Abstract
Lately, Raman spectroscopy has become powerful tool for quality assessment of graphene analogues with identification of intensity ratio of Raman active D-band and G-band (ID/IG ratio) as a vital parameter for quantification of defects. However, during chemical reduction of graphitic oxide (GrO) to reduced GrO (RGrO), the increased ID/IG ratio is often wrongly recognized as defect augmentation, with “formation of more numerous yet smaller size sp2 domains” as its explanation. Herein, by giving due attention to normalized peak height, full-width half-maxima and integrated peak area of Raman D- and G-bands, and compliment the findings by XRD data, we have shown that in-plane size of sp2 domains actually increases upon chemical reduction. Particularly, contrary to increased ID/IG ratio, the calculated decrease in integrated peak area ratio (AD/AG ratio) in conjunction with narrowing of D-band and broadening of G-band, evinced the decrease in in-plane defects. Finally, as duly supported by reduction induced broadening of interlayer-spacing characteristic XRD peak and narrowing of ~ 43° centered XRD hump, we have also shown that the sp2 domains actually expands in size and the observed increase in ID/IG ratio is indeed due to increase in across-plane defects, formed via along-the-layer slicing of graphitic domains.
Similar content being viewed by others
References
Vecera P, Julio C, Torres C, Pichler T, Reich S, Soni HR, Gorling A, Edelthalhammer K, Peterlik H, Hauke F, Hirsch A (2017) Precise determination of graphene functionalization by in situ Raman spectroscopy. Nat Commun 8:15192. https://doi.org/10.1038/ncomms15192
Park K-D, Raschke MB, Atkin JM, Lee YH, Jeong MS (2017) Graphene: probing bilayer grain boundaries in large-area graphene with tip-enhanced Raman spectrosco. Adv Mater. https://doi.org/10.1002/adma.201770048
Niu C, Jin B, Peng R, Shang Y, Liu Q (2017) Preparation and characterization of insensitive HMX/rGO/G composites via in situ reduction of graphene oxide. Rsc Adv 7:32275–32281. https://doi.org/10.1039/C7RA03863A
Gustavo Cançado L, da Silva MG, Ferreira EHM, Hof F, Kampioti K, Huang K, Penicaud A, Achete CA, Capaz RB, Jorio A (2017) Disentangling contributions of point and line defects in the Raman spectra of graphene-related materials. 2d Mater 4:025039. https://doi.org/10.1088/2053-1583/aa5e77
Kudin KN, Ozbas B, Schniepp HC, Prud’homme RK, Akshay IA, Car R (2008) Raman spectra of graphite oxide and functionalized graphene sheets. Nano Lett 8:36–41. https://doi.org/10.1021/nl071822y
Ferrari AC, Robertson J (2004) Raman spectroscopy of amorphous, nanostructured, diamond-like carbon, and nanodiamond. Philos Trans R Soc Math Phys Eng Sci 362:2477–2512. https://doi.org/10.1098/rsta.2004.1452
Dresselhaus MS, Jorio A, Hofmann M, Dresselhaus G, Saito R (2010) Perspectives on carbon nanotubes and graphene Raman spectroscopy. Nano Lett 10:751–758. https://doi.org/10.1021/nl904286r
Hong J, Park MK, Lee EJ, Lee D, Hwang DS, Ryu S (2013) Origin of new broad Raman D and G peaks in annealed graphene. Sci Rep 3:2700. https://doi.org/10.1038/srep02700
King AAK, Davis BR, Noorbehesht N, Newman P, Church TL, Harris AT, Razal JM, Minett AI (2016) A new Raman metric for the characterisation of graphene oxide and its derivatives. Sci Rep 6:19191. https://doi.org/10.1038/srep19491
Cançado LG, Jorio A, Ferreira EHM, Stavale F, Achete CA, Capaz RB, Moutinho MVO, Lambardo A, Kulmala TS, Ferrari AC (2011) Quantifying defects in graphene via raman spectroscopy at different excitation energies. Nano Lett 11:3190–3196. https://doi.org/10.1021/nl201432g
Zion E, Butenko A, Kaganvoiskii Y, Richter V, Wolfson L, Sharoni A, Kogan E, Kaveh M, Shlimak I (2017) Effect of annealing on Raman spectra of monolayer graphene samples gradually disordered by ion irradiation. J Appl Phys 121:114301. https://doi.org/10.1063/1.4978312
Wei Z, Pan R, Hou Y, Yang Y, Liu Y (2015) Graphene-supported Pd catalyst for highly selective hydrogenation of resorcinol to 1, 3-cyclohexanedione through giant π-conjugate interactions. Sci Rep. https://doi.org/10.1038/srep15664
Moon IK, Lee J, Ruoff RS, Lee H (2010) Reduced graphene oxide by chemical graphitization. Nat Commun 1:1–6. https://doi.org/10.1038/ncomms1067
Cançado LG, Takai K, Enoki T (2006) General equation for the determination of the crystallite size La of nanographite by Raman spectroscopy. Appl Phys Lett 88:163106. https://doi.org/10.1063/1.2196057
Bäuml C, Korn T, Lange C, Schuller C, Strunk C, Paradiso N (2017) Polarized surface-enhanced Raman spectroscopy of suspended carbon nanotubes by Pt-Re nanoantennas. Phys Rev B. https://doi.org/10.1103/PhysRevB.96.035408
Zafar Z, Zafar A, Tian Y, Cao Z, Jin B, Shi Z (2017) An easy approach to reveal the metallic nature of graphene by Breit-Wigner-Fano lineshapes using Raman spectroscopy: revealing the metallic nature of graphene using Raman spectroscopy. J Raman Spectrosc 48:1318–1322. https://doi.org/10.1002/jrs.5239
Claramunt S, Varea A, Diaz DL, Velazquez MM, Cornet A, Cirera A (2015) The importance of interbands on the interpretation of the Raman spectrum of graphene oxide. J Phys Chem C 119:10123–10129. https://doi.org/10.1021/acs.jpcc.5b01590
Park S, An J, Potts JR, Velamakanni A, Murali S, Ruoff RS (2011) Hydrazine-reduction of graphite- and graphene oxide. Carbon 49:3019–3023. https://doi.org/10.1016/j.carbon.2011.02.071
Yang D, Velamakanni A, Bozoklu G, Park S, Stoller M, Piner RD, Stankovich S, Jung I, Field DA, Ventrice Jr CA, Ruoff RS (2009) Chemical analysis of graphene oxide films after heat and chemical treatments by X-ray photoelectron and Micro-Raman spectroscopy. Carbon 47:145–152. https://doi.org/10.1016/j.carbon.2008.09.045
Stankovich S, Dikin DA, Piner RD, Kohlkaas KA, Kleinhammes A, Jia Y, Wu Y, Nguyen ST, Ruoff RS (2007) Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide. Carbon 45:1558–1565. https://doi.org/10.1016/j.carbon.2007.02.034
Fan X, Peng W, Li Y, Li X, Wang S, Zhang G, Zhang F (2008) Deoxygenation of exfoliated graphite oxide under alkaline conditions: a green route to graphene preparation. Adv Mater 20:4490–4493. https://doi.org/10.1002/adma.200801306
Compton OC, Jain B, Dikin DA, Abouimrane A, Amine K, Nguyen ST (2011) Chemically active reduced graphene oxide with tunable C/O ratios. ACS Nano 5:4380–4391. https://doi.org/10.1021/nn1030725
Fernández-Merino MJ, Guardia L, Paredas JI, Villar-Rodil S, Solis-Fernandaz P, Martinez-Alonso A, Tascon JMD (2010) Vitamin C is an ideal substitute for hydrazine in the reduction of graphene oxide suspensions. J Phys Chem C 114:6426–6432. https://doi.org/10.1021/jp100603h
Beekman M, Rodriguez G, Atkins R, Kunert J, Moore DB, Johnson DC (2015) Detection of nanoscale embedded layers using laboratory specular X-ray diffraction. J Appl Phys 117:185306. https://doi.org/10.1063/1.4920928
Wang G, Yang J, Park J, Gou X, Wang B, Liu H, Yao J (2008) Facile synthesis and characterization of graphene nanosheets. J Phys Chem C 112:8192–8195. https://doi.org/10.1021/jp710931h
Sharma R, Chadha N, Saini P (2017) Determination of defect density, crystallite size and number of graphene layers in graphene analogues using X-ray diffraction and Raman spectroscopy. Indian J Pure Appl Phys 55:625–629. https://doi.org/10.1021/jp710931h
Hummers WS, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339
Saini P, Kaushik S, Sharma R, Chakravarty D, Raj R, Sharma J (2016) Excellent electromagnetic interference shielding effectiveness of chemically reduced graphitic oxide paper at 101 GHz*. Eur Phys J B. https://doi.org/10.1140/epjb/e2016-60624-7
Saini P, Jalan R, Dhawan SK (2008) Synthesis and characterization of processable polyaniline doped with novel dopant NaSIPA. J Appl Polym Sci 108:1437–1446. https://doi.org/10.1002/app.27827
Li ZQ, Lu CJ, Xia ZP, Zhou Y, Luo Z (2007) X-ray diffraction patterns of graphite and turbostratic carbon. Carbon 45:1686–1695. https://doi.org/10.1155/2019/5963148
Acknowledgements
The authors are thankful to Director, CSIR-National Physical laboratory, New Delhi, for providing necessary research facilities. Authors are also thankful to Dr. Kumar, Delhi University for Raman Data and Dr. N Vijayan, NPL for XRD patterns. R.S. and N. C. gratefully acknowledge the UGC for JRF fellowships. The work is partially supported by the DST-Young Scientist Fast Track Proposal (GAP141232) and the CSIR-Young Scientist Research Grant (OLP152832).
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Information
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Chadha, N., Sharma, R. & Saini, P. A new insight into the structural modulation of graphene oxide upon chemical reduction probed by Raman spectroscopy and X-ray diffraction. Carbon Lett. 31, 1125–1131 (2021). https://doi.org/10.1007/s42823-021-00234-5
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s42823-021-00234-5