Selective CO2 Adsorption by Nitro Functionalized Metal Organic

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Selective CO2 Adsorption by Nitro Functionalized Metal Organic Frameworks Dilip Kumar Maity, Arijit Halder, Biswajit Bhattacharya, Anamika Das, and Debajyoti Ghoshal Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.5b01686 • Publication Date (Web): 12 Feb 2016 Downloaded from http://pubs.acs.org on February 14, 2016

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Crystal Growth & Design

Selective CO2 Adsorption by Nitro Functionalized Metal Organic Frameworks Dilip Kumar Maity, Arijit Halder, Biswajit Bhattacharya, Anamika Das and Debajyoti Ghoshal* Department of Chemistry, Jadavpur University, Jadavpur, Kolkata, 700 032, India E-mail: [email protected] ___________________________________________________________________________ ABSTRACT: Two nitro functionalized Cu(II)-MOFs exhibit high CO2 uptake with nice selectivity over the other gases like H2, N2 and CH4; which is potentially important for the removal of carbon dioxide from industrial flue gas and natural gas. Here the selective CO2 adsorption by these MOFs are primarily due to the presence of suitable void with –NO2 group functionalized pore wall in the dehydrated framework which is unprecedented. ___________________________________________________________________________

The selective trapping of carbon dioxide using carbon capture and sequestration (CCS) technologies1,2 become highly connected to the enduring of civilization nowadays due to the alarming increase of CO2 concentration which may cause several environmental disorders.3,4 Presently, along with traditional CCS methods, the use of porous coordination polymers (PCPs), which are prevalently known as metal organic frameworks (MOFs)5-7 took enormous attention for the selective CO2 adsorption8-11 due to their presence of highly ordered pores, large surface areas, high thermal/solution stability. To make a MOF suitable for selective CO2 sequestration, the first criteria is to have a porosity of the MOF which is comparable to the kinetic

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diameter of CO2. Moreover, as the CO2 being a molecule with quadruple moment, a polar pore decorated with –NH2, –OH, –N=N–, –N=C(R)– moieties are necessary to increase the CO2-framework affinity which enable the resulting MOF for highly selective separation of CO2 from the mixtures of gases.12,13 In this context, the use of above functional group containing MOFs are exhaustedly explored and it has been almost established that the amino group is the most suitable one among the various functional group as the amino functionalized MOFs show nice selectivity on CO2.14-16 The nitro group having the polar nature and a possibility for the better interaction with the quadruple moment of CO2 can also be a good stuff for showing such selectivity. But the nitro functionalized MOFs are not yet been found so effective in CO2 sequestration17,18 as it is very difficult to embedded the nitro group centric towards the pore void. This is probably due to the large size of the nitro group which deflects its location from the pore wall. Moreover the bulky nitro groups can block the pore volume which also acts negatively for their use in designing MOFs for selective CO2 separation. But if some suitable design is made in the fabrication of pore wall of the MOFs with nitro functionalized linkers, that can also shows remarkable CO2 uptake with a high selectivity.

Scheme 1. Schematic representation of the role of –NO2 gr. and –NH2 gr. in CO2 adsorption.


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By the use of comparable pillar and layer linkers in mixed ligand MOF, here we have prepared a 3D porous Cu-MOF {[Cu(azbpy)(2-ntp)].H2O}n (1) which shows high CO2 uptake volume due to the presence of nitro group oriented towards the pore void. The slight increase in the length of pillar linker produces {[Cu(4-bpdb)(2-ntp)].2(H2O)}n (2) which have a comparable pore size as that of 1, but the nitro groups are not properly faced towards the pore like 1 and that has been reflected by its comparatively less CO2 uptake. Block shaped greenish crystals of 1 and 2 were obtained at room temperature by slow diffusion technique of aqueous solutions of Cu(NO3)2 and disodium salt of 2nitroterephthalic acid, [Na2(2-ntp)] with the methanolic solution of 4,4´-azobispyridine (azbpy) and N,N′-bispyridin-4-ylmethylenehydrazine (4-bpdb) linkers for 1 and 2 respectively. Compound 1 exhibits a 3D structure and its asymmetric unit contains one Cu(II) ion, one azbpy linker, one 2-ntp2- and one disorder lattice water molecule splits into three fragments with 0.25, 0.25 and 0.5 occupancy individually. The five coordinated Cu(II) centre with CuO3N2 coordination environment is connected by three carboxylate oxygen atoms (O1, O3a and O4b) from three 2-ntp2- and two nitrogen atoms (N1 and N4c) of two different azbpy linker (Figure 1a) exhibiting a distorted trigonal bipyramidal structure. Here each 2-ntp2- ligand bridges with three Cu(II) centres in a bridging monodentate-bidentate fashion and exhibits a 2D sheet of [Cu(2ntp)]n in crystallographic ab plane (Figure 1b) through the formation of a Cu3(CO2)5 trinuclear secondary building units (SBUs) (Figures S8a and S8b). The 2D sheets are further connected by azbpy ligand to form a 3D framework with water filled 1D channel along b-axis (Figure 1c) with the channel dimension of about 6.5×3.0 Å2 (Figure S10a). Interestingly the nitro groups are embedded in the pore wall of the said channel and even in the presence of bulky nitro groups; the total solvent accessible



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void without the lattice water molecule is pretty high as 773.5 Å3 estimated by PLATON,19 which is 32.7% of the total crystal volume of 2362.18 Å3. Structural analysis with TOPOS20,21 suggests that the overall framework of 1 exhibits a 3,5-c binodal net (Figure 1d) with stoichiometry (3-c)(5-c) and the corresponding Schläfli symbol is {63}{69.8}. Compound 2 shows a 3D paddle-wheel structure and its asymmetric unit contains one Cu(II) ion, one 4-bpdb linker, one 2-ntp2- and two lattice water molecules. The Cu(II) centre is coordinated by three carboxylate oxygen atoms (O1, O2a and O3b) from three different 2-ntp2- and two nitrogen atoms (N1 and N4c) from two different 4-bpdb linkers (Figure 2a) and exhibits a distorted trigonal bipyramidal structure. Here each 2-ntp2- ligand bridges with three Cu(II) centre like 1 to form a 2D sheet of [Cu(2-ntp)]n in bc plane (Figure 2b) but the bonding of the 2ntp2- ligand is little different than that of 1. In 2 the bidentate carboxylate groups of two different 2-ntp2- bridges two metal centres resulting the formation of a paddle wheel dinuclear Cu2(CO2)4 SBU along with the formation of another Cu4(CO2)8 SBU (Figure S9). The 2D sheets are pillared by 4-bpdb ligands to form the 3D framework with 1D channel along b-axis containing the guest water molecules (Figure 2c). Although the length of the N,N´-donor linker is higher in 2, but the dimension of the channel is about 6.1×3.8 Å2 which is slightly smaller due to the bent nature of the 4bpdb (Figure S11a). Moreover, the nitro groups are not directed towards the channel but the solvent accessible void estimated by PLATON19 is 710.7 Å3 which is 28.5 % of the total crystal volume of 2491.5 Å3. Structural analysis with TOPOS20,21 suggests that the overall framework of 2 exhibits a 3,5-c binodal (Figure 2d) net with stoichiometry (3-c)(5-c) and the corresponding Schläfli symbol is {4.64.83.102}{4.82}. Thermo gravimetric analysis (TGA) of 1, 2 and the dehydrated species of 1 (1a) has been carried out at the temperature range 30-600 oC and the as synthesized PXRD


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patterns of both 1 and 2 (Figures S6 and S7) confirm the phase purity of the bulk materials with the simulated pattern. Compound 1 shows a weight loss of ~3.55 % around 75°C corresponding to the loss of one lattice water molecule (calc. wt % 3.79; Figure S4); and the dehydrated framework is stable up to ~285 °C without any further weight loss but dehydrated 1a exhibits no weight loss up to 270 °C (Figure S4) indicating the absence of guest water molecule which is lost during the dehydration process; after that the dehydrated framework collapses into unidentified products by further heating. The PXRD pattern of dehydrated framework 1a, which is obtained by heating 1 at 150 oC under reduced pressure (Figure S6); shows almost identical peak position to the as synthesized 1 which indicates the rigidity of the framework after the removal of the water molecule. The PXRD pattern of the rehydrated framework 1b (Figure S6) also exhibits the identical peak positions to the as-synthesized 1 after exposing the dehydrated 1a in water vapor for seven days indicating the reversible robustness of the framework of 1. Retention of the single crystallinity of 1 at high temperature encouraged us to do the corresponding crystal structure after removing the guest volatile from the parent framework through evacuation at 150 oC. Herein the single-crystal-to-single-crystal (SC-SC) reversibility22,23 study of 1 (deep green) has been performed which represents the dehydrated 1a (dark green) and rehydrated 1b structures with almost analogues cell parameters (Tables S3 and S4, Scheme 2) showing the complete reversibility of the framework. It is needless to mention that the type of the crystal systems and space groups in all three structures (1, 1a and 1b) are equivalent whereas, the bond lengths and angles are almost equal with little bit difference (Tables S2-S4). In TGA, compound 2 shows a weight loss of ~7.13% at ~85 °C corroborating the loss of two lattice water molecules (calc. wt % 6.95; Figure S5) and the dehydrated framework which is further stable up to ~235 °C. The PXRD



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patterns (Figure S7) of dehydrated 2 (activated at 130 °C) is identical with the assynthesized 2 indicating the rigidity of the framework after the removal of guest volatiles, however unlike 1 the single crystallinity of 2 are not exist at high temperature.

Scheme 2. Schematic representation of the single-crystal-to-single-crystal (SC-SC) reversibility of 1; where 1, 1a and 1b are parent, dehydrated and rehydrated form of 1 respectively.

Looking on the stability of the framework confirmed by TGA and PXRD and having appreciably large solvent accessible void in both the dehydrated frameworks of 1 and 2, different gas (N2 at 77K and 298 K, H2 at 77K, CH4 at 298 K and CO2 at 195, 273 and 298 K) as well as vapor sorption (H2O and EtOH at 298 K) have been investigated. Both the


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compounds show selective CO2 adsorption (Figure 3) over other gases. These moderately high selective CO2 adsorption is quite logical due to the presence of highly polar –NO2 group24-27 with the polarization of significant negative charge density on O atom which may interact with the Lewis acidic C centre of CO2 molecule on the basis of dipole-quadruple interaction. In addition to that the presence of N-based Lewis basic functional polar surface (–N=N– and –CH=N–N=CH–) in the framework28,29 may also acts additively for the high CO2 selectivity. The space filling models of dehydrated framework of 1 show a unidirectional channel along b-axis (Figure S10) which attributes its non porosity towards N2 due to the blocking of 1D channel through diffusion of N2 molecule. It also shows a very little uptake at surface for H2 at 77 K and CH4 at 298 K. It is evident in Figure 3 that 1 exhibits type I profile in CO2 adsorption at 195 K with a high uptake of CO2. Interestingly, it shows a remarkable step rise up to ~134 cc/g at very low pressure region (from 0.001 to 0.16 bar); after that very slow uptakes of CO2 was observed with the increase of pressure which finally reaches at ~185 cc/g at 1 bar. It also shows reversible CO2 desorption along with adsorption isotherm with a small hysteresis which is originated probably due to adsorbent and adsorbate interaction.30-33 At the beginning, the isosteric heat of adsorption (Qst) of 1 is ~44 KJ/mol obtained from two adsorption data of CO2 (Figures S12 and S13) at two different temperature (i.e. 273 and 298 K) using Clausius Clapeyron equation which is (dlnp/dT) = Qst/RT2. After that, the isosteric heat of adsorption of 1 decreases with the uploading of adsorbate signifying the filling of their maximum affinity sites.34 The high Qst value of CO2 adsorption for 1 indicates strong interaction between NO2···CO2; N=N···CO2; aromatic π···CO2 and cooperative CO2···CO2 interactions operating mutually or in an individual manner.35 Dehydrated framework of 1 shows appreciable uptake of CO2 at room temperature/273 K which are 34 cc/g and 44 cc/g respectively (Figure S12). Similar to 1, dehydrated framework of 2 also shows non porosity towards N2 molecule with the similar reason of the presence of



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unidirectional channels along b-axis (Figure S11) and the H2 uptake and CH4 adsorption is also negligible as that of 1. But CO2 adsorption isotherm shows interesting type V profile with good selectivity (Figure 3) over all other above mentioned gases. In the CO2 adsorption profile of 2, it is observed that up to P = 0.55 bar, nearly no adsorption is occurred, but after this pressure, there is a sharp uptake of CO2 is observed which reaches up to 103 cc/g at P = 0.85 bar and then gradually reaches the final value of 126 cc/g at P = 0.99 bar. After that it regenerates the reversible desorption profile with a large hysteresis30-33 and an incomplete desorption which may be due to strong adsorbate-adsorbent interaction in 2. The gateopening behaviour36,37of 2

at P = 0.55 bar may be attributed to the expansion of the

framework owing to the flexible nature of the pore which is constructed by a flexible ligand, 4-bpdb. The dehydrated 2 also shows nice CO2 uptake at room temperature/273 K up to 10 cc/g and 15 cc/g respectively (Figure S14). At the onset, the isosteric heat of adsorption (Qst) of 2 has been calculated like 1, taking two different CO2 adsorption data measured at 273 K and 298 K (Figures S14 and S15) and found similarly with a high value (~43 KJ/mol) as that of 1 due to similar reason discussed above.35 To investigate the CO2 selectivity of both the compounds 1 and 2 over N2 and CH4, their single component gas sorption isotherms of CO2, N2 and CH4 have been also performed at room temperature i.e. at 298 K up to 1 bar pressure (Figures S16 and S17). The uptake of CO2 over N2 and CH4 for both the compounds at room temperature are found comparable, or even higher from the previously reported similar kind of MOFs.38-40 For selectivity measurement, the initial slopes of the adsorption isotherms were calculated individually, and the ratios of the initial slopes of respective isotherms were used to estimate the adsorption selectivity of CO2 over N2 and CH4 for both the compounds based on initial slope calculation.41-42 Based on that, the CO2/N2 and CO2/CH4 selectivities for 1 are 13.5 and 2.3 while for 2, these are 15 and 5 respectively (Figures S18 and S19).


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We have also measured the solvent sorption isotherms of two polar solvents, H2O and EtOH at 298 K for both the compounds; to observe the solvent-framework interaction. Dehydrated framework of 1 shows a lower uptake up to P/P0 ≈ 0.35 and after that an almost steep uptake up to a volume of ~126 cc/g at P/P0 ≈ 0.95 (Figure S20). The said volume indicates the uptake of 2.5 water molecules per formula unit, which is much greater than the calculated value (1.0 water per formula unit), observed possibly due to the expansion of the layered structure which occurs at higher pressure region. The EtOH vapor sorption of 1 gives simple type I adsorption profile with saturation value of ~107 cc/g at P/P0 ≈ 0.9 (Figure S20). On the other hand for dehydrated 2, the H2O and EtOH vapor sorption isotherms at 298 K (Figure S21) shows nearly same pattern and comparatively greater hysteresis as that of 1 with final uptake of EtOH vapour 44 cc/g at P/P0 ≈ 0.89 and water vapor 75 cc/g at P/P0 ≈ 0.9 corresponds to 1.6 water molecules per formula unit which closely supports the value obtained in TGA study of 2. In both the H2O and EtOH adsorption-desorption curve of 1 and 2 hysteresis are observed which is due the strong adsorbent-adsorbate interaction.30-33 It has been noticed in previous reports that the –NH2, –OH functionalized MOFs43-45 significantly enhances the CO2 adsorption selectively over other, due to Lewis acidbase type interactions as well as H-bonding interaction in between polar –NH2, –OH groups and Lewis acidic quadrupolar CO2 molecule. But the prospect of –NO2 functionalized MOFs had not been explored for CO2 adsorption due to the unsatisfied results18 with such MOFs, both in terms of amount of CO2 uptake as well as the selectively. But here we have synthesized two robust MOFs which show extremely enhanced CO2 uptake with remarkable selectivity which clearly established the utility of –NO2 functionalized MOFs for selective CO2 uptake rather than non-functionalized



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or other polar functionalized MOFs containing –NH2, –OH groups in the pore wall.18,35,46-50 The high Qst value for CO2 for both the compounds evidently supports the strong adsorbent-adsorbate interactions, which strongly correlates the interaction of O atoms of the nitro group with the quadruple moment of the CO2 mentioned earlier. It is clear from the above discussion that if the projection of bulky –NO2 group is not blocking the void of the framework, it can be an equally able or sometime more efficient to produce MOFs with CO2 capture selectivity. In a one liner, this work will add some new thinking on the traditional protocol of synthesizing MOFs with CO2 selectivity. ASSOCIATED CONTENT Supporting Information The experimental procedure, IR, PXRD patterns, TGA of 1, 1a and 2 along with different application based figures of both complexes and the tables related to the crystal structures reported in this paper are available as SI. The structure reported in this paper having the CCDC reference numbers 1434675-1434678 can be obtained CIF format along with the SI; free of charge via the internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author Debajyoti Ghoshal, e–mail: [email protected], FAX: +9133 2414 6223 Note: The authors declare no competing financial interest. ACKNOWLEDGMENTS Authors gratefully acknowledge the financial assistance given by SERB [No. SB/S1/IC-06/2014, grant to DG] Govt. of India. DKM and AD acknowledges UGC for the research fellowship. REFERENCES


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Figures

Figure 1. (a) View of coordination environment around penta coordinated Cu(II) with atom labelling scheme in 1 (azbpy ligand has been omitted for clarity); Cu (green), O (red), N (blue) and C (black). (b) 2D arrangement in 1 constructed by both metal and 2nitroterephthalate moiety (azbpy has been omitted for clarity). (c) View of the 3D structure of 1 pillared by azbpy ligand with 1D water channel. (d) Simplified topological representation of 3,5- connected binodal 3D net in 1.



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Figure 2. (a) View of coordination environment around penta coordinated Cu(II) with atom labelling scheme in 2 (4-bpdb ligand has been omitted for clarity); Cu (green), O (red), N (blue) and C (black). (b) 2D arrangement in 2 constructed by both metal and 2nitroterephthalate moiety (4-bpdb has been omitted for clarity). (c) View of the 3D structure of 2 pillared by 4-bpdb ligand with 1D water channel. (d) Simplified topological representation of 3,5-connected binodal 3D net in 2.

Figure 3. Different gas sorption isotherms of 1 and 2 respectively; (CO2 at 195K; N2 at 77K; H2 at 77K and CH4 at 298K); Filled symbols indicate adsorption and the open symbols show desorption curve.


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Table of Contents

Selective CO2 Adsorption by Nitro Functionalized Metal Organic Frameworks Dilip Kumar Maity, Arijit Halder, Biswajit Bhattacharya, Anamika Das and Debajyoti Ghoshal*

A challenging syntheses of nitro functionalized Cu(II)-MOFs encapsulating -NO2 group in the pore wall with appreciable void spaces in their dehydrated frameworks; that exhibit enhanced selective CO2 adsorption at 195 K over all other gases.


Selective CO2 Adsorption by Nitro Functionalized Metal Organic

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