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Synthesis of carbon frameworks with N, O and S-lined pores from gallic acid and thiourea for superior CO2 adsorption and supercapacitors

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  • ReceivedDec 5, 2019
  • AcceptedJan 15, 2020
  • PublishedMar 9, 2020

Abstract

“C2N”-species have emerged as a promising material with carbon-like applications in sorption, gas separation and energy storage, while with much higher polarity and functionality. Controlled synthesis of “C2N” structure is still based on complex and less-sustainable monomers, which prohibits its broader industrial application. Here we report a class of well-defined C2(NxOySz)1 carbons with both high content of N/O/S heteroatoms and large specific surface area of up to 1704 m2 g−1, which can be efficiently synthesized through a simple additive condensation process using simple gallic acid and thiourea as the building blocks, without subtractive activation. This 1,4-para tri-doped C2(NxOySz)1 structure leads to sufficient CO2 adsorption capacity (3.0 mmol g−1 at 273 K, 1 bar) and a high CO2/N2 selectivity (47.5 for a 0.15/0.85 CO2/N2 mixture at 273 K). Related to the polarity, the polar frameworks can be used as supercapacitor electrodes, with record specific capacitances as high as 255 F g−1 at 3.5 V for a symmetric supercapacitor in ionic liquid electrolyte. This work discloses a general way for preparing a novel family of multifunctional, high heteroatom-doped porous materials for various applications.


Funded by

Tian Z sincerely acknowledges the financial support provided by Zhengzhou University and the National Natural Science Foundation of China(51873198)


Acknowledgment

The Max Planck Society is gratefully acknowledged for financial support. We thank Regina Rothe for technical assistance. Tian Z sincerely acknowledges the financial support provided by Zhengzhou University and the National Natural Science Foundation of China (51873198).


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Tian Z and Antonietti M conceived the idea and cowrote the paper. Tian Z and Lai F designed and performed the experiments and analyzed the results. Tobias H performed the HRTEM tests. All the authors discussed the results and commented on the manuscript.


Author information

Zhihong Tian obtained her PhD degree in applied chemistry at Zhengzhou University in 2018. She has been working in Zhengzhou University since June 2018. Currently, she is a visiting postdoctor in Professor Markus Antonietti’s Group at Max Planck Institute of Colloids and Interfaces (MPICI). Her research interests lie in the design and synthesis of porous polymer and carbon materials for gas separation, energy storage and conversion.


Markus Antonietti is a professor at MPICI. He studied chemistry in Mainz, where he also received his PhD in 1985. His habilitation on nanogels in 1990 fueled his enthusiasm for complex nanostructures based on polymers and carbon. After a professorship at the University of Marburg, he was appointed director for the Department of Colloid Chemistry at MPICI in 1993. His work deals with modern materials chemistry, energy materials, and sustainability issues within those topics.


Supplement

Supplementary information

Experimental details and supporting data are available in the online version of the paper.


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  • Scheme 1

    Schematic illustration of the synthesis of the C2(NxOySz)1 for CO2 adsorption and supercapacitors.

  • Figure 1

    (a) SEM image of GT13-800. (b) EDX mappings of carbon (red), nitrogen (green), oxygen (blue) and sulphur (yellow) for GT13-800. (c) XRD of the GT13-300, 400, 500, 800. (d) HRTEM image of GT13-800.

  • Figure 2

    Deconvoluted XPS spectra of the GT13-500 and GT13-800. (a, b) N 1s, (c, d) O 1s and (e, f) S 2p.

  • Figure 3

    (a, b) N2 adsorption (filled symbols) and desorption (empty symbols) isotherms at 77 K and pore size distribution curves calculated by QSDFT for the GT13-300, GT13-400, GT13-500 and GT13-800. (c) CO2 and N2 adsorption isotherms of GT13-500 at 273 K. (d) CO2/N2 selectivity as calculated by the IAST method for a CO2꞉N2=0.15꞉0.85 gas mixture at 273 K.

  • Figure 4

    (a) CV curves of GT13-800 electrodes at different scan rates from 2 to 100 mV s−1. (b) Specific capacitance values of GT13-800 calculated from CV curves at different scan rates. (c) Galvanostatic charge-discharge curves at various current densities from 0.1 to 5 A g−1. (d) Nyquist plot of GT13-800.

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