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Enhancement of Intrinsic Proton Conductivity and Aniline Sensitivity by Introducing Dye Molecules into the MOF Channel Lizhen Liu, Zizhu Yao, Yingxiang Ye, Chulong Liu, Quanjie Lin, Shimin Chen, Shengchang Xiang, and Zhangjing Zhang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b22327 • Publication Date (Web): 18 Apr 2019 Downloaded from http://pubs.acs.org on April 18, 2019

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ACS Applied Materials & Interfaces

Enhancement of Intrinsic Proton Conductivity and Aniline Sensitivity by Introducing Dye Molecules into the MOF Channel Lizhen Liu,† Zizhu Yao,† Yingxiang Ye,† Chulong Liu,† Quanjie Lin,† Shimin Chen,† Shengchang Xiang† and Zhangjing Zhang*,† †Fujian

Provincial Key Laboratory of Polymer Materials, College of Chemistry and Materials Science, Fujian Normal University, 32 Shangsan Road, Fuzhou 350007, PR China

ABSTRACT: The encapsulation dyes into metal-organic frameworks (MOFs) have generated variety platforms for luminescent, but little attention has been paid to their application

in

proton

conduction.

Here,

an

cationic

{{[In3OL1.5(H2O)3](NO3)}·(DMA)3·(CH3CN)6·(H2O)30}n

(FJU-10,

H4L=4,4′,4″,4‴-(1,4-Phenylenbis(pyridine-4,2,6-triyl))-tetrabenzoic N,N-Dimethylacetamide)

was

synthesized,

MOF

and

acid,

DMA=

dye

molecule

the

8-hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt (HPTS) was further added the MOF growth solution, but during the reaction, HPTS was nitrated and nitrated HPTS was encapsulated into the FJU-10 to obtain dye@FJU-10. As a result, the intrinsic proton conductivity of dye@FJU-10 is nearly 5 times higher than that of FJU-10 at 90 oC. The dye@FJU-10 exhibits a more sensitive fluorescence quenching toward aniline than FJU-10 in DMF solution (the detection limits of FJU-10 and dye@FJU-10 are as low as 0.58 μΜ and 0.62 μΜ, respectively). Here, it is firstly demonstrated that the proton conductivity can be effectively improved by encapsulating a nitrated HPTS dye into the MOFs.

KEYWORDS: metal-organic frameworks (MOFs); dye encapsulation; one step approach; intrinsic proton conduction; aniline detection

INTRODUCTION Proton conduction materials are the vital components of proton exchange membrane fuel cells (PEMFCs), but commercial Nafion-based electrolytes are limited large-scale application due to high relative humidity, narrow operating temperatures, and freezing damage induces by freeze/thaw cycles.1-4 Metal-organic frameworks (MOFs) as an emerging electrolyte material have attracted attention as a promising platform for their adjustable porosity and modifiable features.5-10 Although these MOFs exhibited good prospects, it is still a challenge to develop MOFs with high conductivity and wide operating temperature, especially in the sub-zero 1

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temperature range. There are some practical strategies have been introduced into MOF for proton conduction, one is to modify the skeleton, such as introducing the sulfonic or free carboxylate group in the skeleton,

11-13

and the other is to regulate the channels, like loading

some proton carriers (eg. imidazole, H3PO4 and H2SO4) into the pores.

14-19

Dyes are organic molecules with excellent luminescent properties, which are often encapsulated into MOF or macrocycles as host/guest composite for fluorescence applications.20-24 In addition to good optical properties, some dye molecules with functional group (eg. -COOH or -SO3H) can be used as outstanding proton carries. J. M. Dawlaty25 and S. Kitagawa26 doped 8-hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt (HPTS) into the organic polymers and coordination polymers to enhance photoinduced proton conductivity, respectively, but dye molecules encapsulated into MOF as proton conduction material has not been reported yet. Here, we reported a MOF-based material through one-step fabrication of embedding in-situ

nitrated

HPTS

into

the

channels

of

In(III)-MOF

{{[In3OL1.5(H2O)3](NO3)}·(DMA)3·(CH3CN)6·(H2O)30}n (FJU-10) (Scheme 1), which shows the enhanced intrinsic proton conductivity and fluorescence sensing ability. The dye@FJU-10 displays significantly better intrinsic proton conducting behavior (7.50 × 10-3 σ/cm, 90 oC) and higher sensing ability of aniline (Ksv = 5.82 × 104 M-1 and detection limit 0.62 μΜ) than FJU-10. Their intrinsic proton conductivity and fluorescence detection ability are even better than most of the reported MOF materials (Tables S4-S5). Therefore suitable dye molecules loaded in MOF may be a promising path to improve proton conductivity and fluorescence detection ability.

2


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Scheme 1. Schematic illustration of the encapsulation of dyes into FJU-10 via one step method.

EXPERIMENTAL SECTION Synthesis of 4,4′,4″,4‴-(1,4-phenylenbis(pyridine-4,2,6-triyl))-tetrabenzoic acid(H4L). It was synthesized similarly as reported previously.27-29 Synthesis of {{[In3OL1.5(H2O)3](NO3)}·(DMA)3·(CH3CN)6·(H2O)30}n (FJU-10). H4L (0.02 g, 0.03 mmol) and In(NO3)3·xH2O (0.03 g, 0.1 mmol) were dissolved in DMA/CH3CN (v/v= 1 : 1) mixture solution with the addition of HNO3 at 85 oC for 48 h afforded bright yellow block crystal of FJU-10. The crystals were collected and air dried. Elemental analysis calcd (%) for FJU-10, C90H147N13O52In3: C 41.77, H 5.73, N 7.04; found: C 40.56, H 5.63, N 7.36. IR spectrum (KBr, cm−1): 3051(w), 2925(s), 1704(w), 1602(s), 1376(s), 1253(m), 1171(m), 1101(w), 1014(s), 782(s), 586(s), 484(s), 412(m). Synthesis of {{[In3OL1.5(H2O)3](NO3)0.7(C16H4O14N5S)0.3}·(DMA)3·(CH3CN)6·(H2O)28}n (dye@FJU-10). H4L (0.02 g, 0.03 mmol), HPTS (0.0052 g, 0.01 mmol) and In(NO3)3·xH2O (0.03 g, 0.1 mmol) were dissolved in DMA/CH3CN (v/v= 1 : 1) mixture solution with the addition of HNO3 at 85 oC for 48 h afforded fuchsia block crystal of dye@FJU-10. The crystals were collected and washed by DMF to remove the dyes on the surface of MOF. Through

the

control

experiment,

the

fuchsia

is

the

color

of

3-Hydroxy-2,5,6,8,9-pentanitro-pyrene-1-sulfonic acid (nitrated HPTS) of HPTS nitrification and the molecular formula is C16H4O14N5S (see Experimental Section in ESI). Elemental 3



analysis calcd (%) for dye@FJU-10, C94.8H144.2N14.2O53.3S0.3 In3: C 42.33, H 5.40, N 7.39, S 0.36; found: C 42.35, H 5.64, N 7.37, S 0.37. IR spectrum (KBr, cm−1): 3056(w), 2935(w), 1714(w), 1610(s), 1406 (m), 1307(m), 1297(m), 1184(m), 1178(w), 1043(w), 864(w), 788(s), 742(m), 703(s), 594(m).

RESULTS AND DISCUSSION

Figure 1. The structure of FJU-10: (a) trinuclear In(III) unit and (b) ligand H4L; (c) a cubic cage in the framework of FJU-10; (d) 3D network in FJU-10. Crystal Structure Analysis. Bright yellow block crystals of FJU-10 were afforded by solvothermal reaction of H4L and In(NO3)3·xH2O in DMA/CH3CN mixed solution with the addition of HNO3 at 85 oC for 48 h. The single-crystal X-ray diffraction analysis showed FJU-10 belongs to the cubic space group Pm3n, with trimeric [In3O(COO)6] clusters as the secondary building units (SBUs) (Figure 1a). The trimeric SBUs are further connected by six independent ligands L to form a 3D structure, which is isostructure with the Fe-MOF crystal30 (Figure 1d). The framework of FJU-10 is cationic, and the disordered NO3- as counterions. The whole framework contains embedded cubic cages (the dimensions cal. 18.6 Å) and two different types channels (with or without water molecules suspended in the channels, with sizes of 17.5 × 17.5 Å2 and 22.1 × 22.1 Å2, respectively) (Figure 1c-1d), which accounts for 4


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82 % of the accessible volume calculation using PLATON software.31 By the elemental analyses, charge balance and TG analysis, the molecular formula of FJU-10 was determined as {{[In3OL1.5(H2O)3](NO3)}·(DMA)3·(CH3CN)6·(H2O)30}n, in which there are 24 DMA, 48 CH3CN, and 240 H2O molecules per unit cell.

Dye Encapsulation. Inspired by the structure features of FJU-10, we attempted to encapsulate the photosensitive dye molecules HPTS into pores by adding HPTS to the MOF growth solution, and as a result, we harvested the fuchsia block crystals of dye@FJU-10 (Scheme 1). The obtained crystals were washed with DMF to remove dye on the surface of the MOF. By control experiment, we found that the fuchsia is the color of the product of HPTS nitrification. Compared to FJU-10, the color change of crystal from bright yellow to fuchsia confirms that the dye molecules have successfully introduced into the channels of MOF. The UV-Vis spectrum of the dye@FJU-10 showed a large red shift, and the red shift phenomenon is very similar to the nitrification experiment of HPTS, indicating that the dye molecule of nitrified HPTS does enter the framework22,23,32,33 (Figure S12-S13 and Experimental Section in ESI). As expected, the structure of dye@FJU-10 was characterized by single crystal X-ray analysis, and its structure was similar to FJU-10, however, owing to the low occupancy and highly disordered of dye, we cannot obtain the detailed location of dye in the framework by single crystal X-ray diffraction. The powder X-ray diffraction patterns of dye@FJU-10 is consistent with the simulation and as-synthesis of FJU-10, indicating that the dye molecules were encapsulated into channels of MOF without changing the framework of FJU-10 (Figure S3). By the elemental analyses, charge balance, TG analysis and control experiments,

the

molecular

formula

of

dye@FJU-10

was

determined

as

{{[In3OL1.5(H2O)3](NO3)0.7(C16H4O14N5S)0.3}·(DMA)3·(CH3CN)6·(H2O)28}n, in which there are 2.4 dye, 24 DMA, 48 CH3CN, and 224 H2O molecules per unit cell, indeed the amount of dye molecules embedded at a very low level.

5



Figure 2. Nyquist plots of FJU-10 (a) and dye@FJU-10 (b) at various temperatures under no additional humidity conditions (scatters represent experiment data, and lines do fitting data from equivalent circuits); (c) Proton conductivities of FJU-10 and dye@FJU-10 at -40 oC, 30 oC and 90 oC under no additional humidity conditions, respectively; (d) Arrhenius plots of FJU-10 and dye@FJU-10. Proton conduction. The nitrated HPTS also retains the -OH and -SO3H of HPTS and therefore acts as good proton carrier.25,26 In addition, FJU-10 and dye@FJU-10 are confined to abundant water molecules in the channels, so we can study their intrinsic proton conduction under no additional humidity conditions. The alternating current (AC) impedance spectrums were applied to characterize proton conductivity of two compounds from -40~90 oC under no additional humidity conditions. The Nyquist plots of two compounds at different temperature are exhibited in Figure 2a-2b and S7-S8. Under sub-zero temperature (-40 oC), the proton conductivities (σ) of FJU-10 and dye@FJU-10 is 3.45 × 10-7 σ/cm and 3.32 × 10-6 σ/cm, respectively. With temperature increasing, the proton conductivity of two MOFs rapidly increases, but the magnitude of the rise is very different. As Figure 2c shown, the proton conductivity of FJU-10 is 2.05 × 10-4 σ/cm at 30 oC, while the proton conductivity of dye@FJU-10 is 1.25 × 10-3 σ/cm, and its conductivity is six times higher than FJU-10 at the 6


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same condition. At 90 oC, dye@FJU-10 reaches the highest value of 7.50 × 10-3 σ/cm, close to 5-fold higher values than FJU-10, and higher than most MOF conductors under no additional humidity conditions, eg. [Eu2(CO3)(ox)2(H2O)2]·4H2O34, [Zn(H2PO4)2(TzH)2]n35, ZrP,36 (Me2NH2)[Eu(L)]37 and FJU-31@Hq3, and comparable to some high-performing MOF

conductors,

such

as

HCl⊂(C2N2H10)(C2N2H9)2Cu8Sn3S1238,

[ImH2][Cu(H2PO4)1.5(HPO4)0.5·Cl0.5]39 and FJU-177. These results clearly indicate that the proton conductivity of dye@FJU-10 is higher than of FJU-10 in the whole temperature range, implying that the dye in MOF plays an important role in improving proton conductivity. Based the concept for photoswitchable proton conducting materials, we further investigated the proton conductivity of dye@FJU-10 under illumination. Unfortunately, there is no significant change of the ohmic resistance for dye@FJU-10 observed under UV irradiation (Figure S9), which may be due to the low amount of dye in MOF or the loss of photoacidity of nitrified HPTS. Although we did not achieve photoswitchable proton conducting materials, we did succeed in enhancing the intrinsic proton conduction of FJU-10 by encapsulating dye into MOF. Besides, the DC conductivity of two MOFs (Figure S11) were tested and found to show very low electronic conductivity (5.87 × 10-10 S/cm for FJU-10 and 3.13 × 10-9 S/cm for dye@FJU-10), indicating that the two MOFs are indeed proton conducting materials. To elucidate the possible mechanism of two compounds, the activation energies (Ea) of both were estimated using the Arrhenius equation (shown in the ESI) .The Ea of FJU-10 and dye@FJU-10 were calculated to be 0.50 eV and 0.45 eV, respectively (Figure 2d). Generally, the behavior of proton conduction can be determined by the value of Ea form two mechanisms: Grotthuss mechanism (Ea: 0.1-0.4 eV) and vehicle mechanism (Ea: 0.5-0.9 eV)40,41. The Ea of FJU-10 is on the boundary of vehicle mechanism, and the process of proton transport may be coordinated water or lattice water molecules produces proton H3O+ that diffuse into the channels, while other water molecules move in opposite direction, resulting in a higher activation energy.42-44 After the dye molecules were incorporated into FJU-10, introducing the proton carriers (-OH and -SO3H) is helpful for the formation of hydrogen-bonds between water molecules and dye molecules to facilitate the proton transportation.3,11,45 Two mechanisms in dye@FJU-10 should coexist in the temperature 7



range of -40~90 oC, that is, besides the diffusion of water molecules, the hydrogen bonding formed by dye and water molecules also exist in the channel, which make them have lower Ea and higher conductivity than FJU-10.44,46

Figure 3. The fluorescence spectra for H4L (Ex= 470 nm), HPTS (Ex= 430 nm), FJU-10 (Ex= 350 nm) and dye@FJU-10 (Ex= 450 nm) in solid, and the nitrated HPTS in DMF. Fluorescence property. The solid-state emission spectra of H4L, HPTS, FJU-10 and dye@FJU-10 were investigated at room temperature (Figure 3). FJU-10 exhibits two different broad bands at 385 nm and 545 nm, which is different from the emission peaks of ligand H4L, mainly attributed to intramolecular and intermolecular electron transitions.47 The nitrated HPTS is red-shifted by 149 nm compared to the emission peak of HPTS. It is noteworthy that dye@FJU-10 exhibits strong emission peak at 662 nm, which is highly red-shifted (Δ=77 nm) with respect to ligand H4L and slightly blue-shifted (Δ=15 nm) with respect to that for nitrated HPTS. This phenomenon may be due to π…π complexation between ligand in the skeleton and nitrated HPTS in the channel.32,48 Aniline as a typical aromatic amine is an indispensable chemical precursor widely applied in rubber industries49, dyes intermediates50, pharmaceuticals51 and other field.52 However, on account of their severe toxicity and suspected carcinogenic properties, once the leakage is occurred even at very low concentrations, it will jeopardize environmental security and human health.53 Therefore, the rapid and efficient detection of aniline is extremely urgent for public security and environmental protection. Considering two MOFs excellent and unique fluorescence properties, aniline as an electron donor may affect the interaction 8


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between two MOFs and aniline. The difference of the interaction may provide a means to improve the sensitivity of detecting aniline. Therefore, we tested their ability to detect aniline in DMF by the titration tests. As expected, as the aniline concentration increases, their fluorescence intensity gradually decreases (Figure 4a and 4c). The quenching efficiency can be evaluated by the Stern-Volmer (SV) equation: I0/I =1 + Ksv[M] (I0 and I are the luminescence intensities before and after the addition of aniline; Ksv is the quenching constant (M-1); [M] is the molar concentration of aniline ). The SV plots for aniline show good linear relationship at low concentration, and the plots subsequently deviate from linearity at high concentration, which is likely to self-absorption

54-56(Figure

4b and 4d). The Ksv constants of

FJU-10 and dye@FJU-10 for aniline are 1.87×104 and 5.82×104 M-1, respectively. In addition, the detection limits of FJU-10 and dye@FJU-10 are 0.58 μΜ and 0.62 μΜ, respectively, according to 3δ/k.57,58 The sensitivities and detection limits for our two materials are comparable with the best materials reported ever (Table S5), and the slight enhancement of the sensitivities and detection limits in dye@FJU-10 may be attributed the extra interactions between aniline and the introducing dye molecules (Figure S14).

Figure 4. The luminescence of FJU-10 (a) and dye@FJU-10 (c) dispersed in DMF with different concentrations of aniline. The Stern-Volmer plots of I0/I versus aniline concentration in FJU-10 (b) and dye@FJU-10 (d) in DMF suspension. 9



CONCLUSIONS In summary, the nitrified HPTS was loaded into the FJU-10 by one-step approach, which not only its intrinsic proton conductivity is increased by close to 5-fold higher values and the sensitivities and detection limits of detection aniline were slightly enhanced. Therefore, suitable dye molecules loaded in MOF may be a promising path to improve proton conductivity and fluorescence detection ability. Further work will be required to unravel the microscopic mechanism leading to the enhance proton conductivity and fluorescence sensitivity.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.xxxxxx. additional experimental details; selected bond lengths and angles; PXRD analysis; FT-IR spectra; TGA curves; DSC curves; Nyquist plots; UV-Vis absorption spectra (PDF) X-ray crystallographic data for FJU-10 (CIF) X-ray crystallographic data for dye@FJU-10 (CIF)

AUTHOR INFORMATION Corresponding Authors *E-mail: [email protected].(Z.Z) Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS This work was financially supported by the National Natural Science Foundation of China (21573042, 21673039, and 21805039), Fujian Science and Technology Department (2018J07001 and 2016J01046).

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