One-step functionalization of graphene via Diels--Alder reaction for improvement of dispersibility

Abstract

Good dispersibility of graphene in a medium or matrix is a critical issue in practical applications. In this work, graphene was functionalized using N-(4-hydroxyl phenyl) maleimide (4-HPM) via the Diels–Alder (DA) reaction by a one-step catalyst-free approach. The optimal reaction condition was found to be 90 °C for 12 h using dimethylformamide (DMF) as the solvent. FTIR, Raman spectroscopy, XPS and EDS proved that 4-HPM moieties were successfully grafted onto the surface of graphene. UV-vis and TGA confirmed that the grafting amount of 4-HPM was 3.75%–3.97% based on the mass of graphene. Functionalized graphene showed excellent dispersion stability when dispersed in common solvents such as ethanol, DMF, water, tetrahydrofuran and p-xylene. Meanwhile, functionalized graphene also exhibited pH sensitivity in aqueous due to the phenolic hydroxyls from the 4-HPM moieties. As a result of good dispersion stability and pH sensitivity, compared with graphene, functionalized graphene had better adsorption capacity for methylene blue (MB) from aqueous solution.

Keywords

graphene / functionalization / dispersibility / Diels--Alder reaction

References

[1] Novoselov K S, Geim A K, Morozov S V, . Electric field effect in atomically thin carbon films. Science, 2004, 306(5696): 666–669

[2] Du X, Skachko I, Barker A, . Approaching ballistic transport in suspended graphene. Nature Nanotechnology, 2008, 3(8): 491–495

[3] Nair R R, Blake P, Grigorenko A N, . Fine structure constant defines visual transparency of graphene. Science, 2008, 320(5881): 1308

[4] Lee C, Wei X, Kysar J W, . Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science, 2008, 321(5887): 385–388

[5] Balandin A A, Ghosh S, Bao W, . Superior thermal conductivity of single-layer graphene. Nano Letters, 2008, 8(3): 902–907

[6] Wu J B, Lin M L, Cong X, . Raman spectroscopy of graphene-based materials and its applications in related devices. Chemical Society Reviews, 2018, 47(5): 1822–1873

[7] Kuila T, Mishra A K, Khanra P, . Recent advances in the efficient reduction of graphene oxide and its application as energy storage electrode materials. Nanoscale, 2013, 5(1): 52–71

[8] Zhu C, Liu T, Qian F, . Supercapacitors based on three-dimensional hierarchical graphene aerogels with periodic macropores. Nano Letters, 2016, 16(6): 3448–3456

[9] Brownson D A C, Kampouris D K, Banks C E. An overview of graphene in energy production and storage applications. Journal of Power Sources, 2011, 196(11): 4873–4885

[10] Bai S, Shen X. Graphene-inorganic nanocomposites. RSC Advances, 2012, 2(1): 64–98

[11] Huang X, Qi X, Boey F, . Graphene-based composites. Chemical Society Reviews, 2012, 41(2): 666–686

[12] Liang Y, Wang H, Zhou J, . Covalent hybrid of spinel manganese-cobalt oxide and graphene as advanced oxygen reduction electrocatalysts. Journal of the American Chemical Society, 2012, 134(7): 3517–3523

[13] Xiang Q, Yu J, Jaroniec M. Graphene-based semiconductor photocatalysts. Chemical Society Reviews, 2012, 41(2): 782–796

[14] Lee H, Choi T K, Lee Y B, . A graphene-based electrochemical device with thermoresponsive microneedles for diabetes monitoring and therapy. Nature Nanotechnology, 2016, 11(6): 566–572

[15] Qiu X, Liu X, Zhang W, . Dynamic monitoring of microRNA-DNA hybridization using DNAase-triggered signal amplification. Analytical Chemistry, 2015, 87(12): 6303–6310

[16] Yan L, Zheng Y B, Zhao F, . Chemistry and physics of a single atomic layer: strategies and challenges for functionalization of graphene and graphene-based materials. Chemical Society Reviews, 2012, 41(1): 97–114

[17] Xu Y, Zhao L, Bai H, . Chemically converted graphene induced molecular flattening of 5,10,15,20-tetrakis(1-methyl-4-pyridinio)porphyrin and its application for optical detection of cadmium(II) ions. Journal of the American Chemical Society, 2009, 131(37): 13490–13497

[18] Parviz D, Das S, Ahmed H S T, . Dispersions of non-covalently functionalized graphene with minimal stabilizer. ACS Nano, 2012, 6(10): 8857–8867

[19] Park S, An J, Piner R D, . Aqueous suspension and characterization of chemically modified graphene sheets. Chemistry of Materials, 2008, 20(21): 6592–6594

[20] Ayán-Varela M, Paredes J I, Guardia L, . Achieving extremely concentrated aqueous dispersions of graphene flakes and catalytically efficient graphene-metal nanoparticle hybrids with flavin mononucleotide as a high-performance stabilizer. ACS Applied Materials & Interfaces, 2015, 7(19): 10293–10307

[21] Pei S, Wei Q, Huang K, . Green synthesis of graphene oxide by seconds timescale water electrolytic oxidation. Nature Communications, 2018, 9(1): 145

[22] Hummers W S, Offeman R E. Preparation of graphitic oxide. Journal of the American Chemical Society, 1958, 80(6): 1339

[23] Robinson J T, Burgess J S, Junkermeier C E, . Properties of fluorinated graphene films. Nano Letters, 2010, 10(8): 3001–3005

[24] Nair R R, Ren W, Jalil R, . Fluorographene: a two-dimensional counterpart of Teflon. Small, 2010, 6(24): 2877–2884

[25] Lundstedt A, Papadakis R, Li H, . White-light photoassisted covalent functionalization of graphene using 2-propanol. Small Methods, 2017, 1(11): 1700214

[26] Lomeda J R, Doyle C D, Kosynkin D V, . Diazonium functionalization of surfactant-wrapped chemically converted graphene sheets. Journal of the American Chemical Society, 2008, 130(48): 16201–16206

[27] Konios D, Stylianakis M M, Stratakis E, . Dispersion behaviour of graphene oxide and reduced graphene oxide. Journal of Colloid and Interface Science, 2014, 430: 108–112

[28] Cao Y, Lai Z, Feng J, . Graphene oxide sheets covalently functionalized with block copolymers via click chemistry as reinforcing fillers. Journal of Materials Chemistry, 2011, 21(25): 9271–9278

[29] Beck M T, Szépvölgyi J, Szabó P, . Heterogeneous Diels–Alder reaction between cyclopentadiene and different solid carbons. Carbon, 2001, 39(1): 147–149

[30] Zhu J, Hiltz J, Mezour M A, . Facile covalent modification of a highly ordered pyrolytic graphite surface via an inverse electron demand Diels–Alder reaction under ambient conditions. Chemistry of Materials, 2014, 26(17): 5058–5062

[31] Zydziak N, Hübner C, Bruns M, . One-step functionalization of single-walled carbon nanotubes (SWCNTs) with cyclopentadienyl-capped macromolecules via Diels–Alder chemistry. Macromolecules, 2011, 44(9): 3374–3380

[32] Le C M Q, Cao X T, Lim K T. Ultrasound-promoted direct functionalization of multi-walled carbon nanotubes in water via Diels–Alder “click chemistry”. Ultrasonics Sonochemistry, 2017, 39: 321–329

[33] Sarkar S, Bekyarova E, Haddon R C. Chemistry at the Dirac point: Diels–Alder reactivity of graphene. Accounts of Chemical Research, 2012, 45(4): 673–682

[34] Cao Y, Osuna S, Liang Y, . Diels–Alder reactions of graphene: computational predictions of products and sites of reaction. Journal of the American Chemical Society, 2013, 135(46): 17643–17649

[35] Denis P A. Diels–Alder reactions onto fluorinated and hydrogenated graphene. Chemical Physics Letters, 2017, 684: 79–85

[36] Yuan J, Chen G, Weng W, . One-step functionalization of graphene with cyclopentadienyl-capped macromolecules via Diels–Alder “click” chemistry. Journal of Materials Chemistry, 2012, 22(16): 7929–7936

[37] Liu J, Zeng X, Zhang X, . Synthesis and curing properties of a novel curing agent based on N-(4-hydroxyphenyl) maleimide and dicyclopentadiene moieties. Journal of Applied Polymer Science, 2011, 120(1): 56–61

[38] Sarkar S, Bekyarova E, Niyogi S, . Diels–Alder chemistry of graphite and graphene: graphene as diene and dienophile. Journal of the American Chemical Society, 2011, 133(10): 3324–3327

[39] Ferrari A C, Meyer J C, Scardaci V, . Raman spectrum of graphene and graphene layers. Physical Review Letters, 2006, 97(18): 187401

[40] Wu J B, Lin M L, Cong X, . Raman spectroscopy of graphene-based materials and its applications in related devices. Chemical Society Reviews, 2018, 47(5): 1822–1873

[41] Cledera-Castro M, Santos-Montes A, Izquierdo-Hornillos R, . Comparison of the performance of different reversed-phase columns for liquid chromatography separation of 11 pollutant phenols. Journal of Separation Science, 2007, 30(5): 699–707

[42] Zhang Y, Xu Y. Simultaneous electrochemical dual-electrode exfoliation of graphite toward scalable production of high-quality graphene. Advanced Functional Materials, 2019, 29(37): 1902171

[43] Seo J, Jeon I, Baek J. Mechanochemically driven solid-state Diels–Alder reaction of graphite into graphene nanoplatelets. Chemical Science, 2013, 4(11): 4273–4277

[44] Redelius P. Bitumen solubility model using Hansen solubility parameter. Energy & Fuels, 2004, 18(4): 1087–1092

[45] Jang B N, Wang D, Wilkie C A. Relationship between the solubility parameter of polymers and the clay dispersion in polymer/clay nanocomposites and the role of the surfactant. Macromolecules, 2005, 38(15): 6533–6543

Disclosure of potential conflicts of interest

There is no conflict of interest to declare.

Acknowledgement

The authors would like to thank the National Natural Science Foundation of China (Grant No. 51573211) for financial support.

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2020 Higher Education Press