journal article·2018-12Open access

Preparation and characterization of partially reduced graphene oxide aerogels doped with transition metal ions

Krzysztof Tadyszak, Łukasz Majchrzycki, Łukasz Szyller, Błażej Scheibe

Journal of Materials Science· Volume 53· Issue 23

Abstract

This work presents the preparation and characterization of pristine and transition metal doped partially reduced graphene oxide aerogels. The step-by-step preparation of aerogels from graphene oxide with an assistance of VCl 3 , CrCl 3 , FeCl 2 ·4H 2 O, CoCl 2 , NiCl 2 and CuCl 2 chlorides as reducing agents is shown and explained. The influence of reducing agents on the structural and magnetic properties of prepared aerogels is investigated. The use of electron paramagnetic resonance in purification during synthesis of GO and characterization afterwards is shown. It was found that VCl 3 was the strongest reducing agent leading to the formation of the most dense reduced graphene oxide aerogel, whereas vanadium is visible in EPR spectrum in form of V 4+ complex as a VO 2+ groups.
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Research context

OpenAlex topics: Supercapacitor Materials and Fabrication · Graphene research and applications · Transition Metal Oxide Nanomaterials

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References (64)

Show source-provided references
1. Pierre AC (2011) Aerogels handbook. Springer, New York
2. Mi X, Huang G, Xie W, Wang W, Liu Y, Gao J (2012) Preparation of graphene oxide aerogel and its adsorption for Cu2+ions. Carbon 50:4856–4864. https://doi.org/10.1016/j.carbon.2012.06.01310.1016/j.carbon.2012.06.013 ↗
3. Sassin MB, Greenbaum SG, Stallworth PE et al (2013) Achieving electrochemical capacitor functionality from nanoscale LiMn2O4 coatings on 3-D carbon nanoarchitectures. J Mater Chem A 1:2431–2440. https://doi.org/10.1039/C2TA00937D10.1039/C2TA00937D ↗
4. Voiry D, Shin HS, Loh KP, Chhowalla M (2018) Low-dimensional catalysts for hydrogen evolution and CO2 reduction. Nat Rev Chem 2:0105. https://doi.org/10.1038/s41570-017-010510.1038/s41570-017-0105 ↗
5. Cao L, Liu Y, Zhang B, Lu L (2010) In situ controllable growth of Prussian blue nanocubes on reduced graphene oxide: facile synthesis and their application as enhanced nanoelectrocatalyst for H2O2 reduction. ACS Appl Mater Interfaces 2:2339–2346. https://doi.org/10.1021/am100372m10.1021/am100372m ↗
6. Żelechowska K, Trawiński B, Dramińska S, Majdecka D, Bilewicz R, Kusz B (2017) Oxygen biosensor based on carbon nanotubes directly grown on graphitic substrate. Sens Actuators B Chem 240:1308–1313. https://doi.org/10.1016/j.snb.2016.09.08110.1016/j.snb.2016.09.081 ↗
7. George G, Costas G (2017) Graphene aerogels: a review. 2D Mater 4:03200110.1088/2053-1583/aa7883 ↗
8. Yanqiu J, Zhen X, Tieqi H et al (2018) Direct 3D printing of ultralight graphene oxide aerogel microlattices. Adv Funct Mater 28:1707024. https://doi.org/10.1002/adfm.20170702410.1002/adfm.201707024 ↗
9. Le Huong TX, Bechelany M, Cretin M (2017) Carbon felt based-electrodes for energy and environmental applications: a review. Carbon 122:564–591. https://doi.org/10.1016/j.carbon.2017.06.07810.1016/j.carbon.2017.06.078 ↗
10. Bai H, Li C, Wang X, Shi G (2011) On the gelation of graphene oxide. J Phys Chem C 115:5545–5551. https://doi.org/10.1021/jp112029910.1021/jp1120299 ↗
11. Gao W (ed) (2015) Graphene oxide: reduction recipes, spectroscopy, and applications. Springer, Cham
12. Toh RJ, Poh HL, Sofer Z, Pumera M (2013) Transition metal (Mn, Fe Co, Ni)-doped graphene hybrids for electrocatalysis. Chem Asian J 8:1295–1300. https://doi.org/10.1002/asia.20130006810.1002/asia.201300068 ↗
13. Zhou S, Liu N, Wang Z, Zhao J (2017) Nitrogen-doped graphene on transition metal substrates as efficient bifunctional catalysts for oxygen reduction and oxygen evolution reactions. ACS Appl Mater Interfaces 9:22578–22587. https://doi.org/10.1021/acsami.7b0575510.1021/acsami.7b05755 ↗
14. Cui J, Yao S, Huang JQ et al (2017) Sb-doped SnO2/graphene-CNT aerogels for high performance Li-ion and Na-ion battery anodes. Energy Storage Mater 9:85–95. https://doi.org/10.1016/j.ensm.2017.06.00610.1016/j.ensm.2017.06.006 ↗
15. Zhu J, Zhu T, Zhou X et al (2011) Facile synthesis of metal oxide/reduced graphene oxide hybrids with high lithium storage capacity and stable cyclability. Nanoscale 3:1084–1089. https://doi.org/10.1039/c0nr00744g10.1039/c0nr00744g ↗
16. Si W, Wu X, Zhou J et al (2013) Reduced graphene oxide aerogel with high-rate supercapacitive performance in aqueous electrolytes. Nanoscale Res Lett 8:247. https://doi.org/10.1186/1556-276X-8-24710.1186/1556-276X-8-247 ↗
17. Shudo Y, Karim MR, Wakata K, Ohmagari H, Kameda N, Hayami S (2018) Reduced graphene oxide-transition metal hybrids for hydrogen generation by photocatalytic water splitting. J Incl Phenom Macrocycl Chem. https://doi.org/10.1007/s10847-018-0795-z10.1007/s10847-018-0795-z ↗
18. Hummers WS Jr, Offeman RE (1958) Preparation of Graphitic Oxide. J Am Chem Soc 80:133910.1021/ja01539a017 ↗
19. Yordanov ND (1994) Quantitative EPR spectrometry—“State of the art”. Appl Magn Reson 6:241–257. https://doi.org/10.1007/BF0316249310.1007/BF03162493 ↗
20. Compton OC, An Z, Putz KW et al (2012) Additive-free hydrogelation of graphene oxide by ultrasonication. Carbon 50:3399–3406. https://doi.org/10.1016/j.carbon.2012.01.06110.1016/j.carbon.2012.01.061 ↗
21. Luxbacher T (2014) The zeta guide a practical guide to streaming potential measurements Anton Paar GmbH, Austria
22. Bai H, Li C, Wang X, Shi G (2010) A pH-sensitive graphene oxide composite hydrogel. Chem Commun 46:2376–2378. https://doi.org/10.1039/C000051E10.1039/C000051E ↗
23. Inagaki M (2009) Pores in carbon materials-importance of their control. New Carbon Mater 24:193–232. https://doi.org/10.1016/S1872-5805(08)60048-710.1016/S1872-5805(08)60048-7 ↗
24. Bai H, Chen Y, Delattre B, Tomsia AP, Ritchie RO (2015) Bioinspired large-scale aligned porous materials assembled with dual temperature gradients. Sci Adv. https://doi.org/10.1126/sciadv.150084910.1126/sciadv.1500849 ↗
25. Yang M, Zhao N, Cui Y et al (2017) Biomimetic architectured graphene aerogel with exceptional strength and resilience. ACS Nano 11:6817–6824. https://doi.org/10.1021/acsnano.7b0181510.1021/acsnano.7b01815 ↗
26. Wang C, Chen X, Wang B et al (2018) Freeze-casting produces a graphene oxide aerogel with a radial and centrosymmetric structure. ACS Nano. https://doi.org/10.1021/acsnano.8b0174710.1021/acsnano.8b01747 ↗
27. Chabot V, Higgins D, Yu A, Xiao X, Chen Z, Zhang J (2014) A review of graphene and graphene oxide sponge: material synthesis and applications to energy and the environment. Energy Environ Sci 7:1564. https://doi.org/10.1039/C3EE43385D10.1039/C3EE43385D ↗
28. Maciejewska BM, Warowicka A, Baranowska-Korczyc A et al (2015) Magnetic and hydrophilic MWCNT/Fe composites as potential T2-weighted MRI contrast agents. Carbon 94:1012–1020. https://doi.org/10.1016/j.carbon.2015.07.09110.1016/j.carbon.2015.07.091 ↗
29. Amirov RR, Shayimova J, Nasirova Z, Dimiev AM (2017) Chemistry of graphene oxide. Reactions with transition metal cations. Carbon 116:356–365. https://doi.org/10.1016/j.carbon.2017.01.09510.1016/j.carbon.2017.01.095 ↗
30. Sing KSW (1982) Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity. Pure Appl Chem 54:1217–1230. https://doi.org/10.1351/pac19825411220110.1351/pac198254112201 ↗
31. Fan LZ, Hu YS, Maier J, Adelhelm P, Smarsly B, Antonietti M (2007) High electroactivity of polyaniline in supercapacitors by using a hierarchically porous carbon monolith as a support. Adv Funct Mater 17:3083–3087. https://doi.org/10.1002/adfm.20070051810.1002/adfm.200700518 ↗
32. Repp S, Harputlu E, Gurgen S et al (2018) Synergetic effects of Fe3+ doped spinel Li4Ti5O12 nanoparticles on reduced graphene oxide for high surface electrode hybrid supercapacitors. Nanoscale 10:1877. https://doi.org/10.1039/C7NR08190A10.1039/C7NR08190A ↗
33. Genc R, Alas MO, Harputlu E et al (2017) High-capacitance hybrid supercapacitor based on multi-colored fluorescent carbon-dots. Sci Rep 7:11222. https://doi.org/10.1038/s41598-017-11347-110.1038/s41598-017-11347-1 ↗
34. Nazaruk E, Karaskiewicz M, Żelechowska K, Biernat JF, Rogalski J, Bilewicz R (2012) Powerful connection of laccase and carbon nanotubes. Electrochem Commun 14:67–70. https://doi.org/10.1016/j.elecom.2011.11.00510.1016/j.elecom.2011.11.005 ↗
35. Nitze F, Agostini M, Lundin F, Palmqvist AEC, Matic A (2016) A binder-free sulfur/reduced graphene oxide aerogel as high performance electrode materials for lithium sulfur batteries. Sci Rep 6:39615. https://doi.org/10.1038/srep3961510.1038/srep39615 ↗
36. Wu X-L, Xu A-W (2014) Carbonaceous hydrogels and aerogels for supercapacitors. J Mater Chem A 2:4852–4864. https://doi.org/10.1039/C3TA13929H10.1039/C3TA13929H ↗
37. Hui F, Grustan-Gutierrez E, Long S et al (2017) Graphene and related materials for resistive random access memories. Adv Electron Mater 3:1600195. https://doi.org/10.1002/aelm.20160019510.1002/aelm.201600195 ↗
38. Qiu L, Liu JZ, Chang SLY, Wu Y, Li D (2012) Biomimetic superelastic graphene-based cellular monoliths. Nat Commun 3:1241. https://doi.org/10.1038/ncomms225110.1038/ncomms2251 ↗
39. Tang H, Gao P, Bao Z et al (2015) Conductive resilient graphene aerogel via magnesiothermic reduction of graphene oxide assemblies. Nano Res 8:1710–1717. https://doi.org/10.1007/s12274-014-0672-z10.1007/s12274-014-0672-z ↗
40. Gómez-Navarro C, Weitz RT, Bittner AM et al (2007) Electronic transport properties of individual chemically reduced graphene oxide sheets. Nano Lett 7:3499–3503. https://doi.org/10.1021/nl072090c10.1021/nl072090c ↗
41. Haiyan S, Zhen X, Chao G (2013) Multifunctional, ultra-flyweight. Synergistically assembled carbon aerogels. Adv Mater 25:2554–2560. https://doi.org/10.1002/adma.20120457610.1002/adma.201204576 ↗
42. Ferrari AC, Meyer JC, Scardaci V et al (2006) Raman spectrum of graphene and graphene layers. Phys Rev Lett 97:18740110.1103/PhysRevLett.97.187401 ↗
43. Hayes WI, Joseph P, Mughal MZ, Papakonstantinou P (2015) Production of reduced graphene oxide via hydrothermal reduction in an aqueous sulphuric acid suspension and its electrochemical behaviour. J Solid State Electrochem 19:361–380. https://doi.org/10.1007/s10008-014-2560-610.1007/s10008-014-2560-6 ↗
44. Fan Z, Wang K, Wei T, Yan J, Song L, Shao B (2010) An environmentally friendly and efficient route for the reduction of graphene oxide by aluminum powder. Carbon 48:1686–1689. https://doi.org/10.1016/j.carbon.2009.12.06310.1016/j.carbon.2009.12.063 ↗
45. Ganguly A, Sharma S, Papakonstantinou P, Hamilton J (2011) Probing the thermal deoxygenation of graphene oxide using high-resolution in situ x-ray-based spectroscopies. J Phys Chem C 115:17009–17019. https://doi.org/10.1021/jp203741y10.1021/jp203741y ↗
46. Ghorbani M, Abdizadeh H, Golobostanfard MR (2015) Reduction of graphene oxide via modified hydrothermal method. Proc Mater Sci 11:326–330. https://doi.org/10.1016/j.mspro.2015.11.10410.1016/j.mspro.2015.11.104 ↗
47. Cançado LG, Jorio A, Ferreira EHM et al (2011) Quantifying defects in graphene via Raman spectroscopy at different excitation energies. Nano Lett 11:3190–3196. https://doi.org/10.1021/nl201432g10.1021/nl201432g ↗
48. Eckmann A, Felten A, Verzhbitskiy I, Davey R, Casiraghi C (2013) Raman study on defective graphene: effect of the excitation energy, type, and amount of defects. Phys Rev B 88:03542610.1103/PhysRevB.88.035426 ↗
49. Blank A, Twig Y, Ishay Y (2017) Recent trends in high spin sensitivity magnetic resonance. J Magn Reson 280:20–29. https://doi.org/10.1016/j.jmr.2017.02.01910.1016/j.jmr.2017.02.019 ↗
50. Pham CV, Repp S, Thomann R, Krueger M, Weber S, Erdem E (2016) Charge transfer and surface defect healing within ZnO nanoparticle decorated graphene hybrid materials. Nanoscale 8:9682–9687. https://doi.org/10.1039/C6NR00393A10.1039/C6NR00393A ↗
51. Augustyniak-Jabłokow MA, Tadyszak K, Maćkowiak M, Lijewski S (2013) ESR study of spin relaxation in graphene. Chem Phys Lett 557:118–122. https://doi.org/10.1016/j.cplett.2012.12.01810.1016/j.cplett.2012.12.018 ↗
52. Augustyniak-Jabłokow MA, Yablokov YV, Andrzejewski B et al (2010) EPR and magnetism of the nanostructured natural carbonaceous material shungite. Phys Chem Miner 37:237–247. https://doi.org/10.1007/s00269-009-0328-910.1007/s00269-009-0328-9 ↗
53. Augustyniak-Jabłokow MA, Tadyszak K, Maćkowiak M, Yablokov YV (2011) EPR evidence of antiferromagnetic ordering in single-layer graphene. Phys Stat Solidi (RRL): Rapid Res Lett 5:271–273. https://doi.org/10.1002/pssr.20110523410.1002/pssr.201105234 ↗
54. Tadyszak K, Maćkowiak M, Augustyniak-Jabłokow MA, Strzelczyk R (2014) FMR evidence of ferromagnetic correlations at zigzag edge states in single-layer graphene. J Mol Struct 1076:31–34. https://doi.org/10.1016/j.molstruc.2014.07.04710.1016/j.molstruc.2014.07.047 ↗
55. Tadyszak K, Strzelczyk R, Coy E, Maćkowiak M, Augustyniak-Jabłokow MA (2016) Size effects in the conduction electron spin resonance of anthracite and higher anthraxolite. Magn Reson Chem 54:239–245. https://doi.org/10.1002/mrc.437310.1002/mrc.4373 ↗
56. Tampieri F, Silvestrini S, Ricco R, Maggini M, Barbon A (2014) A comparative electron paramagnetic resonance study of expanded graphites and graphene. J Mater Chem C 2:8105–8112. https://doi.org/10.1039/C4TC01383B10.1039/C4TC01383B ↗
57. Singh V, Joung D, Zhai L, Das S, Khondaker SI, Seal S (2011) Graphene based materials: past, present and future. Prog Mater Sci 56:1178–1271. https://doi.org/10.1016/j.pmatsci.2011.03.00310.1016/j.pmatsci.2011.03.003 ↗
58. Ćirić L, Sienkiewicz A, Náfrádi B, Mionić M, Magrez A, Forró L (2009) Towards electron spin resonance of mechanically exfoliated graphene. Phys Stat Solidi (b) 246:2558–2561. https://doi.org/10.1002/pssb.20098232510.1002/pssb.200982325 ↗
59. Majchrzycki Ł, Augustyniak-Jabłokow MA, Strzelczyk R, Maćkowiak M (2015) Magnetic centres in functionalized graphene. Acta Phys Polon A 12710.12693/APhysPolA.127.540 ↗
60. Kempiński M, Florczak P, Jurga S, Śliwińska-Bartkowiak M, Kempiński W (2017) The impact of adsorption on the localization of spins in graphene oxide and reduced graphene oxide, observed with electron paramagnetic resonance. Appl Phys Lett 111:084102. https://doi.org/10.1063/1.499691410.1063/1.4996914 ↗
61. Luka Ć, Andrzej S, Djokic DM et al (2010) Size dependence of the magnetic response of graphite oxide and graphene flakes—an electron spin resonance study. Phys Stat Solidi (b) 247:2958–2961. https://doi.org/10.1002/pssb.20100044810.1002/pssb.201000448 ↗
62. Ćirić L, Sienkiewicz A, Gaál R et al (2012) Defects and localization in chemically-derived graphene. Phys Rev B 86:195139. https://doi.org/10.1103/PhysRevB.86.19513910.1103/PhysRevB.86.195139 ↗
63. Tanaka K, Koike T, Yamabe T, Yamauchi J, Deguchi Y, Yata S (1987) Electron-spin-resonance studies of pristine and heavily doped polyacenic materials. Phys Rev B 35:8368–837310.1103/PhysRevB.35.8368 ↗
64. Pham CV, Krueger M, Eck M, Weber S, Erdem E (2014) Comparative electron paramagnetic resonance investigation of reduced graphene oxide and carbon nanotubes with different chemical functionalities for quantum dot attachment. Appl Phys Lett 104:132102. https://doi.org/10.1063/1.487029710.1063/1.4870297 ↗