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

doi:10.1007/s11706-020-0501-0

Front. Mater. Sci.

2020, Vol. 14

Issue (2) : 198-210 https://doi.org/10.1007/s11706-020-0501-0

RESEARCH ARTICLE

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

Jinxing ZHANG, Kexing HU, Qi OUYANG, Qilin GUI(

), Xiaonong CHEN(

)

Beijing Laboratory of Biomedical Materials, Beijing University of Chemical Technology, Beijing 100029, China

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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

Corresponding Author(s): Qilin GUI,Xiaonong CHEN

Online First Date: 06 May 2020 Issue Date: 27 May 2020

Cite this article:

Jinxing ZHANG,Kexing HU,Qi OUYANG, et al. One-step functionalization of graphene via Diels--Alder reaction for improvement of dispersibility[J]. Front. Mater. Sci., 2020, 14(2): 198-210.

URL:

https://academic.hep.com.cn/foms/EN/10.1007/s11706-020-0501-0
https://academic.hep.com.cn/foms/EN/Y2020/V14/I2/198

Fig.1 Scheme 1 Pathway for surface functionalization of graphene with 4-HPM via the DA reaction.

Fig.2 Characterization of the graphene sample (G) and the functionalized graphene sample (FG): (a) FTIR spectra; (b) Raman spectra; (c) UV-vis absorbance spectra; (d) TG and DTG curves. FG was prepared at 90 °C for 12 h using DMF as the solvent.

Tab.1 Grafting amounts of 4-HPM on the graphene surface under different reaction conditions^a)

Fig.3 XPS analyses: (a) the graphene sample (G); (b) the functionalized graphene sample (FG). FG was prepared at 90 °C for 12 h using DMF as the solvent.

Fig.4 EDS diagrams: (a) the graphene sample (G); (b) the functionalized graphene sample (FG). FG was prepared at 90 °C for 12 h using DMF as the solvent.

Fig.5 Dispersion and turbidity of the graphene sample (G) and the functionalized graphene sample (FG) in different solvents (0.1 mg·mL⁻¹) (FG was prepared at 90 °C for 12 h using DMF as the solvent).

Fig.6 SEM images of (a) graphene and (b) functionalized graphene. (c) The AFM image of functionalized graphene.

Fig.7 Zeta potentials of graphene (a) and functionalized graphene (b) at different pH values.

Fig.8 UV spectra of MB solutions (adsorption condition: 25 °C, 24 h, pH= 11.5): initial solution (a); after adsorption using graphene (b); after adsorption using functionalized graphene (c).

Fig. S1 UV-vis spectra of filtrates collected from different washing times of functionalized graphene samples.

Fig. S2 The DSC result of the functionalized graphene sample (at a heating rate of 10 °C·min⁻¹ under N₂ atmosphere). FG was prepared at 90 °C for 12 h using DMF as solvent.

Fig. S3 The FTIR spectrum of functionalized graphene. FG was prepared at 90 °C for 12 h using DMF as solvent.

Fig. S4 FTIR spectra of functionalized graphene obtained at different temperatures (reaction solvent: DMF; reaction time: 12 h): 60 °C (a); 70 °C (b); 80 °C (c); 90 °C (d); 100 °C (e); 110 °C (f); 120 °C (g).

Table S1R value from FTIR spectra of functionalized graphene obtained at different reaction temperatures (reaction solvent: DMF; reaction time: 12 h)

Table S2R values from FTIR spectra of functionalized graphene obtained at 90 °C for different reaction time (reaction solvent: DMF)

Fig. S6 FTIR spectra of functionalized graphene samples obtained at 90 °C for 12 h in different solvents: H₂O (a); PX (b); DMF (c); NMP (d).

Table S3R values from FTIR spectra of functionalized graphene obtained by using different reaction solvents

Fig. S7 The absorbance of 4-HPM in the DMF solution at different concentrations (225 nm).

Fig. S8 Dispersion of graphene and functionalized graphene in different solvents and setting for different periods (FG was prepared at 90 °C for 12 h using DMF as the solvent).

Fig. S9 Time dependence of the turbidity of graphene and functionalized graphene dispersion in different solvents (0.1 mg·mL⁻¹) (FG was prepared at 90 °C for 12 h using DMF as the solvent).

Fig. S10 Absorbance of MB aqueous solutions at different concentrations (pH= 11.5, 664 nm).

1	K S Novoselov, A K Geim, S V Morozov, et al.. Electric field effect in atomically thin carbon films. Science, 2004, 306(5696): 666–669 https://doi.org/10.1126/science.1102896 pmid: 15499015
2	X Du, I Skachko, A Barker, et al.. Approaching ballistic transport in suspended graphene. Nature Nanotechnology, 2008, 3(8): 491–495 https://doi.org/10.1038/nnano.2008.199 pmid: 18685637
3	R R Nair, P Blake, A N Grigorenko, et al.. Fine structure constant defines visual transparency of graphene. Science, 2008, 320(5881): 1308 https://doi.org/10.1126/science.1156965 pmid: 18388259
4	C Lee, X Wei, J W Kysar, et al.. Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science, 2008, 321(5887): 385–388 https://doi.org/10.1126/science.1157996 pmid: 18635798
5	A A Balandin, S Ghosh, W Bao, et al.. Superior thermal conductivity of single-layer graphene. Nano Letters, 2008, 8(3): 902–907 https://doi.org/10.1021/nl0731872 pmid: 18284217
6	J B Wu, M L Lin, X Cong, et al.. Raman spectroscopy of graphene-based materials and its applications in related devices. Chemical Society Reviews, 2018, 47(5): 1822–1873 https://doi.org/10.1039/C6CS00915H pmid: 29368764
7	T Kuila, A K Mishra, P Khanra, et al.. Recent advances in the efficient reduction of graphene oxide and its application as energy storage electrode materials. Nanoscale, 2013, 5(1): 52–71 https://doi.org/10.1039/C2NR32703A pmid: 23179249
8	C Zhu, T Liu, F Qian, et al.. Supercapacitors based on three-dimensional hierarchical graphene aerogels with periodic macropores. Nano Letters, 2016, 16(6): 3448–3456 https://doi.org/10.1021/acs.nanolett.5b04965 pmid: 26789202
9	D A C Brownson, D K Kampouris, C E Banks. An overview of graphene in energy production and storage applications. Journal of Power Sources, 2011, 196(11): 4873–4885 https://doi.org/10.1016/j.jpowsour.2011.02.022
10	S Bai, X Shen. Graphene-inorganic nanocomposites. RSC Advances, 2012, 2(1): 64–98 https://doi.org/10.1039/C1RA00260K
11	X Huang, X Qi, F Boey, et al.. Graphene-based composites. Chemical Society Reviews, 2012, 41(2): 666–686 https://doi.org/10.1039/C1CS15078B pmid: 21796314
12	Y Liang, H Wang, J Zhou, et al.. 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 https://doi.org/10.1021/ja210924t pmid: 22280461
13	Q Xiang, J Yu, M Jaroniec. Graphene-based semiconductor photocatalysts. Chemical Society Reviews, 2012, 41(2): 782–796 https://doi.org/10.1039/C1CS15172J pmid: 21853184
14	H Lee, T K Choi, Y B Lee, et al.. A graphene-based electrochemical device with thermoresponsive microneedles for diabetes monitoring and therapy. Nature Nanotechnology, 2016, 11(6): 566–572 https://doi.org/10.1038/nnano.2016.38 pmid: 26999482
15	X Qiu, X Liu, W Zhang, et al.. Dynamic monitoring of microRNA-DNA hybridization using DNAase-triggered signal amplification. Analytical Chemistry, 2015, 87(12): 6303–6310 https://doi.org/10.1021/acs.analchem.5b01159 pmid: 25962779
16	L Yan, Y B Zheng, F Zhao, et al.. 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 https://doi.org/10.1039/C1CS15193B pmid: 22086617
17	Y Xu, L Zhao, H Bai, et al.. 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 https://doi.org/10.1021/ja905032g pmid: 19711892
18	D Parviz, S Das, H S T Ahmed, et al.. Dispersions of non-covalently functionalized graphene with minimal stabilizer. ACS Nano, 2012, 6(10): 8857–8867 https://doi.org/10.1021/nn302784m pmid: 23002781
19	S Park, J An, R D Piner, et al.. Aqueous suspension and characterization of chemically modified graphene sheets. Chemistry of Materials, 2008, 20(21): 6592–6594 https://doi.org/10.1021/cm801932u
20	M Ayán-Varela, J I Paredes, L Guardia, et al.. 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 https://doi.org/10.1021/acsami.5b00910 pmid: 25915172
21	S Pei, Q Wei, K Huang, et al.. Green synthesis of graphene oxide by seconds timescale water electrolytic oxidation. Nature Communications, 2018, 9(1): 145 https://doi.org/10.1038/s41467-017-02479-z pmid: 29321501
22	W S Hummers, R E Offeman. Preparation of graphitic oxide. Journal of the American Chemical Society, 1958, 80(6): 1339 https://doi.org/10.1021/ja01539a017
23	J T Robinson, J S Burgess, C E Junkermeier, et al.. Properties of fluorinated graphene films. Nano Letters, 2010, 10(8): 3001–3005 https://doi.org/10.1021/nl101437p pmid: 20698613
24	R R Nair, W Ren, R Jalil, et al.. Fluorographene: a two-dimensional counterpart of Teflon. Small, 2010, 6(24): 2877–2884 https://doi.org/10.1002/smll.201001555 pmid: 21053339
25	A Lundstedt, R Papadakis, H Li, et al.. White-light photoassisted covalent functionalization of graphene using 2-propanol. Small Methods, 2017, 1(11): 1700214 https://doi.org/10.1002/smtd.201700214
26	J R Lomeda, C D Doyle, D V Kosynkin, et al.. Diazonium functionalization of surfactant-wrapped chemically converted graphene sheets. Journal of the American Chemical Society, 2008, 130(48): 16201–16206 https://doi.org/10.1021/ja806499w pmid: 18998637
27	D Konios, M M Stylianakis, E Stratakis, et al.. Dispersion behaviour of graphene oxide and reduced graphene oxide. Journal of Colloid and Interface Science, 2014, 430: 108–112 https://doi.org/10.1016/j.jcis.2014.05.033 pmid: 24998061
28	Y Cao, Z Lai, J Feng, et al.. Graphene oxide sheets covalently functionalized with block copolymers via click chemistry as reinforcing fillers. Journal of Materials Chemistry, 2011, 21(25): 9271–9278 https://doi.org/10.1039/c1jm10420a
29	M T Beck, J Szépvölgyi, P Szabó, et al.. Heterogeneous Diels–Alder reaction between cyclopentadiene and different solid carbons. Carbon, 2001, 39(1): 147–149 https://doi.org/10.1016/S0008-6223(00)00180-9
30	J Zhu, J Hiltz, M A Mezour, et al.. 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 https://doi.org/10.1021/cm502253y
31	N Zydziak, C Hübner, M Bruns, et al.. One-step functionalization of single-walled carbon nanotubes (SWCNTs) with cyclopentadienyl-capped macromolecules via Diels–Alder chemistry. Macromolecules, 2011, 44(9): 3374–3380 https://doi.org/10.1021/ma200107z
32	C M Q Le, X T Cao, K T Lim. Ultrasound-promoted direct functionalization of multi-walled carbon nanotubes in water via Diels–Alder “click chemistry”. Ultrasonics Sonochemistry, 2017, 39: 321–329 https://doi.org/10.1016/j.ultsonch.2017.04.042 pmid: 28732952
33	S Sarkar, E Bekyarova, R C Haddon. Chemistry at the Dirac point: Diels–Alder reactivity of graphene. Accounts of Chemical Research, 2012, 45(4): 673–682 https://doi.org/10.1021/ar200302g pmid: 22404165
34	Y Cao, S Osuna, Y Liang, et al.. Diels–Alder reactions of graphene: computational predictions of products and sites of reaction. Journal of the American Chemical Society, 2013, 135(46): 17643–17649 https://doi.org/10.1021/ja410225u pmid: 24159929
35	P A Denis. Diels–Alder reactions onto fluorinated and hydrogenated graphene. Chemical Physics Letters, 2017, 684: 79–85 https://doi.org/10.1016/j.cplett.2017.06.034
36	J Yuan, G Chen, W Weng, et al.. One-step functionalization of graphene with cyclopentadienyl-capped macromolecules via Diels–Alder “click” chemistry. Journal of Materials Chemistry, 2012, 22(16): 7929–7936 https://doi.org/10.1039/c2jm16433g
37	J Liu, X Zeng, X Zhang, et al.. 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 https://doi.org/10.1002/app.32850
38	S Sarkar, E Bekyarova, S Niyogi, et al.. Diels–Alder chemistry of graphite and graphene: graphene as diene and dienophile. Journal of the American Chemical Society, 2011, 133(10): 3324–3327 https://doi.org/10.1021/ja200118b pmid: 21341649
39	A C Ferrari, J C Meyer, V Scardaci, et al.. Raman spectrum of graphene and graphene layers. Physical Review Letters, 2006, 97(18): 187401 https://doi.org/10.1103/PhysRevLett.97.187401 pmid: 17155573
40	J B Wu, M L Lin, X Cong, et al.. Raman spectroscopy of graphene-based materials and its applications in related devices. Chemical Society Reviews, 2018, 47(5): 1822–1873 https://doi.org/10.1039/C6CS00915H pmid: 29368764
41	M Cledera-Castro, A Santos-Montes, R Izquierdo-Hornillos, et al.. 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 https://doi.org/10.1002/jssc.200600301 pmid: 17461109
42	Y Zhang, Y Xu. Simultaneous electrochemical dual-electrode exfoliation of graphite toward scalable production of high-quality graphene. Advanced Functional Materials, 2019, 29(37): 1902171 https://doi.org/10.1002/adfm.201902171
43	J Seo, I Jeon, J Baek. Mechanochemically driven solid-state Diels–Alder reaction of graphite into graphene nanoplatelets. Chemical Science, 2013, 4(11): 4273–4277 https://doi.org/10.1039/c3sc51546j
44	P Redelius. Bitumen solubility model using Hansen solubility parameter. Energy & Fuels, 2004, 18(4): 1087–1092 https://doi.org/10.1021/ef0400058
45	B N Jang, D Wang, C A Wilkie. 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 https://doi.org/10.1021/ma0508909

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