UiO-67 Based Conductive Composites: Preparation and Thermoelectric Performance

doi:10.15541/jim20230197

Abstract

Abstract:

Thermoelectric materials are functional materials that can realize the direct conversion between heat and electricity, which have great prospects in the field of green refrigeration and waste heat recovery. To date, researches on thermoelectric materials mainly focus on semiconducting inorganic materials and conductive polymers. Although great progress has been made regarding material design and performance improvement, it is still of great significance to explore and expand thermoelectric candidates for potential application. Metal-organic frameworks (MOFs) are porous extended solids formed by coordination bonds between organic ligands and metal ions or metal clusters. They are promising candidates in the field of thermoelectrics due to their unique porous structure as well as tunable composition and structure, which could meet the requirement of "electron crystal-phonon glass". In this work, conductive polymer, poly(3, 4-vinyl dioxythiophene) (PEDOT) was in-situ polymerized in Zr-based MOFs UiO-67 through “conductive guest-promoted transport” approach. The confined effects originated from porous structures of MOFs on molecular chains of PEDOT effectively improve electrical conductivity of the composites. As a result, the prepared composites exhibit an electrical conductivity up to 5.96×10⁻³ S·cm⁻¹ at room temperature, which is one order of magnitude higher than the corresponding PEDOT. Correspondingly, their power factor (PF) is up to 3.67×10⁻² nW·m⁻¹·K⁻² at room temperature. In conclusion, this work uses ordered porous structures of MOFs as reaction platform and constructs conductive polymer/MOFs conductive materials by facile in-situ polymerization methods, providing a reference for further development of MOFs-based thermoelectric materials.

Key words: metal-organic framework, poly(3,4-ethyldioxythiophene), electrical conductivity, thermoelectric property

CLC Number:

TQ174

JIANG Runlu, WU Xin, GUO Haocheng, ZHENG Qi, WANG Lianjun, JIANG Wan. UiO-67 Based Conductive Composites: Preparation and Thermoelectric Performance[J]. Journal of Inorganic Materials, 2023, 38(11): 1338-1344.

Figures/Tables 9

Fig. 1 XRD patterns of UiO-67 and PEDOT/UiO-67

Fig. 2 UV-Vis spectra of UiO-67 and PEDOT/UiO-67 Colorful figures are available on website

Fig. 3 Raman spectra of (a) PEDOT, and (b) UiO-67, EDOT/UiO-67 and PEDOT/UiO-67(126 μL)

Fig. 4 SEM images of (a, b) PEDOT/UiO-67(63 μL), (c, d) PEDOT/UiO-67(94.5 μL), (e, f) PEDOT/UiO-67(126 μL) and (g, h) UiO-67

Fig. 5 (a, b) SEM images, and (c-f) C, O, S, Zr EDS elemental mappings of PEDOT/UiO-67(126 μL)

Fig. 6 Nitrogen adsorption-desorption isotherms of (a) UiO-67 and (b) PEDOT/UiO-67

Fig. 7 Thermoelectric properties of PEDOT and PEDOT/UiO-67 with various PEDOT contents (a) Electrical conductivity and Seebeck coefficient; (b) Power factor. Colorful figures are available on website

Table 1 Electrical conductivities of reported MOFs-conductive polymer pellets with PEDOT/ UiO-67

MOF composite	Conductivity/ (S·cm^-1)	Method	Ref.
MIL-101-PEDOT	1.1×10^-3	EIS^a	[13]
La(BTC)-PEDOT	2.3×10^-8	EIS^a	[13]
UiO-66-PEDOT	~1×10^-3	4-Probe	[21]
MIL-101-PANI	10^-6	-	[26]
NU-1000-polythiophene	1.3×10^-7	EIS	[27]
UiO-66-PPy	~2×10^-2	4-Probe	[21]
Cd₂(NDC)(PCA)₂-PPy	0.2	Hall bar	[28]
Cd₂(NDC)(PCA)₂-PPy	1×10^-3	4-Probe	[28]
PEDOT/UiO-67	3.0×10^-3	4-Probe	This work

Fig.8 Temperature-dependent thermoelectric properties of PEDOT and PEDOT /UiO-67 (a) Seebeck coefficient; (b) Electrical conductivity; (c) Power factor

References 28

[1]	TRITT T M, SUBRAMANIAN M A. Thermoelectric materials, phenomena, and applications: a bird's eye view. MRS Bulletin, 2006, 31(3): 188. DOI URL
[2]	SNYDER G J, TOBERER E S. Complex thermoelectric materials. Nature Materials, 2008, 7(2): 105. DOI PMID
[3]	SINGH S, LEE S, KANG H, et al. Thermoelectric power waves from stored chemical energy. Energy Storage Materials, 2016, 3: 55. DOI URL
[4]	TU S, TIAN T, OECHSLE A L, et al. Improvement of the thermoelectric properties of PEDOT:PSS films via DMSO addition and DMSO/salt post-treatment resolved from a fundamental view. Chemical Engineering Journal, 2022, 429: 132295. DOI URL
[5]	LIU X, SHI X L, ZHANG L, et al. One-step post-treatment boosts thermoelectric properties of PEDOT:PSS flexible thin films. Journal of Materials Science & Technology, 2023, 132: 81.
[6]	LI F, WANG H, HUANG R, et al. Recent advances in SnSe nanostructures beyond thermoelectricity. Advanced Functional Materials, 2022, 32(26): 2200516. DOI URL
[7]	ZHOU C, LEE Y K, YU Y, et al. Polycrystalline SnSe with a thermoelectric figure of merit greater than the single crystal. Nature Materials, 2021, 20(10): 1378. DOI PMID
[8]	LI W H, DENG W H, WANG G E, et al. Conductive MOFs. EnergyChem, 2020, 2(2): 100029. DOI URL
[9]	GOETJEN T A, LIU J, WU Y, et al. Metal-organic framework (MOF) materials as polymerization catalysts: a review and recent advances. Chemical Communications, 2020, 56(72): 10409. DOI PMID
[10]	JARAMILLO D E, JIANG H, EVANS H A, et al. Ambient- temperature hydrogen storage via vanadium(II)-dihydrogen complexation in a metal-organic framework. Journal of the American Chemical Society, 2021, 143(16): 6248. DOI URL
[11]	LI P, SHEN Y, WANG D, et al. Selective adsorption-based separation of flue gas and natural gas in zirconium metal-organic frameworks nanocrystals. Molecules, 2019, 24(9): 1822. DOI URL
[12]	LEE H, VASHAEE D, WANG D Z, et al. Effects of nanoscale porosity on thermoelectric properties of SiGe. Journal of Applied Physics, 2010, 107(9): 094308. DOI URL
[13]	LE OUAY B, BOUDOT M, KITAO T, et al. Nanostructuration of PEDOT in porous coordination polymers for tunable porosity and conductivity. Journal of the American Chemical Society, 2016, 138(32): 10088. DOI PMID
[14]	MINNICH A J, DRESSELHAUS M S, REN Z F, et al. Bulk nanostructured thermoelectric materials: current research and future prospects. Energy & Environmental Science, 2009, 2(5): 466.
[15]	XIE L S, SKORUPSKII G, DINCĂ M. Electrically conductive metal-organic frameworks. Chemical Reviews, 2020, 120(16): 8536. DOI PMID
[16]	SUN L, LIAO B, SHEBERLA D, et al. A microporous and naturally nanostructured thermoelectric metal-organic framework with ultralow thermal conductivity. Joule, 2017, 1(1): 168. DOI URL
[17]	CHEN Z, CUI Y, JIN Y, et al. Nanorods of a novel highly conductive 2D metal-organic framework based on perthiolated coronene for thermoelectric conversion. Journal of Materials Chemistry C, 2020, 8(24): 8199. DOI URL
[18]	ERICKSON K J, LEONARD F, STAVILA V, et al. Thin film thermoelectric metal-organic framework with high Seebeck coefficient and low thermal conductivity. Advanced Materials, 2015, 27(22): 3453. DOI URL
[19]	DE LOURDES GONZALEZ-JUAREZ M, FLORE E, MARTIN-GONZALE M, et al. Electrochemical deposition and thermoelectric characterisation of a semiconducting 2-D metal-organic framework thin film. Journal of Materials Chemistry A, 2020, 8(26): 13197. DOI URL
[20]	GUTOV O V, HEVIA M G, ESCUDERO-ADAN E C, et al. Metal-organic framework (MOF) defects under control: insights into the missing linker sites and their implication in the reactivity of zirconium-based frameworks. Inorganic chemistry, 2015, 54(17): 8396. DOI PMID
[21]	JADHAV A, GUPTA K, NINAWE P, et al. Imparting multifunctionality by utilizing biporosity in a zirconium-based metal-organic framework. Angewandte Chemie International Edition, 2020, 59(6): 2215. DOI URL
[22]	PATIL A O, HEEGER A J, WUDL F. Optical properties of conducting polymers. Chemical Reviews, 1988, 88(1): 183. DOI URL
[23]	HU Z, DING Y, HU X, et al. Recent progress in 2D group IV-IV monochalcogenides: synthesis, properties and applications. Nanotechnology, 2019, 30(25): 252001. DOI URL
[24]	LINDFORS T, BOEVA Z A, LATONEN R M. Electrochemical synthesis of poly (3, 4-ethylenedioxythiophene) in aqueous dispersion of high porosity reduced graphene oxide. RSC advances, 2014, 4(48): 25279. DOI URL
[25]	BUTOVA V, BUDNYK A P, CHARYKOV K M, et al. Partial and complete substitution of the 1,4-benzenedicarboxylate linker in UiO-66 with 1,4-naphthalenedicarboxylate: synthesis, characterization, and H₂-adsorption properties. Inorganic Chemistry, 2019, 58(2): 1607. DOI URL
[26]	ALIEV S B, SAMSONENKO D G, MAKSIMOVSKIY E A, et al. Polyaniline-intercalated MIL-101: selective CO₂ sorption and supercapacitor properties. New Journal of Chemistry, 2016, 40(6): 5306. DOI URL
[27]	WANG T C, HOD I, AUDU C O, et al. Rendering high surface area, mesoporous metal-organic frameworks electronically conductive. ACS Applied Materials & Interfaces, 2017, 9(14): 12584.
[28]	DHARE B, NAGARKAR S, KUMAR J, et al. Increase in electrical conductivity of MOF to billion-fold upon filling the nanochannels with conducting polymer. The Journal of Physical Chemistry Letters, 2016, 7(15): 2945. DOI URL