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Cite This: ACS Appl. Mater. Interfaces 2019, 11, 3400−3406

Zr-MOF/Polyaniline Composite Films with Exceptional Seebeck Coefficient for Thermoelectric Material Applications Chih-Chien Lin,† Yi-Chia Huang,† Muhammad Usman,‡ Wen-Hsuan Chao,§ Wei-Keng Lin,∥ Tzuoo-Tsair Luo,‡ Wha-Tzong Whang,† Chun-Hua Chen,*,† and Kuang-Lieh Lu*,‡ †

Department of Materials Science and Engineering, National Chiao Tung University, Hsinchu 300, Taiwan Institute of Chemistry, Academia Sinica, Taipei 115, Taiwan § Material and Chemical Research Laboratory, Industrial Technology Research Institute, Hsinchu 310, Taiwan ∥ Department of Engineering and System Science, National Tsing Hua University, Hsinchu 300, Taiwan ACS Appl. Mater. Interfaces 2019.11:3400-3406. Downloaded from pubs.acs.org by UNIV OF WINNIPEG on 01/25/19. For personal use only.

‡

S Supporting Information *

ABSTRACT: Controlling the polymerization of aniline in the presence of zirconium-based metal−organic frameworks (Zr-MOFs) using polystyrene sulfonic acid as a dopant resulted in the formation of a new type of freestanding thermoelectric composite film. Polyaniline chains interpenetrate into the Zr-MOFs to enhance the crystallinity of polyaniline, resulting in an improved degree of electrical conductivity. In addition, the inherent porosity of the Zr-MOFs functions to suppress the increase in thermal conductivity, thus dramatically promoting a negative Seebeck coefficient. When 20 wt % ZrMOF was used, a power factor of up to 664 μW/(m K2) was obtained, which was accompanied by a surprisingly large, negative Seebeck coefficient. The new class of MOF-based composites offers a new direction for developing new types of efficient thermoelectric materials. KEYWORDS: composites, metal−organic frameworks, polyaniline, Seebeck coefficient, thermoelectric materials

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INTRODUCTION Green energy sources are currently important alternatives in terms of reducing annual CO2 emission. As such, strategies that decrease the speed of global warming and that involve the reuse and transformation of waste heat into useful electrical power are subjects of great interest.1 Thermoelectric (TE) materials that can be used to convert heat flow into electricity are therefore highly desirable for further developing green power.2 Thermoelectric materials composed of organic polymers have been subjects of increasing attention in recent years.3−5 Due to their light weight, low cost, high flexibility, ease of synthesis, ease of processing into versatile forms, and relatively low thermal conductivity, these types of TE materials have great potential for use in developing green energy sources.3−17 Some types of conductive polymers, such as polyaniline (PAn),6−10 poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS),11−14 and polypyrrole,15−17 have been examined as TE materials. Among them, PAn is the most popular because of its excellent stability toward oxidation as well as its electrical, optical, and thermoelectric properties.18 Recent studies indicate that the introduction of nanostructures in composite materials such as PAn/reduced graphene oxide,19 PAn/single-walled nanotube,20,21 and PAn/Bi2Te322,23 can improve TE properties via tuning the crystallinities and morphologies of such materials. Nevertheless, these additives © 2018 American Chemical Society

show diverse values for electrical conductivities and Seebeck coefficients. As a result, further investigations are urgently needed. Porous metal−organic frameworks (MOFs) have recently emerged as an important class of materials because of their advantageous functional properties and topologically diverse architectures.24−33 Their high porosity, ease of surface tunability, and rich coordination chemistry provide an ideal platform for use in a wide array of potential applications in gas storage, catalysis, drug delivery, and microelectronics.34−42 ZrMOFs comprise a unique class of MOFs that are structurally diverse and have excellent water stability.43,44 In particular, UiO-66, which is synthesized from the reaction of [Zr6O4(OH)4] clusters with 1,4-benzodicarboxylate (BDC), has an extremely large surface area and good potential in electronic applications.45,46 Here, we envisaged that a PAn thread-entangled UiO-66 composite blended with a dopant, such as poly(styrene sulfonate) (PSS), would result in the generation of a new type of TE material. The phase junction would allow phonon scattering, which would reduce thermal conductivity, whereas the dopant would enhance electrical conductivity. In addition, the Seebeck coefficient would be Received: October 4, 2018 Accepted: December 23, 2018 Published: December 24, 2018 3400

DOI: 10.1021/acsami.8b17308 ACS Appl. Mater. Interfaces 2019, 11, 3400−3406

Research Article

ACS Applied Materials & Interfaces Scheme 1. Schematic Diagram Showing the Formation of Zr-MOF/PAn Composites

spectrum of a powdered sample Zr-MOF with water (ZB-W) or aniline (ZB-A) absorbed is displayed in Figure S1. The characteristic peaks of the IR absorption for An are at 695 cm−1 (R−NH2 wagging), 1277 cm−1 (C−N stretching), and 1620 cm−1 (N−H scissoring).48 As it can be seen, the three characteristic peaks for An were all present in the IR spectrum of ZB-A but were not seen in that of ZB-W. In addition, the characteristic peak for N−H scissoring in ZB-A was shifted to a slightly higher frequency because of the interaction of PAn with 1,4-benzodicarboxylate of Zr-MOF (ZB). After merging the Zr-MOF with An, a ZB-A/PAn composite was prepared by the in situ polymerization of An. Pristine PAn, ZB-W and ZB-A/PAn display different morphologies, as shown in Figure 1a−c: PAn as flakes, ZB-W as crystal particles, and ZB-A/PAn as crystals linked with threads. As shown in Scheme 1, the key to creating a difference between pristine PAn and PAn in the composite was the “in situ polymerization of An with the Zr-MOF”, which led to the formation of a threadlike structure. During the in situ polymerization, PAn both on the surface and in the pores of the Zr-MOF would be pulled by interactive forces in the highspeed flow of a solution, thus causing the polymeric chain to become stretched. This would result in a change in the morphology of PAn. To verify that such a flow does, in fact, affect the morphology of the complex, we changed the rotational speed of the stirring bar from fast (900 rpm) to slow (300 rpm), which resulted in a clearly observed morphology change, as shown in Figure 1c−e. When the rotational speed was decreased, the PAn morphology changed from a threadlike to a platelike structure. A decrease in the rotational speed caused more PAn to be absorbed onto the surface of the ZrMOF during the in situ polymerization process. A higher stirring speed clearly leads to a PAn with a higher crystallinity, as indicated by the appearance of lattice fringes of PAn in the high-resolution transmission electron microscopy (HRTEM) image (Figures 1f and S3b). The d-spacing of the crystalline polyaniline is estimated to be about 0.36 nm, which is very close to a reported value (0.35 nm).49 The crystallinity is also confirmed by the powder X-ray diffraction (PXRD) characterization (vide infra, Figures S5 and S6). In addition, nitrogen adsorption−desorption studies showed that the N2 uptake for the pristine Zr-MOF, 10-ZB-W/PAn, and 10-ZB-A/PAn follows the following trend: Zr-MOF ≫ 10-ZB-W/PAn > 10-ZB-A/PAn (Figure S2). The pore sizes of 10-ZB-A/PAn and 10-ZB-W/PAn are essentially negligible compared to that of the pristine Zr-MOF. These results support the conclusion that the polyaniline chains are successfully interpenetrated into the Zr-MOFs. The powder X-ray diffraction patterns of the ZB-A and ZBW that are shown in Figure S5 are similar. This suggests that

expected to be significantly improved because of an ionic Soret effect (thermodiffusion) caused by the interaction of each individual component.47 These three factors, in turn, would promote TE performance. To prove this concept, a threadlike interpenetrated network was prepared by inserting aniline into a porous Zr-MOF followed by in situ oxidative polymerization (Scheme 1). The final system contained two different structures that were held together to form a threadlike interpenetrating network (IPN) structure, typically referred to as a semi-interpenetrating network (semi-IPN). A free-standing film of a PSS-blended thread-interpenetrating Zr-MOF/PAn/PSS composite was also prepared (Scheme 2). Significantly, this thread-interpenetratScheme 2. Schematic Diagram Showing the Composition of the Thermoelectric Free-Standing Thin Films

ing composite film showed exceptional TE characteristics, with a large, negative Seebeck coefficient. More importantly, N-type TE materials are still rare and of fundamental importance because a combination of P-type and N-type TE materials is essential for improving the performance of thermoelectric devices.

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RESULTS AND DISCUSSION To produce PAn with the Zr-MOFs, aniline (An) was absorbed onto the MOFs by exchanging water for An. We used Fourier transform infrared spectroscopy to verify that An was successfully merged with the Zr-MOF. An IR absorption 3401

DOI: 10.1021/acsami.8b17308 ACS Appl. Mater. Interfaces 2019, 11, 3400−3406

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ACS Applied Materials & Interfaces

Figure 1. Scanning electron microscopy (SEM) images of (a) PAn; (b) ZB-W; and 10-ZB-A/PAn synthesized using (c) fast, (d) medium, and (e) slow stirring speeds. (f) HRTEM image of the crystalline PAn of 10-ZB-A/PAn synthesized using a fast stirring speed.

Table 1. Thermoelectric Properties of the PAn/PSS Films samples PAn/PSS1a 10-ZB-W/PAn/PSS1a 10-ZB-A/PAn/PSS1a 10-ZB-A/PAn/PSS2b 20-ZB-A/PAn/PSS2b

α∥, μV/K 2325 −2645 −6483 −6257 −17 780

σ∥, S/m −2

2.17 × 10 4.99 × 10−1 2.90 1.67 2.10

power factor, μW/(m K2)

κ⊥, W/(m K)

0.12 3.49 122 65.4 664

0.24 0.39 0.42 0.43 0.46

The molecular weight of PSS1 is 75 000 g/mol of the film. bThe molecular weight of PSS2 is 1 000 000 g/mol of the film.

a

MOF.52 These results show that the Zr-MOF is an important component in the composite for the crystallinity of PAn. The Seebeck coefficient and electrical/thermal conductivity were investigated to determine the thermoelectric behavior of the Zr-MOF/PAn/PSS composite films. The findings indicated that our composite material exhibits a large, unprecedented negative Seebeck coefficient of −17 780 μV/ K when 20 wt % Zr-MOF was used (Table 1). It was recently reported that a composite of a Zr-MOF with P-type polyaniline adopts N-type characteristics.53 In our case, a similar interaction between Zr-MOF and PAn/PSS was also observed, where the two characteristic bands of PAn/PSS2 (400 nm for π to π* excitation and 800 nm for polaron absorption)54,55 are red-shifted (from 400 to 415 nm and from 800 to 830 nm) in the UV−vis absorption spectrum of 20-ZB-A/PAn/PSS2 (Figure S12). This indicates that the band gap is decreased because of interactions of electron clouds of the zirconium (from the Zr-MOF) and nitrogen atoms (from PAn).56,57 Furthermore, the carrier concentration and mobility of the composite films are increased with increasing Zr-MOF content (Table 2). Electron transfer becomes easier in the composite

An and water have no effect on the structure of the MOF. The amorphous pristine PAn displays a broad X-ray pattern, with no characteristic peaks, whereas both the ZB-A/PAn and ZBW/PAn show the characteristic peaks 2θ = 17.4, 25.0, 25.3, and 27.9°. The 17.4, 25.0, and 27.9° peaks arise from the ligand (BDC). The main diffraction peaks for both 5-ZB-A/ PAn and 5-ZB-W/PAn are not clearly seen in the patterns; instead, only the ligand peaks are seen. This suggests that the Zr-MOF had slightly decomposed, presumably because of the low MOF loading. The 25.3° peak is assigned to the repeating unit of PAn with a periodic polymer backbone.49,50 It is important to note that the PXRD peak of PAn backbone is sharper after the incorporation of the Zr-MOF, indicating that the crystallinity of PAn was significantly enhanced when An was in situ polymerized with the Zr-MOF, in particular, under conditions of a high stirring speed (see Figure S6). A previous study reported in the literature also supports our observation that stretching PAn enhances its crystallinity.51 In addition, the powder XRD patterns of Zr-MOF/PAn/PSS films are similar to those of the Zr-MOF/PAn (Figure S7). The characteristic peak at 25.3° became sharper after synthesis with the Zr3402

DOI: 10.1021/acsami.8b17308 ACS Appl. Mater. Interfaces 2019, 11, 3400−3406

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ACS Applied Materials & Interfaces Table 2. Hall Carrier Concentration and Mobility of Filmsa samples

n, cm−3

PAn/PSS1 5-ZB-A/PAn/PSS1 10-ZB-A/PAn/PSS1

2.87 × 10 3.50 × 1014 4.42 × 1015

μ, cm2/(V s)

type

4.39 4.89 5.03

P-type N-type N-type

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be attributed to the improved crystallinity of PAn. A correlation between the crystallinity of PAn and electrical conductivity was also reported in a previous study.51 Furthermore, it is known that the enhanced electrical conductivity also arises partially from the increasing carrier concentration and mobility.62−65 Our experimental results show that the carrier concentration and mobility clearly increase with an increase in the degree of Zr-MOF loading and hence the electrical conductivity of the composite films is significantly increased (see Tables 1 and 2). A composite with an enhanced electrical conductivity and a high Seebeck coefficient would be predicted to have a positive impact on its power factor as well as on its thermoelectric behavior. When 10 wt % ZB-A was used, a power factor of 122 μW/(m K2) was found, which is significantly higher than that for a pure PAn/PSS1 film, which has a power factor of 0.12 μW/(m K2). PSS with a molecular weight of 75 000 g/mol can support free-standing films for composites with MOF concentrations up to 10 wt %. At levels higher than this, the films become brittle. The morphology of the Zr-MOF/PAn/ PSS films shows thread-interpenetrating characteristics, and the surface roughness increases with increasing Zr-MOF content (Figure S4). To obtain better results, we used a longer-chain PSS (PSS2; molecular weight 106 g/mol), which improved the integrity of the membrane. Using PSS2, the highest power factor was 664 μW/(m K2) for a film that contained 20 wt % ZB-A (20-ZB-A/PAn/PSS2 film), as shown in Table 1. To further illustrate the efficiency of this type of semi-IPN composite for use as a thermoelectric material, we investigated its thermal conductivity but only in perpendicular orientation (because of technical limitations associated with the measurements). The results were in the range of 0.24−0.42 W/(m K) depending on the amount of Zr-MOF that had been loaded in the ZB-A/PAn/PSS film (Figure 2). The increase in thermal conductivity is related to the increased electrical conductivity of the composites. Nevertheless, the slope of a plot for thermal conductivity decreased significantly with increasing particle content in the film. As a consequence, the in situ polymerization strategy using Zr-MOFs described herein offers a rare opportunity for substantially increasing the extent of interfacial and phonon scattering on the interface, which would, in turn, suppress the rate of increase in thermal conductivity. Our strategy that involves integrating polymers with ZrMOF results in the formation of new types of composite thermoelectric semi-IPN films with exceptionally high Seebeck coefficients and enhanced electrical conductivities and power factors. In addition, this design also suppresses the rate of increase in thermal conductivity. More importantly, novel composite films that are produced using combinations of PAn/ PSS and a Zr-MOF are of low cost, are light in weight, are easy to synthesize, have better thermoelectric properties, and are composed of free-standing substrates. Such structures represent an ideal choice for applications of various MOF/ polymer composites for use in thermoelectric applications.

n: carrier concentration; μ: carrier mobility.

a

film. As a consequence, the Zr-MOF/PAn/PSS composite films exhibit N-type characteristics, resulting in negative Seebeck coefficients, as shown in Table 1. According to the previous literature,58 Seebeck coefficients increase with increasing carrier mobility. In addition, a strong ionic Soret effect (thermodiffusion) from the polyelectrolyte of PAn/PSS also results in a large Seebeck coefficient.59,60 During the development of a temperature gradient, the Zr-MOFs provide electrons to PAn/PSS by thermal excitation.61 After immobilization of Zr-MOF as an electron donor to PAn/PSS, the ZrMOF builds up a high positive charge at the hot side. PAn/PSS acts as an electron storage area at the cold end, resulting in the formation of a high concentration gradient of negative carriers, which finally result in large, negative Seebeck coefficients (Scheme 3). Scheme 3. Carrier Thermodiffusion in the Composite

The electrical conductivity of the composite films increased significantly with increasing amount of Zr-MOF that was loaded into the PAn/PSS1 film (Table 1 and Figures 2 and S8). The conformation of PAn in the composite films is extended with a slightly coiled arrangement with good crystallinity (Figure 1c,f). This excellent electrical conductivity can mainly

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CONCLUSIONS The strategy outlined in this study, which involves in situ polymerization in the presence of Zr-MOFs, results in the formation of new types of thermoelectric films (Zr-MOF/ PAn/PSS) that exhibit excellent thermoelectric behavior. These thermoelectric composite films exhibit extraordinarily high negative Seebeck coefficients, which can be optimized

Figure 2. Plot of thermoelectric properties (the absolute value of the Seebeck coefficient (|α|), thermal conductivity (κ), electrical conductivity (σ), and power factor value) depending on the loading of Zr-MOF in the ZB-A/PAn/PSS1 film. 3403

DOI: 10.1021/acsami.8b17308 ACS Appl. Mater. Interfaces 2019, 11, 3400−3406

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ACS Applied Materials & Interfaces using 20 wt % Zr-MOF in the preparation. In addition, the electrical conductivities and power factors of the materials are also enhanced significantly compared to those of PAn/PSS films and the increment in thermal conductivity is suppressed. This work offers a new opportunity for taking advantage of the features of highly crystalline porous structures, particularly metal−organic frameworks along with conductive polymers, in developing novel thermoelectric materials.

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EXPERIMENTAL SECTION

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Preparation of Zr-MOFs. Zr-MOFs were synthesized by the method reported in the literature.45,66 A mixture of ZrCl4 (1.25 g), BDC (1.23 g), dimethylformamide (150 mL), and HCl (12 M; 10 mL) was refluxed and stirred at 100 °C for 24 h. Zr-MOF powders were collected by filtering and drying. To remove the unreacted ligand, the Zr-MOFs were refluxed overnight in EtOH at 80 °C, resulting in the isolation of the active Zr-MOFs. For further use, ZrMOF powders were vacuum-dried in vials at 80 °C for 2 h. The ZrMOFs were embedded with different liquids, water and aniline, respectively, for further study. After injecting the liquid into the vial, followed by filtering and washing with ethanol to remove the residual solvent, the sample was dried in an oven at 80 °C for 30 min. Then, liquid-embedded Zr-MOFs were obtained. The samples were named ZB-W and ZB-A, in which W indicates water and A indicates aniline in the Zr-MOF. Preparation of Zr-MOF/PAn Composites. Zr-MOFs/PAn were prepared by first charging vacuum-dried Zr-MOFs into an appropriate proportion of An (ZB-A) and then adding an HCl (1 M; 9 mL) solution followed by stirring on an ice bath. The resulting solution was followed by slowly adding an ammonium persulfate (APS) solution, which was prepared in HCl (1 M; 9 mL). The molar ratio of APS to An was 1.6:1. The reaction mixture was left to stir for 12 h after the final drop and then filtered, washed, and dried overnight at 50 °C.67 The powder was denoted ZB-A/PAn. ZB-W/PAn was prepared by a procedure similar to that mentioned above except that the order of addition of An to HCl was reversed. Preparation of PSS2 Solution from PSSNa (MW = 1 000 000 g/mol). PSSNa (18 g) was dissolved in deionized (DI) water (82 mL) and then stirred with an ion-exchange resin (72 g) for 24 h. After ion exchanging from Na+ to H+ and removing the ion-exchange resin by filtering, an 18 wt % PSSH solution was obtained. Preparation of Zr-MOFs/PAn/PSS Films. Zr-MOFs/PAn/PSS solutions were prepared by charging vacuum-dried Zr-MOFs (74 mg) into An (0.097 mL) and then stirring the solution with DI water (5.5 mL) to give a homogeneous dispersion. An 18 wt % PSS (1.1 mL) solution was then added to the system with the weight ratio of PSS to An equal to 2:1, followed by slowly adding an APS solution dropwise for polymerization in an ice bath. After reacting the sample for 12 h, the color of the Zr-MOFs/PAn/PSS solution changed from yellow to green. Finally, the composite films with thicknesses of about 20−40 μm were produced by dropping the solution on glass slides and drying at room temperature.

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PSS1, 10-ZB-A/PAn/PSS2, and 20-ZB-A/PAn/PSS2; Figure S8, electrical conductivities of ZB-W/PAn/ PSS1, ZB-A/PAn/PSS2, and ZB-A/PAn/PSS1; Figure S9, IR spectra of 0-ZB-A/PAn/PSS2 and 20-ZB-A/PAn/ PSS2; Figure S10, UV−vis absorption spectra; Figure S11, Mott−Schottky plots of Zr-MOF; Figure S12, UV− vis absorption spectra of 0-ZB-A/PAn/PSS2 and 20-ZBA/PAn/PSS2; Scheme 1, mechanism of the polyaniline redox reaction (PDF)

AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (C.-H.C.). *E-mail: [email protected] (K.-L.L.). ORCID

Muhammad Usman: 0000-0003-4518-8281 Kuang-Lieh Lu: 0000-0002-5529-7126 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We appreciate Academia Sinica and the Ministry of Science and Technology (MOST), Taiwan for financial supports (grants MOST 103-2221-E-009-216, MOST 106-2113-M-001032, and MOST 104-2221-E-009-180).

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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/acsami.8b17308. Figure S1, IR spectra of aniline, ZB-A, and ZB-W; Figure S2, nitrogen adsorption−desorption isotherms and pore size distribution; Figure S3, HRTEM image of pristine PAn and crystalline PAn; Figure S4, SEM images of 0ZB-A/PAn/PSS1, 10-ZB-A/PAn/PSS1, 10-ZB-A/PAn/ PSS 2 , and 20-ZB-A/PAn/PSS 2 films; Figure S5, comparison of PXRD patterns; Figure S6, PXRD patterns of a 10 wt % ZB-A composite; Figure S7, PXRD patterns of 0-ZB-A/PAn/PSS1, 10-ZB-A/PAn/ 3404

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