Metal-organic frameworks (MOFs) have been widely investigated for their porosity and functional diversity. Inspired by the flexible designability of MOFs, UiO-66-NH2/CNT with moniliform nanostructure was designed and synthesized successfully. SPEN@UiO-66-NH2/CNT composite proton exchange membranes were prepared by loaded UiO-66-NH2/CNT into sulfonated polyarylene ether nitrile (SPEN). Due to the addition of UiO-66-NH2/CNT, all the properties of composite proton exchange membranes were improved. The composite membranes exhibit excellent thermal stability and dimensional stability. The tensile strength of the composite membranes was improved about twofold compared to that of recast SPEN membrane, which was contributed by the interlaced property and rigid structure of UiO-66-NH2/CNT. Especially, the proton conductivity of the composite membranes was greatly facilitated by the additional proton acceptors and donors provided by the abundant amino groups and carboxyl groups in UiO-66-NH2/CNT. Furthermore, the methanol permeability of SPEN@UiO-66-NH2/CNT reduced consistently (from 6.13 to 0.96 × 10−7 cm2 s−1), which was much lower than that of Nafion membrane (21.36 × 10−7 cm2 s−1). All the results suggest that the design of multifunctional nanofillers based on the skeleton structure of MOFs could provide a new strategy to enhance the performance of PEMs.
ZhaoYLiXWangS, et al.Proton exchange membranes prepared via atom transfer radical polymerization for proton exchange membrane fuel cell: Recent advances and perspectives. Int J Hydrog Energy2017; 42: 30013–30028.
2.
MorenoNGMolinaMCGervasioD, et al.Approaches to polymer electrolyte membrane fuel cells (PEMFCs) and their cost. Renewable Sustainable Energy Rev2015; 52: 897–906.
3.
DekelDR. Review of cell performance in anion exchange membrane fuel cells. J Power Sources2018; 375: 158–169.
4.
WangHZhuangXTongJ, et al.Solution-blown SPEEK/POSS nanofiber-nafion hybrid composite membranes for direct methanol fuel cells. J Appl Polym Sci2015; 132: 42843.
5.
RessamIEl KadibALahciniM, et al.Enhanced proton transport properties of Nafion via functionalized halloysite nanotubes. Int J Hydrog Energy2018; 43: 18578–18591.
6.
KimARVinothkannanMLeeKH, et al.Ameliorated performance of sulfonated poly(arylene ether sulfone) block copolymers with increased hydrophilic oligomer ratio in proton-exchange membrane fuel cells operating at 80% relative humidity. Polymers (Basel)2020; 12: 1871.
7.
JunohHJaafarJNordinN, et al.Performance of polymer electrolyte membrane for direct methanol fuel cell application: perspective on morphological structure. Membranes2020; 10: 34.
BoseABGopuSLiW. Enhancement of proton exchange membrane fuel cells performance at elevated temperatures and lower humidities by incorporating immobilized phosphotungstic acid in electrodes. J Power Sources2014; 263: 217–222.
10.
HuangYChengTZhangX, et al.Novel composite proton exchange membrane with long-range proton transfer channels constructed by synergistic effect between acid and base functionalized graphene oxide. Polymer2018; 149: 305–315.
11.
ChengTZhangXMaY, et al.Constructing continuous proton-conducting highways within sulfonated poly(arylene ether nitrile) composite membrane by incorporating amino-sulfo-bifunctionalized go. Polymers (Basel)2018; 10: 1005.
12.
ChengTFengMHuangY, et al.SGO/SPEN-based highly selective polymer electrolyte membranes for direct methanol fuel cells. Ionics2017; 23: 2143–2152.
13.
LiHEddaoudiMO’KeeffeM, et al.Design and synthesis of an exceptionally stable and highly porous metal-organic framework. Nature1999; 402: 276–279.
14.
DongX-YLiJ-JHanZ, et al.Tuning the functional substituent group and guest of metal–organic frameworks in hybrid membranes for improved interface compatibility and proton conduction. J Mater Chem A2017; 5: 3464–3474.
15.
VegaJAndrioALemusAA, et al.Conductivity study of zeolitic imidazolate frameworks, tetrabutylammonium hydroxide doped with zeolitic imidazolate frameworks, and mixed matrix membranes of polyetherimide/tetrabutylammonium hydroxide doped with Zeolitic Imidazolate Frameworks for proton conducting applications. Electrochim Acta2017; 258: 153–166.
16.
ShiGMYangTChungTS. Polybenzimidazole (PBI)/zeolitic imidazolate frameworks (ZIF-8) mixed matrix membranes for pervaporation dehydration of alcohols. J Membr Sci2012; 415–416: 577–586.
17.
EscorihuelaJSahuquilloOGarcia-BernabeA, et al.Phosphoric acid doped polybenzimidazole (PBI)/zeolitic imidazolate framework composite membranes with significantly enhanced proton conductivity under low humidity conditions. Nanomaterials2018; 8: 775.
18.
KandiahMNilsenMHUsseglioS, et al.Synthesis and stability of tagged UiO-66 Zr-MOFs. Chem Mater2010; 22: 6632–6640.
19.
ChavanSVitilloJGGianolioD, et al.H2 storage in isostructural UiO-67 and UiO-66 MOFs. Phys Chem Chem Phys2012; 14: 1614–1626.
20.
YangXBZhaoLGohK, et al.Ultra-high ion selectivity of a modified nafion composite membrane for vanadium redox flow battery by incorporation of phosphotungstic acid coupled UiO-66-NH2. ChemistrySelect2019; 4: 4633–4641.
21.
MukhopadhyaySDebguptaJSinghC, et al.Designing UiO-66-based superprotonic conductor with the highest metal-organic framework based proton conductivity. ACS Appl Mater Interfaces2019; 11: 13423–13432.
22.
DonnadioANarducciRCasciolaM, et al.Mixed membrane matrices based on nafion/UiO-66/SO3H-UiO-66 Nano-MOFs: revealing the effect of crystal size, sulfonation, and filler loading on the mechanical and conductivity properties. ACS Appl Mater Interfaces2017; 9: 42239–42246.
23.
PhangWJJoHLeeWR, et al.Superprotonic conductivity of a UiO-66 framework functionalized with sulfonic acid groups by facile postsynthetic oxidation. Angew Chem2015; 54: 5142–5146.
24.
RaoZTangBWuP. Proton conductivity of proton exchange membrane synergistically promoted by different functionalized metal-organic frameworks. ACS Appl Mater Interfaces2017; 9: 22597–22603.
25.
MukherjeeSBatesALeeSC, et al.A review of the application of CNTs in PEM fuel cells. Int J Green Energy2015; 12: 787–809.
26.
LiaoSHYenCYHungCH, et al.One-step functionalization of carbon nanotubes by free-radical modification for the preparation of nanocomposite bipolar plates in polymer electrolyte membrane fuel cells. J Mater Chem A2008; 18: 3993–4002.
27.
KimARVinothkannanMSongMH, et al.Amine functionalized carbon nanotube (ACNT) filled in sulfonated poly(ether ether ketone) membrane: effects of ACNT in improving polymer electrolyte fuel cell performance under reduced relative humidity. Compos Part B-Eng2020; 188: 107890.
28.
LinRGeLLiuS, et al.Mixed-matrix membranes with metal-organic framework-decorated CNT fillers for efficient CO2 separation. ACS Appl Mater Interfaces2015; 7: 14750–14757.
29.
SinghIVTanakaMZhangJ, et al.Evaluation of effective thermal conductivity of CNT-based nano-composites by element free Galerkin method. Int J Numer Methods Heat Fluid Flow2007; 17: 757–769.
30.
OdomTWHuangJLKimP, et al.Structure and electronic properties of carbon nanotubes. J Carbon Nanotub2000; 104: 2794–2809.
31.
KimARGabunadaJCYooDJ. Amelioration in physicochemical properties and single cell performance of sulfonated poly(ether ether ketone) block copolymer composite membrane using sulfonated carbon nanotubes for intermediate humidity fuel cells. Int J Energy Res2019; 43: 2974–2989.
32.
VinothkannanMHariprasadRRamakrishnanS, et al.Potential bifunctional filler (CeO2–ACNTs) for nafion matrix toward extended electrochemical power density and durability in proton-exchange membrane fuel cells operating at reduced relative humidity. ACS Sustain Chem Eng2019; 7: 12847–12857.
33.
GahlotSKulshresthaV. Dramatic improvement in water retention and proton conductivity in electrically aligned functionalized CNT/SPEEK nanohybrid PEM. ACS Appl Mater Interfaces2015; 7: 264–272.
34.
ZhangCTianJRaoW, et al.Polypyrrole@metal-organic framework (UIO-66)@cotton fabric electrodes for flexible supercapacitors. Cellulose2019; 26: 3387–3399.
35.
PuYWuWLiuJ, et al.A defective MOF architecture threaded by interlaced carbon nanotubes for high-cycling lithium–sulfur batteries. RSC Adv2018; 8: 18604–18612.
36.
LuuCLNguyenTTVNguyenT, et al.Synthesis, characterization and adsorption ability of UiO-66-NH2. Adv Natural Sci2015; 6: 025004.
37.
LinSGanNCaoY, et al.Selective dispersive solid phase extraction-chromatography tandem mass spectrometry based on aptamer-functionalized UiO-66-NH2 for determination of polychlorinated biphenyls. J Chromatogr A2016; 1446: 34–40.
38.
AbidHRShangJAngH-M, et al.Amino-functionalized Zr-MOF nanoparticles for adsorption of CO2 and CH4. Int J Smart Nano Mater2013; 4: 72–82.
39.
ZhaoZYangZHuY, et al.Multiple functionalization of multi-walled carbon nanotubes with carboxyl and amino groups. Appl Surf Sci2013; 276: 476–481.
40.
KoYGLeeHJParkYS, et al.The mixing effect of amine and carboxyl groups on electrorheological properties and its analysis by in situ FT-IR under an electric field. Phys Chem Chem Phys2013; 15: 16527–16532.
41.
CaiYYYangQZhuZY, et al.Achieving efficient proton conduction in a MOF-based proton exchange membrane through an encapsulation strategy. J Membr Sci2019; 590: 117277.
WangNHuLBabuHV, et al.Effect of tea saponin-based intumescent flame retardant on thermal stability, mechanical property and flame retardancy of natural rubber composites. J Therm Anal Calorim2016; 128: 1133–1142.
44.
SturtevantJLTakebeYEdaM, et al.A new monocyclic fluoropolymer structure for 157-nm photoresists. Proc SPIE2004; 5376: 151–158.
45.
FengMHuangYWeiM, et al.Sulfonated poly(arylene ether nitrile)-based hybrid membranes containing amine-functionalized GO for constructing long-range ionic nanochannels. Int J Hydrog Energy2018; 43: 11214–11222.
46.
GuoYJiangZYingW, et al.A DNA-threaded ZIF-8 membrane with high proton conductivity and low methanol permeability. Adv Mater2018; 30: 1705155.
47.
JingFSunRWangS, et al.Effect of the anode structure on the stability of a direct methanol fuel cell. Energy Fuel2020; 34: 3850–3857.
48.
JiaNLefebvreMCHalfyardJ, et al.Modification of nafion proton exchange membranes to reduce methanol crossover in PEM fuel cells. Electrochem Solid-State Lett2000; 3: 529–531.
49.
SunHTangBWuP. Rational design of S-UiO-66@GO hybrid nanosheets for proton exchange membranes with significantly enhanced transport performance. ACS Appl Mater Interfaces2017; 9: 26077–26087.
