Structural and surface characterization of pristine and boron doped
carbonized hydrothermal carbons (CHTC) is reported. Boron was
introduced into glucose precursor solution with concentration of 0.2% and
1%. Following hydrothermal treatment, samples were carbonized to 1000oC
and examined by Raman spectroscopy and temperature programmed
desorption. Characterization of obtained samples as material for carbon
paste electrode was performed by cyclic voltammetry measurements of the
Fe (CN)6
3-/4- redox couple. Structural analysis showed that lower boron
content in precursor solution induced structure ordering, while higher
amount of boron caused structural disorder of CHTC sample. Boron
presence in CHTC samples reduced number of surface active sites for
oxygen adsorption and consequently improved their electrochemical
response as electrode material for carbon paste electrode

Kalijadis, Ana

Laušević, Zoran

Trtić-Petrović, Tatjana M.

Đorđević, Jelena

Repository of the Vinča Nuclear Institute (VinaR)

     PHYSICAL CHEMISTRY 2014  12th International Conference on Fundamental and Applied Aspects of Physical Chemistry          The Conference is dedicated to the 25. Anniversary of the Society of Physical Chemists of Serbia            September 22-26, 2014  Belgrade, Serbia   II   ISBN 978-86-82475-30-9 Title: PHYSICAL CHEMISTRY 2014 (Proceedings) Editors: Ž. Čupić and S. Anić Published by: Society of Physical Chemists of Serbia, Studenski trg 12-16, 11158, Belgrade, Serbia Publisher: Society of Physical Chemists of Serbia For Publisher: S. Anić, President of Society of Physical Chemists of Serbia Printed by: “Jovan” Priting and Publishing Company; 200 Copies; Number of pages: 6+ 441; Format: B5; Printing finished in September 2014.  Text an Layout: “Jovan”  Neither this book nor any part may be reproduced or transmitted in any form or by any means, including photocopying, or by any information storage and retrieval system, without permission in writing from the publisher.  200 - Coppy priting    IV  PHYSICAL CHEMISTRY 2014  12th International Conference on  Fundamental and Applied Aspects of Physical Chemistry     Organized by The Society of Physical Chemists of Serbia  in co-operation with   Institute of Catalysis Bulgarian Academy of Sciences   Boreskov Institute of Catalysis of Siberian Branch of the Russian Academy of Sciences  Faculty of Physical Chemistry, University of Belgrade, Serbia  Institute of Chemistry Technology and Metallurgy,  University of Belgrade, Serbia  Vinča Institute, University of Belgrade, Serbia  Institute of General and Physical Chemistry, Serbia    Faculty of Pharmacy, University of Belgrade, Serbia    VInternational Organizing Committee  Chairman:  S. Anić (Serbia) Vice-chairman:  M. Gabrovska (Bulgaria)                             V. A. Sadykov  (Russia)  Members: N. Cvjetičanin (Serbia), S. N. Blagojević (Serbia), M. Daković (Serbia), T. Grozdić (Serbia), D. Jovanović (Serbia), M. Kuzmanović (Serbia), D. Marković (Serbia), J. Marković-Dimitrić (Serbia), B. Milosavljević (USA), M. Mojović (Serbia), N. Ostrovski (Serbia), I. Pašti (Serbia), M. Petković (Serbia), A. Popović-Bjelić (Serbia),  B. Simonović (Serbia), D. Stanisavljev (Serbia),  B. Šljukić (Serbia), N. Vukelić (Serbia), V. Vukojević (Sweden)  International Scientific Committee  Chairman:  Ž. Čupić (Serbia) Vice-chairmans: V. N. Parmon (Russia)                                   S. Rakovsky (Bulgaria) Members: B. Adnađević (Serbia), S. Anić (Serbia), A. Antić-Jovanović (Serbia), G. Bačić (Serbia), A. Kelarakis (Greece), R. Cervellati (Italy), V. Dondur (Serbia), Ivan Gutman (Serbia), S. D. Furrow (USA), K. Hedrih (Serbia), M. Jeremić (Serbia), A. V. Knyazev (Russia), Lj. Kolar-Anić (Serbia), V. Kuntić (Serbia), Z. Marković (Serbia),  S. Mentus (Serbia), Š. Miljanić (Serbia), M. Perić (Serbia), M. Plavšić (Serbia), D. M. F. Santos (Portugal), G. Schmitz (Belgium), I. Schreiber (Czech), P. Sevčik (Slovakia), B. C. Simionescu (Romania), N. Stepanov (Russia), D. Todorović (Serbia), M. Trtica (Serbia), V. Vasić (Serbia), D. Veselinović (Serbia)   Local Executive Committee  Chairman:              S. Blagojević Vice-chairmans:    A. Ivanović-Šašić  Members: P. Banković,  N. Bošnjaković, J. Dostanić,  A. Đerić, A. Ignjatović, A. Jović, N. Jović-Jovičić, D. Lončarević, J. Krstić, J. Maksimović, V. Marković, M. Milenković, S. Maćešić, V. Marković, B. Nedić, N. Potkonjak, D. Ranković, M. Stević, M. Žunić, M. Ristić,          PHYSICAL CHEMISTRY 2014  H-21-P   675THE EFFECT OF BORON DOPING ON THE STRUCTURE AND PROPERTIES OF CARBONIZED HYDROTHERMAL CARBON  A. Kalijadis, J.  Đorđević, T. Trtić-Petrović and Z. Laušević  Laboratory of Physics, Vinča Institute of Nuclear Sciences, University of Belgrade, P. O. Box 522, 11001 Belgrade, Serbia (anaudovicic@vinca.rs)   ABSTRACT Structural and surface characterization of pristine and boron doped carbonized hydrothermal carbons (CHTC) is reported. Boron was introduced into glucose precursor solution with concentration of 0.2% and 1%. Following hydrothermal treatment, samples were carbonized to 1000oC and examined by Raman spectroscopy and temperature programmed desorption. Characterization of obtained samples as material for carbon paste electrode was performed by cyclic voltammetry measurements of the Fe (CN)63-/4- redox couple. Structural analysis showed that lower boron content in precursor solution induced structure ordering, while higher amount of boron caused structural disorder of CHTC sample. Boron presence in CHTC samples reduced number of surface active sites for oxygen adsorption and consequently improved their electrochemical response as electrode material for carbon paste electrode.   INTRODUCTION In recent years hydrothermal carbonization has demonstrated its capability of converting carbohydrate into highly functionalized carbon materials under mild processing conditions [1]. After additional carbonization, hydrothermal carbons (HTC) with various shape size, chemical compositions, and surface functional groups have shown novel and interesting intrinsic properties which allow widespread use of these materials [2]. Incorporation of heteroatoms into carbon materials affects their surface properties and oxidation resistance. Boron is by far the most widely used doping element in carbon. It enters the graphite lattice by substituting for carbon at the trigonal sites and consequently alters the electronic properties of the material [3]. The aim of this study was to investigate the effect of boron incorporation on the structural and surface characteristics of carbonized HTC. Additionally,        PHYSICAL CHEMISTRY 2014  H-21-P   676electrochemical characterization of carbonized boron doped HTC as material for carbon paste electrode was examined.   EXPERIMENTAL To produce HTC, 2M water solution of D(+)-Glucose was prepared. Boric acid was used as source of boron and it was added in the starting solution to obtained boron concentration of 0.2% and 1%. After sealing, the autoclave was heated in programmable oven for 24 h at 180oC. All HTC samples were additionally carbonized in nitrogen to 1000oC. Obtained samples were marked as CHTC (undoped carbonized hydrothermal carbon) and boron doped samples as CHTCB0.2 and CHTCB1. Raman spectra were taken with an Advantage 532 Raman spectrometer (DeltaNu Inc.).  Temperature programmed desorption (TPD) in combination with mass spectrometry was used to investigate the quantity of surface oxygen groups. Evolution of CO and CO2 to 1000oC was monitored with a quadrupole mass spectrometer (Extorr). Carbon paste was made by intimate hand-mixing of carbonized HTC powders with the paraffin oil as a liquid binder. All pastes, homogenized at the same ratio of 1.2 g of material and 0.4 cm3 paraffin oil, were packed into a piston-driven Teflon holder.  A 797 VA Computrace analyzer (Metrohm) controlled by 797 VA Computrace software ver. 1.2 was applied for all voltammetric measurements.   RESULTS AND DISCUSSION Table 1. Raman spectra parameters for CHTC,CHTCB0.2 and CHTCB1  Table 1 shows Raman spectra parameters. The main features of these spectra are two broad peaks at 1350 cm-1 (D band) and at 1590 cm-1 (G band), commonly observed in mixture of graphitic and disordered sp2-bonded carbon. There are no significant changes in G and D peak positions Sample Peak Peak position (cm-1) Bandwidth (cm-1) ID/IG CHTC D G 1347 1579 205 106 2.22 CHTCB0.2 D G 1345 1575 200 90 1.95 CHTCB1 D G 1345 1580 215 103 2.6        PHYSICAL CHEMISTRY 2014  H-21-P   677 for CHTCH and CHTCB1. However, the D peak bandwidth increased because of higher amount of B atoms, which occupy the lattice points to a greater extent and behave as defects for Raman scattering (higher values for ID/IG). For CHTCB0.2 sample all Raman parameters indicate increasing of structure ordering.   Table 2. Amounts of evolved CO, CO2 and CO+CO2 for CHTC, CHTCB0.2 and CHTCB1  Amounts of evolved CO2, CO obtained by TPD are summarized in Table 2. It can be noted that amounts of released CO2 and CO for B doped samples are several times less compared to CHTC. This indicates that boron incorporation induced changes in electronic structure by reducing number of surface active sites for oxygen adsorption.                Figure 1. Cyclic voltammograms (50 mVs-1) for 1mmol K3Fe(CN6)/ K4Fe(CN6) for electrode made from CHTC, CHTCB0.2 and CHTCB1  Figure 1. shows cyclic voltammograms of Fe (CN)63-/4- for carbon paste electrodes made from carbonized HTC samples (CPE-CHTC, CPE-Sample QCO (μmol/g) QCO2 (μmol/g) QCO2+CO (μmol/g) CHTC 195.9 115.9 311.8 CHTCB0.2 24.6 15.9 40.5 CHTCB1 73.6 21.5 95.1        PHYSICAL CHEMISTRY 2014  H-21-P   678CHTCB0.2, and CPE-CHTCB1). It can be noted that on CPE-CHTC Fe (CN)63-/4- exhibited a poor electrochemical behavior with broadened wave shape and high capacitive background current. Granger et al. [4] previously reported that several factors are known to influence redox-reaction kinetics at sp2 carbon electrode: surface cleanliness, presence of adsorbed layers and fraction of edge plane exposed. According TPD results, the highest amount of surface oxygen groups was obtained for CHTC sample (Table 2), which caused the poor electrochemical behavior. Contrary to this, for boron doped samples drastically improved electrochemical responses were obtained and results are in compliance with TPD results. However, boron fraction of 1% worsens peaks intensity as well as the peak to peak potential separation compare to fraction of 0.2%.  CONCLUSION Results showed that the different amount of boron allows obtaining carbonized hydrothermal carbons with modified structural, chemical and electrochemical characteristics compared to the pristine sample. It was shown that boron concentration of 0.2% in precursor solution generates structure ordering of carbonized sample, which induced a greater extent of surface active sites reduction for oxygen adsorption compared with sample with higher boron concentration. Modification of hydrothermal carbon with boron and its additional carbonization facilitate preparation of the material with good surface properties, which are important for the development and application of this material as a carbon paste electrode.  ACKNOWLEDGEMENT  We acknowledge the support to this work provided by the Ministry of Education and Science of Serbia through project Physics and Chemistry with Ion Beams, No. III 45006.  REFERENCES [1] B. Hu, K. Wang, L. Wu, S.-H. Yu, M. Antonietti, and M.-M. Titirici, Advanced Materials, 2010, 22, 813–828. [2] J. Hu, H. Li, X. J. Huang, Solid State Ionics, 2007, 178, 265-271. [3] X. Wu, L.R. Radovic, Carbon, 2005, 431, 1768–1777. [4] M. C. Granger, M. Witek, J. Xu, J. Wang, M. Hupert, A. Hanks, M. D. Koppang, J. E. Butler, G. Lucazeau, M. Mermoux, J. W. Strojek, and G. M. Swain, Analytical Chemistry, 2000, 72, 3793-3804.   

The effect of boron doping on the structure and properties of carbonized hydrothermal carbon

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The effect of boron doping on the structure and properties of carbonized hydrothermal carbon

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