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Frontiers of Materials Science

Front. Mater. Sci.    2018, Vol. 12 Issue (2) : 105-117
A general synthesis strategy for the multifunctional 3D polypyrrole foam of thin 2D nanosheets
Jiangli XUE1, Maosong MO1,2(), Zhuming LIU1, Dapeng YE2(), Zhihua CHENG3, Tong XU3, Liangti QU3
1. Institute of Electrical Engineering, Chinese Academy of Sciences, Beijing 100190, China
2. College of Mechanical and Electronic Engineering, Fujian Agriculture and Forestry University, Fuzhou 350002, China
3. Beijing Key Laboratory of Photoelectronic/Electrophotonic Conversion Materials, Key Laboratory of Cluster Science (Ministry of Education), Beijing Institute of Technology, Beijing 100081, China
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A 3D macroporous conductive polymer foam of thin 2D polypyrrole (PPy) nanosheets is developed by adopting a novel intercalation of guest (monomer Py) between the layers of the lamellar host (3D vanadium oxide foam) template-replication strategy. The 3D PPy foam of thin 2D nanosheets exhibits diverse functions including reversible compressibility, shape memory, absorption/adsorption and mechanically deformable supercapacitor characteristics. The as-prepared 3D PPy foam of thin nanosheets is highly light weight with a density of 12 mg·cm−3 which can bear the large compressive strain up to 80% whether in wet or dry states; and can absorb organic solutions or extract dye molecules fast and efficiently. In particular, the PPy nanosheet-based foam as a mechanically deformable electrode material for supercapacitors exhibits high specific capacitance of 70 F·g−1 at a fast charge–discharge rate of 50 mA·g−1, superior to that of any other typical pure PPy-based capacitor. We envision that the strategy presented here should be applicable to fabrication of a wide variety of organic polymer foams and hydrogels of low-dimensional nanostructures and even inorganic foams and hydrogels of low-dimensional nanostructures, and thus allow for exploration of their advanced physical and chemical properties.

Keywords intercalation polymerization      polypyrrole      nanosheet      supercapacitor      foam      multifunctionality     
Corresponding Authors: Maosong MO,Dapeng YE   
Issue Date: 29 May 2018
 Cite this article:   
Jiangli XUE,Maosong MO,Zhuming LIU, et al. A general synthesis strategy for the multifunctional 3D polypyrrole foam of thin 2D nanosheets[J]. Front. Mater. Sci., 2018, 12(2): 105-117.
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Jiangli XUE
Maosong MO
Zhuming LIU
Dapeng YE
Zhihua CHENG
Tong XU
Liangti QU
Fig.1  Schematic illustrations of the general fabrication strategy for the 3D CP foams of thin nanosheets: (a) The 3D V2O5 foam with dropwise Py monomer feeding. (b) V2O5?Py hybrid with Py monomer uniformly intercalating between the layers of V2O5 nanosheets. (c) A complete hydrogel of V2O5?PPy hybrid. (d) A net PPy foam. (e) Schematic illustration of the inner structure of the V2O5/Py hybrid after the solvothermal treatment: slice layers of V2O5 nanosheets is swelling, enabling uniform distribution and intercalation of Py monomer between the layers of V2O5 nanosheets.
Fig.2  (a)(b) Typical SEM images of the 3D PPy foam under different magnifications showing its inner macroporous network and framework morphology of interconnected nanosheets. Inset of (a): the photos of the PPy foam. Inset of (b): the enlarged view of the edge-on walls of the 3D PPy foam. (c) TEM image of an individual PPy nanosheet. Inset of (c): the corresponding HRTEM image of the edge of the individual PPy nanosheet. (d) EDS of the resulting 3D PPy foam. (e) Raman spectra and (f) XRD pattern of the 3D PPy foam.
Fig.3  Elasticity of the PPy hydrogel. (a)(b)(c) Macroscopic visualization, showing that the PPy hydrogel can recover to its original shape after a circle of compression of 50% and decompression. (d) σ Versus ε curves for the PPy hydrogel along the loading direction during loading?unloading cycles at ε = 40%?80%. (e) Fatigue resistance of the PPy hydrogel at 80% strain for 5 cycles.
Fig.4  Elastic property of the PPy hydrogel and adsorption property of the PPy foam. (a) Illustrated photos showing shape-memory elasticity of the PPy hydrogel. When PPy hydrogels were compressed and the water was squeezed-out, the PPy hydrogel kept the compressed shape. Given solvent again, PPy hydrogel recovered to its original shape gradually. (b) Adsorption efficiency of the 3D PPy foam in terms of weight gain. And, digital photos showing fast removal of (c)(d) methyl red and (e)(f) prussian blue from waste water with the PPy foam in a syringe.
Fig.5  Electrochemical performance of the 3D PPy foam of nanosheets//3D PPy foam of nanosheets symmetric supercapacitor tested in a two-electrode system. (a) CV curves of the 3D PPy nanosheet-based foam supercapacitor measured at various scan rates of 10?500 mV·s−1. (b) Galvanostatic charge/discharge curves of the 3D PPy nanosheet-based foam supercapacitor when operated at current densities from 50 to 500 mA·g−1. (c) The Nyquist plot of the impedance of the 3D PPy nanosheet-based foam electrode obtained over the frequency range of 0.1 Hz to 100 kHz by applying a sine wave with the amplitude of 5.0 mV. (d) Capacitance values calculated from individual galvanostatic curves in (b) as a function of the applied discharge current density.
PPy morphology Electrolyte Electrode system Capacitance Ref.
Particle liquid electrolyte two 1.6?14 mF [49]
Particle film PAN?LiCF3SO3?EC?PC gel two N/A [50]
Particle film PVA?H3PO4?H2O gel two N/A [51]
Nanosheet film PVA/LiClO4 gel two 38 F·g−1 [52]
Clusters 0.5 mol/L H2SO4 three 586 F·g−1 [23]
3D nanosheets network LiClO4 two 70 F·g−1 this work
Tab.1  Typical morphologies of pure PPy materials and their capacitance performance
Fig.6  (a) Schematic illustration of compressible PPy nanosheet-based foam supercapacitors. (b) CVs of the compressible supercapacitor based on the 3D PPy nanosheet-based foam electrodes under 0% and 50% compression for one cycle with the scan rate of 50 mV·s−1. (c) The cyclic stability of the supercapacitor under the initial state and the 50% compressed state for 2000 cycles at a constant current density of 100 mA·g−1.
  Fig. S1(a) A typical optical photograph of the 3D V2O5 foam after the freeze-drying treatment. (b) SEM image and (c) TEM image of the 3D V2O5 architecture, revealing its inner macroporous network and structure of interconnected nanosheets. (d) XRD pattern of the 3D foam of V2O5 nanosheets. 3D macroporous V2O5 foam of nanosheets was prepared by the following procedure. In a typical procedure, 0.36 g of V2O5 powder was dissolved in 30 mL H2O and then 5 mL H2O2 was added. The solution was stirred while maintaining continuous ultrasonication until becoming a clearly red solution (~30 min). The fresh red solution was then sealed in a 50 mL Teflon autoclave and maintained at 190°C for 18 h in the air oven. And then it was allowed to cool down to room temperature, and the bright yellow V2O5 gel was obtained. Finally, the 3D V2O5 foam of nanosheets was obtained by freeze-dring treatment of freshly prepared V2O5 gel [S1?S2].
  Fig. S2 XRD patterns of the pure V2O5 foam and the V2O5/PPy hybrid samples, and the corresponding HRTEM images.
  Fig. S3 SEM images of the porous PPy aggregates of spherical particles prepared without the solvothermal treatment before the Py polymerization, revealing the typical inner structure of the PPy aggregate sample. The PPy aggregates of spherical particles were prepared by directly chemical polymerization with V2O5 as the template and FeCl3 as the initiator. The polymerization was carried out in a refrigerator for 8 h for slow growth of PPy. After that, the product was washed several times by diluted hydrochloric acid (HCl) and deionized water to remove the residue and template. Then it was freeze-dried by liquid nitrogen.
  Fig. S4(a) N2 adsorption isotherms of the 3D foam of PPy nanosheets. (b) Pore size distribution of the 3D foam of PPy nanosheets.
  Fig. S5(a) Digital photograph of two pieces of 3D PPy foams located on a dandelion. (b)σ Versus ε curves for the 3D PPy foams along the loading direction during loading?unloading cycles at ε = 40%?80%.
  Fig. S6 Ragone plots of the 3D PPy foam of nanosheets//3D PPy foam of nanosheets symmetric supercapacitor.
  Fig. S7 The Nyquist plot of the 3D PPy nanosheet-based foam electrode under compressible states which obtained over the frequency range from 0.1 Hz to 100 kHz by applying a sine wave with an amplitude of 5.0 mV. It is similar to the original value which confirms the stable electrochemical performance.
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