

carboxylpyridine, 2). Single crystal X-ray diffraction analysis indicates that the In3+ centers in 1 are all coordinated by eight oxygen atoms from four carboxylate groups, resulting in a 3D framework with two different channels A and B with the size of 14.4 × 8.75 Å2 and 7.24 × 6.7 Å2, respectively. In 2, each In3+ center was coordinated by six carboxylate oxygen atoms and a pyridine N atom, forming a 2D layer-like structure. These 2D layers are further fused together via electrostatic interactions into a 3D supermolecular framework, showing two kinds of channels A´ and B´ with the pore sizes of 5.25 × 9.69 Å2 and 4.29 × 8.66 Å2, respectively. In this work, the coordination of N to In3+ center in 2 was firstly achieved by regulating carboxyl sites in 3-phenylpyridine, thus increasing the stability of In-based MOF. Detail structural study reveals that the formation of In-N bonds promotes the conversion of 3D framework of 1 into supermolecular structure of 2. However, the supermolecular structure in 2 is more stable in air and methanol than the 3D framework of 1, confirming the important role of In-N bond in enhancing the framework stability. Thus, 2 could be used as stable adsorbent to selective capture CO2 from CO2/N2 mixture, while 1 broke down sharply in air and in the methanol solution.


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INTRODUCTION Metal–organic frameworks (MOFs), a great class of porous crystalline materials constructed from metal cation/cluster and polydentate organic ligand, have received considerable interest in the past decades.1-6 Because of their easily adjustable compositions and structures, they possess of various potential applications, such as gas storage and separation, catalysis, and photoelectric devices.7-12 In this field, a number of methods have been proposed to design and synthesize novel and multifunctional MOFs by decorating organic ligands and inorganic metal cation/cluster-based nodes.13-18 One significant trend for synthesizing novel and multifunctional MOFs is the use of polydentate ligands containing both carboxylate units and N-heterocyclic rings, which greatly contribute to construct MOFs with high stability.19-23 Apart from organic linkers, metal cations with different oxidation states also play an important role in the construction of stable MOFs. As well known, most of the divalent transition-metal (TM2+) ions, usually coordinated by O or N-donor ligands forming four to six-coordination environments. In this process, TM2+-N MOFs are usually more stable than those of TM2+-carboxylate MOFs. The tetravalent and trivalent TM cations, such as Zr4+ and In3+, usually tend to form MOFs with TM-O coordination modes by forming six to eight coordination numbers.24-30 However, compared to TM2+ and Zr4+-based MOFs, In3+-based MOFs are comparatively fewer in literature reports.31-35 In this filed, the In3+ ions were used to react with organic di-, tri- and tetra-carboxylic ligands, resulting in several In-based 2D and 3D frameworks,31-43 which have been widely used for gas separation, pollutant removal and catalytic reactions.12,43, Among these structures, it could be found that most of the In3+ centers tend to coordinate with carboxylate oxygen atoms, although several 3 ACS Paragon Plus Environment


ligands containing N and S heteroatoms.35,36,39,41 Up to date, design and synthesis of In-based framework materials is still in its infantile, and represents a promising way to construct stable MOFs for various applications, especially for introducing polydentate ligands with both carboxylate and N-heterocyclic rings into the In-MOFs to promote the formation of In-N bonds.44 Herein, two organic linkers with same composition (Scheme 1) were used to construct new In-based MOFs with different structures by adjusting the position of carboxyl groups in 3-phenylpyridine. All the In3+ centers in 1 are coordinated by eight carboxylate oxygen atoms, exhibiting a 3D framework with two different channels with the size of 14.4 × 8.75 Å2 and 7.24 × 6.7 Å2, respectively. In 2, an In3+ center was coordinated by six carboxylate oxygen atoms, and a pyridine N atom to form a 2D layer-like structure, which was fused together via the electrostatic interactions into a 3D supermolecular framework. It is surprisingly that the supermolecular structure in 2 is more stable in air and methanol than that of the 3D framework in 1 as the formation of In-N bonds. Thus, 2 could be used as the stable adsorbent to selective capture CO2 from CO2/N2 mixture, while 1 broke down sharply in air and the exchanged solvents. EXPERIMENTAL SECTION Synthesis of In3L14·(CH3NH2CH3)3 (1). H3L1 (10 mg, 0.03 mmol) and In(NO3)3·4H2O (11 mg, 0.03 mmol) were added into a DMF (2 mL) solution containing glacial acetic acid (100 μL). Then, the mixture was stirred for half an hour at room temperature and added into a 25 mL Teflon-lined autoclave. Further, the solution was heated at 150 °C, and maintained for 72 hours. Next, the mixture was slowly cooled to room temperature at a rate of 5 °C h−1. 4 ACS Paragon Plus Environment

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Colorless crystals were harvested by centrifugation with a yield of 42 % based on In. IR (KBr pellet) for 1: ν̃ 1620 (s), 1360 (s), 1300 (w), 1246 (s), 1047 (w), 1019 (s), 938 (m), 863 (m), 841 (m), 783 (s), 721 (s), 699 (s), 663 (m), 442 (m) cm−1. Synthesis of In2L22(CH3COO)2·(CH3)2NH2·(CH3)3NH·H2O (2). H3L2 (8 mg, 0.028 mmol) and In(NO3)3·4H2O (20 mg, 0.053 mmol) were added into a DMF (2 mL) solution containing glacial acetic acid (200 μL), the above mixture was stirred for half an hour at room temperature and added into a 25 mL Teflon-lined autoclave. After heating at 130°C for 72 hours, the mixture was cooled down to room temperature at a rate of 5 °C h−1. Colorless block crystals were harvested with a yield of 73 % based on In. IR (KBr pellet) for 2: ν̃ 1667 (s), 1367 (s), 1255 (w), 1097 (m), 1026 (w), 908 (w), 778 (s), 750 (w), 704 (m), 662 (m), 450 (m) cm-1.

Scheme 1. Structure of (a) H3L1 and (b) H3L2 showing different positions of the carboxyl groups in 3-phenylpyridine. RESULTS AND DISCUSSION Synthesis and Structure. Reaction of H3L1 with In(NO3)3 in DMF at 150 °C affords colorless crystals of 1. Single-crystal X-ray diffraction analysis shows that 1 crystallizes in orthorhombic crystal system with Fddd space group (Table S1). As shown in Figure 1a, one crystallographic asymmetric unit of 1 contains a H3L1 ligand and two In3+ ions. It is worthy mentioning that the In3+ center tends to combine with carboxylate O atoms, thus each In3+ ion is surrounded by eight carboxylate O atoms from four different H3L1 ligands (Figure 1b). 5 ACS Paragon Plus Environment


Thus, each carboxylate group binds to the In3+center via bidentate-chelate mode, and the bond lengths of In-O bonds are in the range of 2.148(6) to 2.449(11) Å. Also, each L1 in 1 coordinates with three In3+ ions through three carboxylate groups, thus generating a (3,4)-connected 3D framework with two different channels A and B with the size of 14.4 × 8.75 Å2 and 7.24 × 6.7 Å2, respectively (Figure 1c, 1d and S1-S4). In the synthesis of 1, although the acetic acid does not exist in the final product, it plays a key role in the formation of 1 as a pH value regulator. In the absence of acetic acid, compound 1 could not be obtained under the similar conditions. And it can be seen that the N atom disconnects with In3+ center, which may be a potential coordination site for further enhancing the stability of the MOFs by formation In-N bonds.34, 37-40

Figure 1. (a) The asymmetric unit of 1. (b) The coordination mode of In3+. (c) Ball and stick 6 ACS Paragon Plus Environment

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and (d) space filling representation of the 3D structure of 1. The H atoms are omitted for clearity.

Figure 2. (a) The coordination mode of In3+ in 2. (b) 2D layer in 2 along a-axis. (c) Ball and stick representation of 3D supramolecular structure of 2 along c-axis. (d) 2D layer in 2 viewed along c-axis. The H atoms are omitted for clearity. The H3L2 ligand with only different carboxyl positions (Scheme 1) was used to replace H3L1 to react with In(NO3)3 in the DMF solution, resulting in colorless block crystals of 2. Structural analysis reveals that 2 crystallizes in monoclinic crystal system and C2/c space group (Table S1). In one crystallographic asymmetric unit, there is one L2 ligand, one In3+ ion and one acetic acid. As shown in Figure 2a, the In3+ centers in 2 are all in a hepta-coordinated environment completed by six carboxylate oxygen atoms and a pyridine N atom. Thus, each In3+ connected with three L2 ligands forming a seven-coordinated environment completed by two oxygen atoms from two monodentately coordinated carboxylate groups, four oxygen atoms from two bidentate-chelate carboxylate groups, and an N donor, and each L2 ligand 7 ACS Paragon Plus Environment


coordinated with three In3+ ions, resulting in a (3,3)-connected 2D layer-like structure (Figure 2b). As shown in Figure 2d, the acetate ligands chelate the In centers on both sides of the layer to prevent further extending the 2D layer along a-axis.

Figure 3. (a) Ball and stick and (b) space filling representation of 2 along c-axis. (c, d) structure of 2 showing the channel B´ with the size of 4.29 × 8.66 Å2. The H atoms are omitted for clearity. Further, these layers are fused together via the electrostatic interactions into a 3D supermolecular framework (Figure S5), possessing of two kinds of channels A´and B´ with the size of 5.25 × 9.69 Å2 and 4.29 × 8.66 Å2, respectively (Figure 2c and S6). In pore A´, abundant uncoordinated carboxylate oxygen atoms reside in the channel resulting hydrophilic surface of channel. As shown in Figure 3c and 3d, there is another channel A´ in 2 with the size of 4.29 × 8.66 Å2. In the synthesis of 2, the acetic acid not only acts as a pH value adjuster, but also as the chelate ligand in constructing 2D layer-like structure. More 8 ACS Paragon Plus Environment

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importantly, it could be found that the change of carboxyl position in 3-phenylpyridine has important effect on the final structure of the In-based MOFs. Detail structural analysis indicates that the coordination of N to In3+ center in 2 is achieved by regulating carboxyl sites in the 3-phenylpyridine ligand, thus increasing the stability of In-based MOF.

Figure 4. (a) PXRD patterns of 1 of the simulated, as-synthesized samples, and the samples exposed in the air or soaking in MeOH for 24 hours. (b) PXRD patterns of 2 of the simulated, and as-synthesized samples, the samples exposed in the air or soaking in MeOH for 24 hours, the samples after adsorption experiments and the activated samples (pretreated for three times with MeOH and subsequently evacuated under vacuum). Stability. In order to verify the phase purity of as-synthesized 1 and 2, powder X-ray diffraction (PXRD) measurements were carried out on these two compounds. The PXRD patterns of the freshly prepared 1 and 2 matched well with their simulated PXRD patterns simulated from single-crystal data, indicating the phase purity of bulk products (Figure 4).41,42 Further, 1 and 2 were exposed in the air and doped into the MeOH, which has been widely used as exchanged solvent to replace guest molecules in the channels of MOFs for absorption measurement. As shown in Figure 4a, the diffraction peaks in the PXRD of 1 completely disappeared if the sample was exposed in the air or soaking in MeOH for 24 hours, revealing 9 ACS Paragon Plus Environment


the full collapse of the framework of 1. For 2, the PXRD patterns of the sample exposed in the air for 24 hours, soaking in MeOH for 24 hours and the activated samples for gas sorption (Figure 4b), are similar to the simulated pattern, which can confirm the stability of the framework of 1 in the air and the MeOH solvent. This result also reveals that the formation of In-N bonds helps to enhance the stability of the In-based MOFs, which can be further used for gas absorption and separation. The thermal behavior of 1 and 2 was evaluated by TGA under N2 flow with a ramp rate of 10 °C/min from 35 to 800 °C. For compound 1, the TG curve presents two weight losses. The first step is associated with the elimination of entrapped organic counter cations [CH3NH2CH3]+ with a weight loss of ca. 10.1 % in the temperature regime of 201 °C to 264 °C (Cal. 8.53 %), and the other weight loss with the temperature above 275 °C belongs to the collapse of skeleton and the loss of the linking ligands. For 2, there are three weight losses appeared in the TGA curve. The initial weight loss of ca. 4.03 % is attributed to the release of lattice water molecules in the temperature of 35-117 °C (Cal. 1.73 %), then [(CH3)2NH2]+ and [(CH3)3NH]+ (ca. 11.6 %) began to lose with increasing the temperature to around 214 °C (Cal. 10.20 %), and the last weight loss starts with the temperature above 350 °C corresponds to the degradation of the framework (Figure S8). Gas sorption properties. CO2 and N2 are the main components of flue gas which is caused of burning coal, oil and other fossil fuels. Capturing CO2 from existing emission sources will greatly contribute to environmental protection.43 In this work, N2 adsorption at 77 K and CO2 adsorption (at 273 and 298 K) experiments were conducted to verify the stability and porosity of compounds 1 10 ACS Paragon Plus Environment

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and 2. The samples were pretreated for three times with MeOH (once for 24 h) and subsequently evacuated under vacuum at 100 °C for 12 h. It could be found that the framework of 1 collapsed after being activated, which was confirmed by the XRD (Figure 4a). For 2, it was still intact after being activated, indicating its potentially suitable for gas sorption and separation. As shown in Figure 5a, N2 adsorption and desorption isotherms of compound 2 reveals that the N2 uptake of 2 is only 4.73 cm3/g at 77 K at a relative pressure of P/P0 = 1. For CO2, the saturated CO2 uptake can reach to 12.6 cm3/g at 273 K with a relative pressure (P/P0) approaching 1.0. It's worth mentioning that compound 2 shows much higher volumetric uptake of CO2 at ambient conditions than that of N2 at a much lower temperature of 77K, indicating an excellent adsorption selectivity for CO2 over N2.

Figure 5. (a) N2 adsorption and desorption isotherms of 2 recorded at 77 K. (b) CO2 adsorption and desorption isotherms of 2 recorded at 273 K and 298 K. (c) Comparison of the adsorption and desorption isotherms of CO2 at 273 K and N2 at 77 K.



Conclusion Two new In-based framework materials were design and synthesized by reaction of pyridine polycarboxylic and indium ions. Detail study indicates that the coordination of N to In3+ center in 2 is achieved by regulating carboxyl sites in 3-phenylpyridine, thus dramatically increasing the stability of In-based MOF. Although the coordination of N and acetate ligands to In3+ promotes the conversion of 3D framework of 1 into supermolecular structure of 2, the supermolecular structure of 2 is more stable in air and methanol than that of the 3D framework of 1. Thus, compound 2 could be used as stable adsorbent to selective capture CO2 from CO2/N2 mixture, while compound 1 broke down sharply in air and the exchanged solvent methanol. This work may shed light on the design and synthesis of other MOF materials with high-valence TM centers with N-donors to improve the their stability.

Acknowledgments We are grateful for the financial support from National Natural Science Foundation of China (21722104 / 21671032), Natural Science Foundation of Tianjin City of China (18JCJQJC47700 / 17JCQNJC05100), 131 Innovative Talent Project of Tianjin City of China, Science and Technology Research Foundation of the Thirteenth Five Years of Jilin Educational Committee ([2015]0056/JJKH20170605KJ), the Scientific Research Foundation for the Returned Overseas Scholars. References (1) Long, J. R.; Yaghi, O. M. The pervasive chemistry of metal–organic frameworks. Chem. Soc. Rev. 2009, 38, 1213-1214. (2) Liao, P.-Q.; Huang, N.-Y.; Zhang, W.-X.; Zhang, J.-P.; Chen, X.-M. Controlling guest 12 ACS Paragon Plus Environment

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Table of Contents Graphic Nitrogen Coordination to Dramatically Enhance the Stability of In-MOF for Selectively Capturing CO2 from CO2/N2 mixture Ye-Wang Peng,†,‡ Rui-Juan Wu,†,‡ Meng Liu,§ Shuang Yao,*,†,‡ Ai-Fang Geng † and Zhi-Ming Zhang*,§

Two In-based MOFs with different structures were obtained by adjusting the position of carboxyl groups in 3-phenylpyridine, which confirmed the nitrogen coordination to In3+ center playing important role in dramatically enhancing the stability of In-based MOFs.


Nitrogen Coordination to Dramatically Enhance the Stability of

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