| Functionalization Reaction |
Methodology |
Referenece |
characterization |
| 1.with amines |
Treatment of acid functionalized graphene (AFG) with SO2Cl2 followed by dodecylamine |
[23] |
Soluble in different organic solvents |
| 2. with alkyl amines of varying chain length |
1. Amidation reaction
2. Nucleophilic substitution reaction between amine and epoxy group |
[24] |
Results in hydrophobic surfaces |
| 3. with trimethoxy silane |
Reaction of GO with dodecyl, octyl, propyl, trimethoxysilane and
subsequent reduction with N2H4.H2O |
[28] |
|
| 4. with alkyl lithium reagents |
Reaction of graphite fluoride with R-Li reagent resulting in alkane
functionalized graphene |
[29] |
|
| 5. with oxygen plasma |
Reaction of graphene bi-layer with mild oxygen plasma |
[39] |
Results in single-sided and doublesided
functionalization |
| 6. chlorination |
Gas-phase photochemical chlorination of graphene |
[40] |
8 at% chlorine coverage |
| 7. chlorination |
Irradiation of graphene with UV light in a liquid chlorine medium |
[41] |
chlorinated up to 56 wt.% |
| 8. quaterthiophene molecules (T4) |
microwave-assisted silanization reaction of graphene oxide with T4 |
[42] |
GO-T4 can disperse in water/
organic solvents |
| 9. Graphene with diethyl melonate/
extended tetrathiafulvalene moieties |
Few layer graphene under Bingel reaction conditions i.e.,with CBr4 and
base (DBU) under microwave irradiation get functionalized with diethyl
melonate /extended tetrathia- fulvalene moieties |
[43] |
This hybrid material containing
covalently grafted cyclopraponated
melonate unit is soluble in organic
solvents |
| 10. with organic donor:
oligo(phenylenevinylene) (OPV) |
Functionalized graphene (-COCl)+OPV-amine refluxed in presence of
DMF/Et3N |
[45] |
Self-organization into ordered
assemblies |
| 11. NEt3-graphene |
Via consecutive deprotonation /carbometalation (i.e., nBuLi) and
electrophilic attack (i.e., Br-CH2CH2-NEt2) |
[48] |
amino-group grafted graphene |
| 12. GO electrophile with carbon
nucleophile such as melanonitrile anion |
Reaction of GO nucleophile with (NC)2CH-Na+ in THF, 60° C,
24 h |
[51] |
Formation of surface bound lynchpins |
| 13. GO with 5-(4-aminophenyl)-
10,15,20-triphenyl-21,23H-porphyrin
(H2P) |
Graphene treated with (i) H2SO4/HNO3 (2 : 1 v/v), (ii) KClO2, 96 h, (iii)
(COCl)2, 80° C, 24 h, then with 5-(4 aminophenyl)-10,15,20-triphenyl-
21,23H-porphyrin, THF, r.t., 72 h. |
[53] |
Forms stable dispersion with DMF |
| 14. GO with benzoxazole and
Benzimidazole moieties |
Cyclization reaction of carboxylic groups of GO which were converted
to benzoxazole and benzimidazole by the reaction of carboxylic groups
on GO with the hydroxyl and amino groups of o-aminophenol and
o-phenylenediamine respectively at room temperature. |
[56,57] |
|
| 15. Reduced GO with dichlorocarbene |
Reduced graphene oxide reacted with CHCl3 in presence of NaOH and
PTC |
[60] |
|
| 16. Reduced GO with 4-aminobenzoic
acid |
Reduced graphene oxide reacted through Friedel–Crafts reactions by
using polyphosphoric-acid/phosphorus-pentoxide with 4-aminobenzoic
acid. |
[61] |
|
| 17. peptide-directed 2-D arrays of
various nanoparticles (Pt, Au, Pd) on
graphene sheets |
Sequences of peptides were encoded by the combination of glutamic
acid (E), glycine (G), and phenylalanine (F) amino acids as follows:
(E-G-F)3-G, F and G for the interaction with graphenes (reduction EDC/
NHS) and E for the interaction with NPs (ultrasonication). |
[63] |
high electrocatalytic activity in the
electro-oxidation of methanol |
| 18. with polyhedral oligomeric
silsesquioxane (POSS) |
POSS-graphene formed via amide formation between aminefunctionalized
POSS and oxygen-containing groups (e.g., epoxy and
carboxyl groups) in graphene oxide (GO) |
[66] |
highly soluble in organic solvents,
shows superhydrophobic properties
with a water/air contact angle of
∼157° |
| 19. GO with imidazolium ionic liquids
(IL) (1,3-didodecylimidazolium bromine) |
Aqueous solution of GO (1 mg mL−1) (PH = 9) with negative
charges (COO−) are added to the solution of ILs (8 mg mL−1) (1-methyl-
3-butylimidazolium bromine (MBIB), 1-methyl-3-dodecylimidazolium
bromine (MDIB), 1,3-didodecylimidazolium bromine (DDIB)) in ODCB,
followed by shaking. The functionalization of GO takes place through
ionic interactions. |
[69] |
Homogeneous DDIB-GO sheets are
well dispersed in ODCB |
| 20. GO with 1,3-dipolar cycloaddition of
azomethine ylides |
1.5 equiv with respect to graphene of modified amino acid and
paraformaldehyde was added to the graphene suspension. The
reaction mixture was heated at 125 °C under stirring, the reagents
were added each 24 h for 5 days. After washing, followed with HCl, the
dispersion in DMF was mixed with 2 mL of Au-nanorod solution in DMF. |
[74] |
Used as scaffold in the construction
of organized composite
nanomaterials |
| 21. GO with a poly(amidoamine), or
PAMAM dendron |
By adding polyamidoamine, PAMAM, dendron (0.8 mmol, 5 equiv. per
graphene carbon atom), EDC (1.6 mmol, 10 equiv.), DMAP (1.6 mmol,
10 equiv.) and HOBT (1.6 mmol, 10 equiv.) as coupling agents in DMF
(35 ml), the mixtures were kept under Ar, stirred for 48 h. The resulting
suspensions were filtered and washed with DMF and then methanol.
For the cleavage of the Boc protecting groups, the precipitates were
dispersed in dioxane (20 ml) and HCl (12 M, 10 ml) was finally added.
The dispersions were kept under magnetic stirring overnight at room
temperature. The final mixtures were
filtered and washed thoroughly with DMF and methanol. |
[75] |
free amino groups at the tips of
the dendrons act as ligands in the
complexation of gold nanoparticles
(Au NPs) |
| 22. with benzyne precursor (arynemodified
graphene sheets: AGs) |
2-(Trimethylsilyl)-phenyl triate (5 mmol, 2.5 equiv. per graphene
carbon) was added to an acetonitrile solution of the graphene sheets
(Gs) (24 mg) and caesium fluoride (10 mmol, 5 equiv. per graphene
carbon), the mixture was stirred at 45 °C in air for 24 h. |
[76] |
well dispersed in various solvents
(DMF, Ethanol etc) |
| 23. Diels-Alder reaction |
graphene (as diene) with tetracyanoethylene (dienophile) in
1,4-dioxane/CH2Cl2 at room temperature and graphene as (dienophile)
with 2,3 dimethoxybutadiene (as diene) at 50 °C in xylene |
[77] |
|
| 24. through zwitterion intermediate
approach |
The graphene dispersed in dry toluene was reacted with DMAP, and
acetylenedicarboxylates at 85 °C under Ar atmosphere for 3 days. |
[79] |
Forms stable dispersion in common
solvents (DMF, CHCl3 and H2O |
| 25. via nitrene addition
tetraphenylethylene (TPE) |
Graphene (10 mg), and o-dichlorobenzene (10 mL). The tube was
evacuated under vacuum and then flushed with argon three
times through the side arm. After being sonicated for 20 min at room
temperature, TPE–C4N3 (250 mg) was added and the black suspension
was heated to 110 °C under argon protection and stirred for 3 days. |
[80] |
The resulting composite was totally
soluble in organic solvents |
| 26. with perfluoro-phenylazides
(PFPAs) |
Starting from solvent-exfoliated graphene flakes, thermal reaction was
carried out by heating the graphene flakes with PFPA derivatives in
o-dichlorobenzene (DCB) at 90 °C for 72 h. For the photochemical
reaction, a solution of PFPA together with graphene flakes in DCB was
irradiated under ambient conditions with a 450 W medium pressure Hg
lamp for 60 min. |
[82] |
Solubility ranging from non-polar
organic to aqueous solvents.
Selective functionalization is
achieved where patterned graphene
structures are fabricated with control
over the spatial features. |
| 27. click coupling: diketopyrrolopyrrole
(DPP)-Cu catalyzed
azide-alkine cycloaddition (CuAAC)
reaction |
2-(2-hexyldecyl)-5-(6-azidohexyl)-3,6-di(thiophen-2-yl) pyrrolo[3,4-c]
pyrrole-1,4(2H,5H)-dione (30 mg, 46.2 μmol), an alkyne-modified
graphene (G-ALK); deprotected T-GS (15 mg) and tetrakis(acetonitrile)
copper (I) hexafluorophosphate (0.86 mg, 2.3 μmol) were dissolved in
DMF (30 mL). After bubbing with N2 for 20 min one equivalent of copper
powder (2.92 mg, 46.2 μmol) was added and the mixture was stirred
for three days at 50°C |
[85] |
Good performance materials for
photovoltaic devices. |
| 28. with 4-bromophenyl using the in
situ diazonium formation |
Thermally expanded graphite is predominantly edge- functionalized
with 4-bromophenyl groups using in situ formation of the corresponding
diazonium salt from 4-bromoaniline. Expanded graphite was
first dispersed in chlorosulfonic acid, showing a relatively high
solubility of 0.97 mg/mL. The diazonium salt was formed in situ from
4-bromoaniline in the presence of sodium nitrite and a catalytic amount
of azobisisobutyronitrile (AIBN) and 4-bromophenyl groups were
grafted mainly on the exposed edges of the expanded graphite |
[90] |
chemically-assisted exfoliated
graphene sheets from the bulk
functionalized graphite is more
soluble than pristine graphene in
DMF |
| 29. with poly(methyl methacrylate |
Typical polymerization: four milligrams of graphene-based macroinitiator
was dispersed in 8 mL of DMF, 3 mL of deionized H2O and 3 mL (28
mmol) of MMA in a 25 mL flask. The mixture was degassed by bubbling
with N2 for 30 min and was then transferred using a cannula to another
25 mL flask charged with 2,2-dipyridyl (175 mg, 1.12 mmol) and CuBr
(40 mg, 0.28 mmol) under argon and this reaction flask was sealed.
The resulting suspension was stirred at room temperature for 48 h. |
[93] |
PMMA chains attached did impart
significantly enhanced solubility to
the nanocomposites in DMF, CHCl3
and THF |
| 30. by the 1,3 dipolar cycloaddition of
azomethine ylide |
10 mg of graphite was bath sonicated with pyridine and the
pyridine dispersion was then mixed with 50 ml DMF affording a
stable gray dispersion. An excess of N-methyl-glycine (50 mg) and
3,4-dihydroxybenzaldehyde (50 mg) were then added in the DMF
phase and the mixture was refluxed at 145–150 °C for 96 h |
[95] |
This functionalization facilitates
the dispersion of graphene-f-OH in
organic or aqueous solvents |
