Three Cd(II) MOFs with Different Functional Groups: Selective CO2

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Three Cd(II) MOFs with Different Functional Groups: Selective CO2 Capture and Metal Ions Detection Zhong-Jie Wang, Li-Juan Han, Xiang-Jing Gao, and He-Gen Zheng* State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210023, P. R. China S Supporting Information *

ABSTRACT: Three Cd(II) iso-frameworks {[Cd(BIPA)(IPA)]·DMF}n (1), {[Cd(BIPA)(HIPA)]·DMF}n (2), and {[Cd(BIPA)(NIPA)]·2H2O}n (3) were synthesized from the self-assembly of the BIPA ligand (BIPA = bis(4-(1H-imidazol-1-yl)phenyl)amine) and different carboxylic ligands (H2IPA = isophthalic acid, H2HIPA = 5-hydroxyisophthalic acid, H2NIPA = 5-nitroisophthalic acid) with Cd(II), which have amino groups, amino and phenolic hydroxyl groups, and amino and nitro groups, respectively. Both 1 and 2 exhibit CO2 uptakes of more than 20 wt %, indicating that amino and phenolic hydroxyl functionalized groups are beneficial to CO2 adsorption. Their applications and mechanisms in detecting metal ions were researched. The results exhibit that 1 and 2 are dual-responsive photoluminescent sensors for Hg2+ and Pb2+ ions with low detection concentration and high quenching constant. Besides, like most MOFs, 3 can detect a trace quantity of Fe3+ and Cu2+.

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INTRODUCTION Metal−organic frameworks (MOFs) are booming materials not only due to their charming and various structures1−4 but also for their multifarious properties, such as gas adsorption and separation,5−10 drug delivery,11−13 fluorescence,14−16 molecular sensing and separation,17−20 catalysis,21−26 magnetic property,27−29 solvatochromism,30,31 postfunctionalization,32−35 and removal of heavy metal ions.36,37 Carbon dioxide (CO2) selective adsorption from other gases is one of the important applications of MOFs for gas adsorption and separation, because CO2 is the major contributor to the greenhouse gas effect.38,39 Although a large number of MOFs are reported, efficiently selective adsorbing CO2 is still full of challenge and difficulty,40,41 because MOFs with large pores often tend to collapse or cause interpenetration and self-interpenetration after removal of guest molecules, which decrease their adsorption capacities.42,43 Therefore, MOFs modified with functional groups to improve adsorption capacities have drawn greater attention. Because of their porosity and luminescence, more and more MOFs are explored to detect inorganic anions (Cl−, I−, NO3−, etc.), metal ions (Cu2+, Fe3+, etc.), or other small organic molecules (2,4,6-trinitrophenol, 2,4,6-trinitrotoluene, 4-nitrophenol, etc.).44−49 Up to now, there are many MOFs applied in detecting Cu2+ and Fe3+, but little MOFs applied in detecting Hg2+ and Pb2+ ions, which are very dangerous and harmful heavy metal ions to human health and environment, with the characteristics of difficult to degrade, longlasting, transferable and bioaccumulative effect in ecosystems.50−53 The toxicology experiments show that Hg2+ and Pb2+ can also enrich in the © XXXX American Chemical Society

human body through the food chain, causing the serious damages of immune, protein synthesis, central nervous systems, and so on. The luminescent intensities of most MOFs have lower response to Hg2+ or Pb2+ ions than Fe3+ or Cu2+, due to lacking interactions between MOFs and metal ions. Herein, it is an effective measure to utilize secondary group participation (SGP) in binding with Hg2+ or Pb2+ to sensitively sense them, but in a subtle and weak fashion, which can hold framework integrity set up by primary links. For example, MOFs with amino and phenolic hydroxyl groups may detect Hg2+ or Pb2+ more sensitively, because they have stronger interactions with Hg2+ or Pb2+ than Fe3+ or Cu2+.53−56 Hence, we design an amino-functionalized “V-shaped” semirigid BIPA ligand (bis(4-(1H-imidazol-1-yl)phenyl)amine) due to amino groups benefiting adsorption capacities, such as CO2 capture (Scheme 1). And it is easy to construct varied interesting MOFs because C−N bonds between amino groups and benzene rings can rotate to modulate coordination orientations. Three rigid coligands H2IPA (isophthalic acid), H2HIPA (5-hydroxyisophthalic acid), and H2NIPA (5-nitroisophthalic acid) were selected to get MOFs, because the coordination modes of them are similar, which is helpful for constructing iso-frameworks to only focus on the influences of different functional groups. As we expected, three isoframeworks {[Cd(BIPA)(IPA)]·DMF}n (1), {[Cd(BIPA)(HIPA)]·DMF}n (2), and {[Cd(BIPA)(NIPA)]·2H2O}n (3) with different functional groups are synthesized. Thus, we focus Received: January 30, 2018

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DOI: 10.1021/acs.inorgchem.8b00272 Inorg. Chem. XXXX, XXX, XXX−XXX

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atom and three carboxylate oxygen atoms locate in the equatorial positions; one nitrogen atom and one carboxylate oxygen atom occupy the axial positions with N(1)−Cd(1)− O(3) angles of 137.49(6)° (Figure S2). The Cd−O distances range from 2.2470(16) to 2.5887(19) Å, and Cd−N distances are 2.2796(18) and 2.2321(19) Å. If BIPA ligands are ignored, the carboxylate groups of IPA2− anions link Cd(II) to develop a 1D Zig-zag chain (Figure 1b). 1D chains and BIPA ligands further form a 2D layered network (Figure 1b−d). And the amino groups are above/below the 2D layer. The framework consists of two kinds of channels (Figure 1c,d). There is an accessible void volume of 533.4 Å3 per unit cell in 1 estimated by PLATON analysis, which is 19.9% of the total volume. If the shape of BIPA ligands is ignored, the Cd ions can be viewed as 3-connected nodes, and 1 represents hcb topology with point symbol of (63) (Figure 1e).57 As shown in Table S3 and Figure S1, the 2D layers are alternately connected into a 3D supramolecular network via Hbonds interactions (N3−H3A···O2#1 = 2.941(3) Å, #1: −x, −y, −z + 1). It is worth noting that N3 is from the amino group of BIPA. As shown in Figures 1f and S1, the interpenetration of 1 is simplified as type Ia, Z = 2 (Zt = 2; Zn = 1). Topologically, the BIPA ligands and Cd centers act as 3-connected and 5connnected nodes, respectively (Figures 1g and S1). The whole structure can be represented as 2-fold interpenetrating 3,5T1 topology with point symbol of (42.65.83) (42.6).

Scheme 1. Structure of Ligands

on discussing the effects of amino, phenolic hydroxyl, and nitro groups in CO2 capture and luminescence sensors for detecting metal ions in this paper.

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RESULTS AND DISCUSSION Crystal Structure of {[Cd(BIPA)(IPA)]·DMF}n (1). MOF 1 crystallizes in monoclinic space group P21/n. The asymmetric unit of 1 consists of one Cd2+ ion, one BPPA ligand, one IPA2− ion, and one lattice DMF molecule. Each Cd1 is sixcoordinated with a distorted {CdN2O4} octahedral coordination geometry by two N atoms from two BIPA ligands and four O atoms from two H2IPA ligands (Figure 1a). One nitrogen

Figure 1. (a) Coordination environment of the Cd(II) ions in 1 (30% ellipsoid probability). Hydrogen atoms and solvent molecules are omitted. Symmetry codes: #1 = 0.5 + x, 0.5 − y, −0.5 + z, #2 = 1 − x, −y, 2 − z. (b−d) Views of the 2D layered network of 1. The two amino groups above the 2D layer are shown with two pink arrows, while two amino groups below the 2D layer shown with two light blue arrows. (e) Schematic representation of hcb topology of 1. (f) Perspective views of 2-fold interpenetrated framework of 1 when considering H-bonding interactions. (g) Views of a single 3D network of 1 when considering H-bonding interactions. B

DOI: 10.1021/acs.inorgchem.8b00272 Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 2. (a) Views of the 2D layered network of 2. Two phenolic hydroxyl groups above the 2D layer are shown with two pink arrows, while two phenolic hydroxyl groups below the 2D layer shown with two light blue arrows. (b) Perpective views of the 2D layered network of 3. Two nitro groups above the 2D layer are shown with two pink arrows, while two nitro groups below the 2D layer shown with two light blue arrows.

Figure 3. (a) N2 adsorption isotherms for 1−3 at 77 K. (b) CO2 adsorption isotherms for 1−3 at 273 K. Filled symbols = adsorption; empty symbols = desorption.

Crystal Structures of {[Cd(BIPA)(HIPA)]·DMF}n (2) and {[Cd(BIPA)(NIPA)]·2H2O}n (3). Single-crystal structure analysis reveals that both 2 and 3 crystallize in monoclinic space group P21/n. Although 1, 2, and 3 are iso-frameworks, there are some differences in coordination modes of Cd1 and conformation of ligands as shown in Figure S2. Interestingly, in 2, there are two phenolic hydroxyl groups above the 2D layer and two phenolic hydroxyl groups below the 2D layer in one hexagonal ring (Figure 2a). So are nitro groups in 3 (Figure 2b). The effective void volumes of the MOFs were calculated to be 17.7% for 2, 5.4% for 3 of the total crystal volume without guest molecules. Thermogravimetric Analyses and Powder X-ray Diffraction. TGA was carried out to examine the thermal stabilities of the three MOFs (Figure S4). For 1, a gradual weight loss of 11.51% (calcd 11.23%) is observed from 120 °C to approximately 240 °C, which is assigned to the loss of one lattice DMF molecule, and after 330 °C, it starts to decompose. The TGA curve of 2 shows that there is a weight loss of 9.66% between 120 and 250 °C, corresponding to the loss of one free DMF molecule (calcd 10.96%). Above 375 °C, the network of 2 subsequently collapses. For 3, there is a gradual weight loss of 4.68% (calcd 5.47%) from 90 to 130 °C, corresponding to the loss of two lattice water molecules. Then above 380 °C, there is a sharp weight loss which is ascribed to the decomposition of 3. To confirm the purities of 1−3, PXRD was carried out. The experimental patterns of 1−3 are nearly consistent with their simulated patterns (Figures S5−S7), which indicate that 1−3 have been successfully obtained as pure crystalline. Gas Sorption Properties. The three Cd(II) MOFs can still retain their porous frameworks after activated (Figures S5−S7), so we focus on their gas sorption properties. The sorption measurements were carried out on the activated samples, using

N2, CO2, and CH4 as the adsorptive gases. The adsorption amount of N2 is 59.7, 45.8, and 31.0 cm3/g for 1−3 at 77 K and 1 atm, respectively (Figure 3a). They all exhibit type IV sorption profiles, showing that only surface adsorption occurs.58,59 The CO2 sorption isotherms of 1−3 were measured at 273 K (Figure 3b). The gas sorption isotherms show the CO2 uptake of 102.1 cm3/g (4.56 mmol/g, 20.1 wt %) for 1, 110.4 cm3/g (4.93 mmol/g, 21.7 wt %) for 2, and 41.9 cm3/g (1.87 mmol/g, 8.23 wt %) for 3 at 273 K and 1.05 atm (800 Torr). There are a few MOFs exhibiting CO2 uptakes of more than 20 wt % under ambient conditions.38−41,60−65 Although the porosity of 2 is lower than that of 1, the CO2 sorption amount of 2 is higher. This may be attributed to the phenolic hydroxyl groups from the H2HIPA ligand, which can be considered as hydrogen-bonding donors benefiting CO2 sorption. The CO2 sorption amount of 3 is the lowest in them, which may be due to the smallest accessible volumes and the influence of nitro groups from the H2NIPA ligand. As shown in Figure S8, the sorption amount of CH4 is negligible compared with CO2, 22.61 cm3/g for 1, 17.59 cm3/g for 2, and 12.39 cm3/g for 3 at 273 K and 1.05 atm (800 Torr). There are two main reasons for the distinct difference of adsorption capacity of CO2/N2 or CO2/CH4: (1) the smaller kinetic diameter of CO2 (3.3 Å) than that of N2 (3.64 Å) and CH4 (3.8 Å); (2) the influences of the amino groups from the BIPA ligand and phenolic hydroxyl groups from H2HIPA ligand. As is well-known, the amino and phenolic hydroxyl groups as hydrogen-bonding donors form H-bonding interactions with CO2 molecules. And the amino groups are also a kind of Lewis basic group benefiting CO2 adsorption. Such high CO2, low N2 and CH4 uptake suggest these MOFs are potential materials for selective adsorption of CO2 and N2/CH4.60−65 Above all, C

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Figure 4. (a) Degree of fluorescence quenches of 1−3 after addition of different metal ions (5 × 10−3 M). (b) Photographs of 1−3 under UV light (310 nm) before (labeled as 1, 2, 3, respectively) and after addition of different metal ions (5 × 10−3 M).

Figure 5. UV−vis spectra of 1−2 before and after addition of Hg2+ or Pb2+ ions.

addition of 70 μL of Hg2+ solution does the photoluminescence intensity of 1 decrease to 8.90%. To our surprise, the photoluminescence intensity of 1 increases to 146.00% with gradual addition of 70 μL of Pb2+ solution. Compared to 1, MOF 2 has higher selectivity for Hg2+ and Pb2+ (Figures 4 and S14). Among the 14 metal ions, Hg2+ has the highest quenching efficiency (88.56%) for 2 when only addition of 55 μL of Hg2+ solution. The photoluminescence intensity of 2 increases to 150.36% by addition of 55 μL of Pb2+ solution. Quantitatively, quenching efficiency is calculated using the Stern−Volmer (SV) equation: (I0/I) = 1 + Ksv[Q], where I0 and I are the luminescence intensities without and with adding metal ions, respectively, Ksv is quenching constant, and [Q] is molar concentration of metal ions. The SV plots of Hg2+ are almost linear at low concentrations (Figure S16). But they bend upward and become nonlinear at higher concentrations because of self-absorption or energy transfer.44−49 Both 1 and 2 show the highest Ksv values (for 1: Ksv = 9.21 × 103 M−1, R2 = 0.9998; for 2: Ksv = 1.28 × 104 M−1, R2 = 0.9999) with Hg2+ in the metal ions. The photoluminescent sensing by Hg2+ and Pb2+could be determined at very low concentration (5.0 × 10−7 M and 7.5 × 10−7 M for 1, respectively; 2.5 × 10−7 M and 5.0 × 10−7 M for 2, respectively). Low detection concentrations of

amino groups and phenolic hydroxyl groups are beneficial to CO2 adsorption. Luminescent Sensing of Metal Ions. The solid-state fluorescences of the BIPA ligand and MOFs 1−3 were measured at room temperature (Figure S9). The luminescences of 1−3 are very similar to that of the free BIPA ligand, showing that the luminescences can be due to the charge transfer within the ligands. And slightly red-shifted emission bands in 1−3 compared with free BIPA ligand might be related to the coordination effect. Besides, 1−3 were soaked in aqueous solutions with different pH values to explore their stability. PXRD patterns clearly showed that the framework integrity of 1−3 can be well-retained in pH = 2−13 aqueous solutions (Figures S10−S12). Considering environmental security, good stability, porous, and strong luminescent properties of 1−3, we investigate their potential sensing metal ions, including Hg2+, Fe3+, Cu2+, Cd2+, Co2+, Zn2+, Ni2+, Ca2+, Ag+, Na+, Al3+, K+, Mg2+, and Pb2+. The photoluminescence response was measured in situ after gradual addition of fresh different metal ions in dimethylformamide (DMF) (5 × 10−3 M) to the suspensions of 1−3 in DMF. As shown in Figures 4 and S13, the fluorescence intensity decreases quickly with adding Hg2+ in 1. Only by gradual D

DOI: 10.1021/acs.inorgchem.8b00272 Inorg. Chem. XXXX, XXX, XXX−XXX

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Figure 6. (a) N 1s, (b) O 1s XPS peaks of 1 before and after immersed in Hg2+ or Pb2+. (c) N 1s, (d) O 1s XPS peaks of 2 before and after immersed in Hg2+ or Pb2+. (e) Hg 4f, (f) Pb 4f XPS peaks of 1−2 after immersed in Hg2+ or Pb2+.

Hg2+ and Pb2+ show 1 and 2 can easily detect a trace quantity of Hg2+ and Pb2+. The emission decay lifetimes of 1 and 2 significantly reduced a lot after the addition of Hg2+, and increased after the addition of Pb2+ (Figure S17). In Figure 4b, there is no obvious emission observed under 310 nm UV light after addition of Hg2+ for 1 and 2. After addition of Pb2+, the emissions of both 1 and 2 increased obviously, which make them easy to distinguish by the naked eye. But there is no obvious photoluminescent change for 3 after addition of Hg2+ and Pb2+. Like most MOFs, an emission could barely be observed after the addition of iron or copper ions under 310 nm UV light, showing that 3 can detect a trace quantity of Fe3+ and Cu2+. Mechanisms of Luminescent Sensing. In most instances, MOFs show higher sensitive and selective detection of Fe3+ or Cu2+ than other metal ions, like MOF 3. Thus, the mechanisms of 1 and 2 for sensing Hg2+ and Pb2+ must be investigated. As shown in UV−vis absorption spectra, the maximum absorption peaks of 1 and Hg2+ ion in DMF appear at 330 and 283 nm, respectively (Figure 5a). After addition of Hg2+ ion, absorption peak of 1 at 330 nm reduces, while a new absorption peak appears at 266 nm. There are similar changes in 1−2 after addition of Hg2+ or Pb2+ ions. This indicates that there are excited electrons transferring from 1 or 2 to Hg2+ or Pb2+ ions.

Considering that amino, phenolic hydroxyl, and nitro groups take no part in coordinating and there are electrons transferring from 1 or 2 to Hg2+ or Pb2+ ions, we suppose that SGP (for example, amino and phenolic hydroxyl groups) in binding to metal ions (Hg2+ or Pb2+) to sensitive luminescence sense, but in a subtle and weak fashion, in order to hold the framework integrity set up by primary links. To verify our supposition, 1 or 2 (5 mg) was immersed in Hg2+ or Pb2+ solution (3 mL, 1 μM). PXRD patterns showed that their structural integrity can be well-retained after being immersed in metal ions for 12 h (Figures S19 and S20). ICP determination was made to detect the concentrations of Hg2+ or Pb2+ ions. The obvious decreased concentrations of Hg2+ or Pb2+ ions display that there are weak interactions between 1−2 and Hg2+ or Pb2+ ions (Table S5). The weak binding between 1−2 and Hg2+ or Pb2+ ions is further verified in X-ray photoelectron spectroscopy (XPS). Two new peaks appear at 99.1 and 103.1 eV in 1 after addition of Hg2+, which belong to the Hg 4f peak, indicating that there are weak interactions between 1 and Hg2+ (Figure 6). After addition of Hg2+, the N 1s peak in 1 is shifted from 396.8 to 397.7 eV, while the O 1s peak at 528.6 eV has no obvious change. The similar changes can also be seen in 1 after addition of Pb2+, showing the weak interactions between only N atoms and Hg2+ or Pb2+. Compared with 1, the O 1s peak is also shifted from 529.6 to 530.6/530.3 eV in 2 after addition of Hg2+/Pb2+, respectively. It shows that both nitrogen atoms E

DOI: 10.1021/acs.inorgchem.8b00272 Inorg. Chem. XXXX, XXX, XXX−XXX

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21701048), and the Natural Science Foundation of Shandong Province (ZR2017MB047).

from amino groups and oxygen atoms from phenolic hydroxyl groups in 2 have weak interactions with metal ions (Hg2+ or Pb2+). 2 has higher selectivity for Hg2+ and Pb2+ because of the more weak interactions with Hg2+ or Pb2+. Although 3 has amino and nitro groups, there is no obvious photoluminescent change by Hg2+ and Pb2+, because its porosity is too small to form weak interactions with metal ions. As reported, stereochemically active lone pairs and the ns2np0 configuration of Pb2+ usually cause substantial luminescent processes including metal centers to increase the photoluminescence intensity.53,66,67 Hence, the photoluminescence intensities of 1−2 increase after addition of Pb2+.

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CONCLUSIONS In summary, we successfully synthesized three iso-frameworks 1−3, which have amino groups, amino and phenolic hydroxyl groups, and amino and nitro groups, respectively. Both 1 and 2 exhibit high CO2 sorption. Although the porosity of 2 is not the highest, 2 uptakes the greatest amount of CO2 because of its porosity, and amino and phenolic hydroxyl functionalized groups, which are beneficial to CO2 adsorption. Both 1 and 2 show a drastic luminescent quenching effect for Hg2+ with low detection concentration (5.0 × 10−7 M and 2.5 × 10−7 M, respectively) and high quenching constant. After addition of Pb2+, the photoluminescence intensities of 1 and 2 increase obviously with a low detection limit (7.5 × 10−7 M and 5.0 × 10−7 M, respectively). Thus, 1 and 2 can be promising dualresponsive photoluminescent sensors for Hg2+ and Pb2+ ions. Besides, like most MOFs, 3 can detect a trace quantity of Fe3+ and Cu2+.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b00272. Crystallographic data, selected bond lengths and angles, experimental details, FT-IR spectra, TGA and DSC curves, PXRD, CH4 adsorption isotherms, photoluminescence spectra, and the luminescence decay curve (PDF) Accession Codes

CCDC 1522031−1522033 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Fax: 86-25-89682309. ORCID

He-Gen Zheng: 0000-0001-8763-9170 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by grants from the National Natural Science Foundation of China (Nos. 21771101, 21371092, and F

DOI: 10.1021/acs.inorgchem.8b00272 Inorg. Chem. XXXX, XXX, XXX−XXX

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DOI: 10.1021/acs.inorgchem.8b00272 Inorg. Chem. XXXX, XXX, XXX−XXX