Communications
ChemistrySelect doi.org/10.1002/slct.202100574
z Materials Science inc. Nanomaterials & Polymers
Crystallization of Diamond from Graphene Oxide
Nanosheets by a High Temperature and High Pressure
Method
Masahiro Fukuda,[a] M. Saidul Islam,[a, b] Yoshihiro Sekine,[a, c] Toru Shinmei,[d]
Leonard F. Lindoy,[e] and Shinya Hayami*[a, b]
Herein we report a high temperature and high pressure driven
crystallization of two-dimensional graphene oxide (GO) nano-
sheets to three-dimensional diamond. The successful phase
transformation was confirmed using X-ray diffraction (XRD),
Raman spectroscopy, and X-ray photoelectron spectroscopy
(XPS). The phase transition platform will available to utilize for
a wide variety of diamond doping employing, for example,
nitrogen or other light elements, in which the correspondingly
doped GO is used as the starting material.
Research interest in synthetic diamonds has persisted over
many decades due to their special physical and chemical
properties. In particular, these include chemical inertness,
unique hardness, high wear resistance and high thermal
conductivity. Applications include their use for cutting and
grinding hard materials well as for incorporation in medical
and dental devices.[1–3] In a major breakthrough in diamond
research, boron-doped diamond obtained using high temper-
ature/high pressure were shown to display type-II super-
[a] M. Fukuda, Dr. M. S. Islam, Prof. Y. Sekine, Prof. S. Hayami
Department of Chemistry, Faculty of Advanced Science and Technology
Kumamoto University
2-39-1 Kurokami, Chuo-ku, Kumamoto 860-8555 (Japan)
E-mail: 204d7202@st.kumamoto-u.ac.jp
islam_saidul@kumamoto-u.ac.jp
sekine@kumamoto-u.ac.jp
hayami@kumamoto-u.ac.jp
[b] Dr. M. S. Islam, Prof. S. Hayami
Institute of Industrial Nanomaterials (IINa)
Kumamoto University
2-39-1 Kurokami, Chuo-ku, Kumamoto 860-8555 (Japan)
[c] Prof. Y. Sekine
Priority Organization for Innovation and Excellence
Kumamoto University
2-39-1 Kurokami, Chuo-ku, Kumamoto 860-8555 (Japan)
[d] T. Shinmei
Geodynamics Research Center
Ehime University
2-5 Matsuyama, Ehime 790-8577 (Japan)
E-mail: shinmei@sci.ehime-u.ac.jp
[e] Prof. L. F. Lindoy
School of Chemistry
The University of Sydney
Sydney, New South Wales 2006 (Australia)
E-mail: len.lindoy@sydney.edu.au
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/slct.202100574
ChemistrySelect 2021, 6, 3399 – 3402
conducting properties below the superconducting transition
temperature of Tc = ∼ 4 K; this indicates the possibility of
forming diamond-based high temperature superconducting
materials.[4] However, using a state of the art diamond synthesis
method from graphite via high temperature (1500 °C or higher)
and high pressure (5–6 GPa or higher), or by employing a
chemical vapor deposition (CVD) process, in which growth on a
substrate occurs following deposition from a vapor phase,
allow only limited control of the elements that can be used for
doping. The design of a synthetic route for diamond that can
be extended to produce a wide range of doped diamond types,
while controlling the percentage of the doped element(s)
present, has remained a significant challenge. In our present
approach towards this goal, we have investigated the use of
graphene oxide (GO) nanosheets as starting materials for
generating synthetic diamonds via a phase transition process.
GO nanosheets have abundant oxygen functional groups on
their surface[5] and the chemical reactivity of these oxygen
groups allow their doping with nitrogen, phosphorus, boron or
even halogen.[6–8] Thus, if as expected diamond could be
synthesized from GO itself, then it seemed feasible to extend
the synthetic procedure to the production of a wide range of
doped diamond types by employing the corresponding doped
GOs as the starting materials.
Over recent decades, GO-based materials have been
demonstrated to have widespread applications in chemistry,
physics, biology, electronics, engineering, and medicine. For
example, particular GO materials have been demonstrated to
display proton conduction, semi-conductivity, light emission,
and to act as catalysts.[9–14] They have also been used for drug
delivery as well as for sensor and transistor fabrication.[15,16] In
the current work we were successful in achieving a phase
transition of pure GO to diamond by the high temperature/
high pressure method using a 2000-ton Kawai type multi-anvil
apparatus (Ehime University ORANGE-2000). The experimental
details are given in the supporting information.
The black GO powder used in the study can be exfoliated
into a monolayer (Figure S1) and the interlayer distance of bulk
sample is about 8 Å (Figure S2). Photographs of the diamond
MgO capsule and the GO diamond Ta capsule after the high
temperature/high pressure process are shown in Figure 1. In
both cases, the samples show significant sintering with a
surface color of ochre for the MgO capsule sample and black
for the Ta capsule sample. Similar colors to these were
3399 © 2021 Wiley-VCH GmbH
 Communications
ChemistrySelect doi.org/10.1002/slct.202100574
Figure 1. Optical photographs of the respective samples after the high
temperature/high pressure process, (a) GO Diamond MgO capsule and (b)
GO Diamond Ta capsule.
maintained for the interiors of the respective samples. The
difference in color between two samples can be attributed to
the use of different capsule types (that is, arising from
impurities derived from the respective capsules) as well as to
the presence of some residual carbon (the latter is supported
by the XRD and XPS data)
The Raman spectra at room temperature of pristine GO, the
GO diamond MgO capsule and the GO Diamond Ta capsule are
shown in Figure 2. The pristine GO sample shows two typical
peaks corresponding to the “D band” and “G band”. The D
band is characteristically located at about 1350 cm 1 and is
assigned to the respiratory mode (a1g). The G band, which is
located at about 1580 cm 1, has been assigned previously to
the in-plane bond stretching mode of the pair of sp2 carbon
atoms (e2g).[17]
In sharp contrast, the GO diamond MgO capsule and GO
diamond Ta capsule samples each showed only a single sharp
peak at 1332 cm 1. Diamond belongs to the face-centered
cubic lattice of the spatial group Fd3 m. Since there are two
carbon atoms in the primitive unit cell, there is a single triple
degenerate primary phonon of symmetry T2g.[18] This mode is
shown as a single, sharp peak at 1332 cm 1 and is in accord
with a phase transition having occurred from the two-dimen-
sional GO nanosheets to diamond under the high temperature
Figure 2. Raman spectra of the pristine GO, GO diamond MgO capsule and
GO diamond Ta capsule
ChemistrySelect 2021, 6, 3399 – 3402
and high pressure conditions employed. The 1332 cm 1 peak is
also clearly observed for the internal sample portion of each
product. This result is in keeping with both samples under-
going uniform phase transitions to diamond (Figure S3).
The XRD spectra shown in Figure 3 are also in strong
agreement with the occurrence of a phase transition from
pristine GO to diamond in both the GO diamond MgO and the
GO diamond Ta samples. The XRD pattern for the internal part
of the GO diamond MgO capsule is shown in Figure 3a. The
peaks at 2θ = 43.9°, 75.3°, and 91.5° are assigned to the (111),
(220) and (311) crystal lattice planes of the diamond,
respectively, with the remaining peaks proposed to arise from
the presence of Mg(CO3) and Mg(OH)2 as contamination which
is in accord with some previous reports.[19,20] It is noted that
Mg(CO3) and Mg(OH)2 exist in their respective most stable
magnesite and brucite states as expected from the experimen-
tal conditions (2100 °C and 15 GPa) employed.[21,22] These states
were detected not only for the inside of the respective samples
but also for their surface layers (Figure S4) and, undoubtedly,
their presence can be attributed to contamination from the
MgO capsule. In this context, it is noted that the calculated pKa
values for GO fall in the range 3.93–3.96.[23] Thus, in general, GO
is a stronger acid than carboxylic acids bearing a single
functional acid group. From this it appears likely that GO is
capable of dissolving the MgO capsule under the experimental
conditions employed to give the observed magnesium contam-
inants. The GO diamond Ta capsule sample also showed
diffraction peaks for diamond (Figure 3b), with the other peaks
present in this case assigned to the presence of tantalum oxide.
The latter were also detected in both the surface and internal
parts of the sample.
Figure 3. XRD spectra of (a) the GO diamond MgO capsule product and (b)
the GO diamond Ta capsule product.
3400 © 2021 Wiley-VCH GmbH
 Communications
ChemistrySelect doi.org/10.1002/slct.202100574
The XPS survey spectra for pristine GO, GO diamond MgO
capsule, and GO diamond Ta capsule are presented in Fig-
ure 4a. The main elements shown to be present are carbon and
oxygen, with only small amounts of capsule-derived Mg
(0.52 %) and Ta (0.24 %) being detected. (Figure S5). Peak
deconvolution of the C1s spectrum of GO (Figure 4b) revealed
the presence of a high percentage (33 %) of oxygenated groups
in the GO. For the oxygenated sites, the epoxy (C O C) group
predominates and yields a peak at 286.8–287.0 eV. The
carbonyl ( C=O) and the carboxyl ( COOH) groups are
assigned to peaks at 287.8–288.0 eV and 289.0–289.3 eV,
respectively.[24] In contrast to the above, for the MgO and Ta
capsule diamond samples the ratio of the oxygenated groups
(epoxy, carbonyl and carboxyl) are significantly reduced
(Figures 4c, 4d). The width at the half maximums of the C1s
spectra of the GO diamond MgO and the GO diamond Ta
capsules are 1.84 eV and 1.45 eV, respectively. In general, the
C1s spectrum of diamond is known to exhibit a symmetric
shape.[25] However, the spectra obtained here are slightly
asymmetric, showing ‘tails’ on the higher binding energy side.
The asymmetry can be ascribed to the presence of water
adhering to each diamond sample.[26,27] Moreover, the binding
state corresponding to low binding energy in the C1s spectrum
is proposed to reflect the presence of residual carbon (that is,
graphite, amorphous carbon and/or carbide). Overall, the above
findings are in full accord with a successful phase transition
from GO to diamond having occurred under the experimental
conditions employed.
Pure diamond exhibits electrical insulating properties at
room temperature, with a very large band gap of about 5.4 eV
and electric resistance of 1010 ∼ 1014 Ω*cm. Nevertheless, P- and
Figure 4. (a) Survey XPS spectra of pristine GO, GO diamond MgO capsule
and GO diamond Ta capsule. (b) C1s XPS spectra of pristine GO, (c) GO
diamond MgO capsule and (d) GO diamond Ta capsule.
ChemistrySelect 2021, 6, 3399 – 3402
N-type semiconductor or superconductor properties have been
observed upon its doping with boron and phosphorus,
respectively, with the conductivity type depending on the
doping concentration.[28–30] Since it is possible to select the
desired doping element (or elements) as well as its percentage
present in the starting GO nanosheet, the strategy for the GO-
based materials for synthesizing homo and heteroatom-doped
diamonds are under experimental investigation. There have
been some recent reports on HPHT growth of diamond with
high phase purity using polycyclic organic compounds such as
naphthalene, which also have the potential of heteroatoms
doping of diamond.[31,32]
In conclusion, we have demonstrated the crystallization of
diamond from GO nano sheets using a high temperature/high
pressure method, with the XRD and Raman spectra confirming
the occurrence of the transition. Moreover, the respective XPS
spectra support the observation that the oxygen functional
groups of GO are removed, in agreement with the structural
phase transition occurring from the initial sp2 carbon sheet
structure to the three-dimensional sp3 carbon diamond
arrangement taking place.
Supporting Information Summary
The supporting information includes, i) experimental details, ii)
AFM images of GO nanosheets, iii) XRD pattern of GO nano-
sheets, iv) Raman spectra of GO Diamond MgO capsule and GO
Diamond Ta capsule, v) XRD spectra of GO Diamond MgO
capsule and GO Diamond Ta capsule and vi) XPS spectra of GO
Diamond MgO capsule and GO Diamond Ta capsule.
Acknowledgements
This work was supported by KAKENHI Grant-in-Aid for Scientific
Research (A) JP17H01200.
Conflict of Interest
The authors declare no conflict of interest.
Keywords: Diamond · Graphene oxide · HTHP method
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Submitted: February 19, 2021
Accepted: March 31, 2021
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