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Kyushu University, Fukuoka, Japan.

Effects of ball-milling treatment on physicochemical properties

and solid base activity of hexagonal boron nitrides

Ball-milling is an established method for obtaining fine particles

with high surface area from bulk materials. This top-down
technique not only increases the surface area of hexagonal boron
nitride (h-BN) by comminution, but it also imparts the material
with chemical functionalities and altered morphology. The
ball-milled h-BN showed catalytic activity for the nitroaldol
reaction and the h-BN milled at 400 rpm was the most
active catalyst.
See Atsushi Takagaki et al.,
Catal. Sci. Technol., 2019, 9, 302.

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Effects of ball-milling treatment on

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physicochemical properties and solid base activity
9, 302 of hexagonal boron nitrides
Shoichiro Namba,a Atsushi Takagaki, *bc Keiko Jimura, d
Shigenobu Hayashi, d

Ryuji Kikuchi a and S. Ted Oyama a

Received 10th May 2018,
Accepted 8th November 2018
DOI: 10.1039/c8cy00940f
rsc.li/catalysis
Hexagonal boron nitride (h-BN) was ball-milled at various rotation speeds (150–600 rpm) using a planetary
ball-mill. Ball-milling disrupted the layered structure of the h-BN, resulting in significant increases of sur-
face area. Ball-milling at 400 rpm gave the highest surface area of 412 m2 g−1 while higher rotation speeds
decreased the surface areas due to agglomeration. Moreover, ball-milling resulted in the emergence of
amino- and hydroxyl groups on the surface which were observed by Fourier transform infrared spectro-
scopy, and partial oxidation of the surface boron by the formation of B–OH groups was confirmed by
X-ray photoelectron spectroscopy. The appearance of trigonal B–O and tetrahedral B–O was observed by
boron-11 magic-angle spinning nuclear magnetic resonance spectroscopy. The number of base sites was
increased with the increase of rotation speeds of milling, corresponding to the formation of amino groups.
The ball-milled h-BN showed catalytic activity for the nitroaldol reaction between nitromethane and benz-
aldehyde in which the h-BN milled at 400 rpm exhibited the highest reaction rate and turnover frequency.
In addition, the ball-milled h-BN could convert glucose with the formation of fructose at 40 °C whereas
pristine h-BN showed no activity. The base sites were mainly responsible for the catalytic activity.

Introduction dehydrogenation (ODH) of light alkanes.17,18 The h-BN and

Ball-milling is an established method for obtaining fine parti-
cles with high surface area from bulk materials. This top-down
technique has been used for the synthesis of a variety of nano-
materials such as zeolites,1,2 metal oxides,3,4 carbon materials,5
and metal–organic frameworks.6 Such ball-milled materials
have broad applications as heterogeneous catalysts,7,8 electro-
catalysts,9 electrode materials,10 electronic devices,11 and hy-
drogen storage materials,12 and in drug delivery.13
Hexagonal boron nitride (h-BN) has a similar crystal struc-
ture as graphite and is sometimes called “white graphite.”
The h-BN is attracting much attention because of its fascinat-
ing properties which are applicable for ultraviolet laser de-
vices,14 dielectric layers for graphene devices,15 and protective
coatings.16 The h-BN is also found to be active for oxidative
a
Department of Chemical System Engineering, School of Engineering, The
University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan
b
Department of Applied Chemistry, Faculty of Engineering, Kyushu University,
744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan.
E-mail: atakagak@cstf.kyushu-u.ac.jp
c
International Institute for Carbon-Neutral Energy Research (I2CNER), Kyushu
University, Motooka, Nishi-ku, Fukuoka, 819-0395, Japan
d
Research Institute for Material and Chemical Measurement, National Institute of
Advanced Industrial Science and Technology (AIST), Central 5, 1-1-1 Higashi,
Tsukuba, Ibaraki 305-8656, Japan
its nanotubes functioned as metal-free catalysts for ODH of
propane and afforded very high selectivity to propylene and
ethylene.17 A hydroxylated BN (ref. 19) and ball-milled h-BN
(ref. 20) also catalyzed ODH of ethane with high selectivity to
ethylene. Furthermore, carbon doped BN nanosheets
exhibited high activity for ODH of ethylbenzene to styrene.21
For ODH reactions, it is considered that the oxidized boron
species formed on the edge sites of BN play an important role
in the activity.17–21
Ball-milling not only increases the surface area of h-BN by
comminution, but also imparts it with chemical functionali-
ties and altered morphology. Ball-milling under a hydrogen
atmosphere afforded hydrogenated boron nitride,22 and in
the presence of ammonia borane23 or aqueous NaOH solu-
tion24 produced exfoliated boron nitride nanosheets.
Recently, we have reported that the ball-milled h-BN func-
tioned as an efficient solid acid–base bifunctional catalyst
owing to the increase of surface area and the emergence of
hydroxyl- and amino groups on the surface.25 The ball-milled
h-BN exhibited high activity for base-catalyzed reactions such
as the nitroaldol reaction and Knoevenagel condensation.
Solid acid–base bifunctionality is well documented for or-
ganic amine-tethered silicas,26–28 but rare for nitride-based
materials, therefore further study of the material is necessary.
The objective of this report is to investigate the effect of ball-

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Catalysis Science & Technology
milling on the physicochemical properties of h-BN and its ac-
tivity as a solid base. Two types of base-catalyzed reactions
were carried out. One is the nitroaldol reaction of nitrometh-
ane and benzaldehyde because the reaction is one of the im-
portant C–C-bond formation reactions and is appropriate to
evaluate the solid acid–base bifunctionality as previously
reported.25 The coexistence of acidic OH groups facilitates
the activation of the aldehyde.25,26,28 The other is the trans-
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formation of glucose because it can be converted to
fructose via isomerization using a base or Lewis acid catalyst.
Conventional solid bases including hydrotalcite and MgO
were used for comparison because these solid bases can cata-
lyze the nitroaldol reaction29 and the isomerization.30,31
Experimental
The ball-milling method was used to exfoliate and disrupt
layered pristine h-BN. A quantity of 0.8 g of h-BN (Wako) was
ball-milled at several rotation speeds (150, 300, 400, 500, 600
rpm) using a planetary ball-mill (Pulverisette 7, Fritsch, zirco-
nia vessel with six zirconia balls (diameter 10 mm)). Ball-
milling was conducted for 24 cycles in which each cycle was
carried out for 30 min with 5 min intervals. The rotational di-
rection was reversed between cycles. The samples prepared
were denoted as BN 150–600 rpm, respectively.
The crystal structure of the h-BN was investigated by X-ray
diffraction (XRD, RINT-2700, Rigaku) with Cu Kα radiation (λ
= 0.1548 nm) at a voltage of 40 kV and a current of 100 mA.
Scans were obtained at a speed of 2° min−1 with a step width
of 0.02° for 2θ values of 10° to 60°.
The surface area was evaluated by the Brunauer–Emmett–
Teller (BET) method using nitrogen adsorption (BELLSORP
mini-II, Microtrac-BEL). The sample was pretreated by evacu-
ation at 200 °C for 1 h before the measurement. The pore
size distribution of the sample was obtained from analysis of
the adsorption branches of the isotherms using the Barrett,
Joyner, and Halenda (BJH) method.
The surface morphology of the h-BN was observed by
scanning electron microscopy (SEM, S-4700IJHitachi), and
JSM-7900F (JEOL)). The surface functional groups of the h-BN
were characterized by Fourier transform infrared spectro-
scopy (FTIR, FT/IR-6100, JASCO) measurements. The sample
was pressed into pellets with KBr for the measurements.
Boron-11 magic-angle spinning nuclear magnetic resonance
(11B MAS NMR) measurement was also carried out. The spec-
tra were recorded with a Bruker Avance III HD 600WB
spectrometer operating at a frequency of 192.63 MHz. A
Bruker MAS probe head was used with a zirconia rotor with
an outer diameter of 4 mm. The measurement was
performed at room temperature with a spinning rate of 12
kHz. The 11B spectrum was measured with a single pulse se-
quence combined with 1H high power decoupling during sig-
nal acquisition. The flip angle of the pulse and the recycle de-
lay were π/6 for solution and 30 s, respectively. The shift was
expressed with respect to neat boron trifluoride diethyl
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etherate (CF3·(C2H5)2O), by setting the signal of NaBH4 spin-
ning at 8 kHz to −42.00 ppm.
The oxidation state of elements and their compositions
over the surface were analyzed by X-ray photoelectron spectro-
scopy (XPS, JPS-9200, JEOL). The samples were exposed to the
atmosphere for these measurements, but the oxidation state
of the components is not expected to change because the
functional groups B–OH and NH2 are unreactive at room tem-
perature. Some adsorption of H2O is likely, but a considerable
amount would be desorbed by sample evacuation.
The base catalytic activity of ball-milled h-BN was deter-
mined through the nitroaldol reaction. The reaction was
conducted using an h-BN catalyst (50 mg) in 2 mL toluene so-
lution with benzaldehyde (0.5 mmol), nitromethane (1.25
mmol) and n-decane (0.1 mmol) as an internal standard. The
reaction was performed at 100 °C. It took 6 minutes to warm
the reaction mixture to this temperature. Aliquots were taken
using a syringe and analyzed by gas chromatography (GC-
FID; GC-2014, column DB-1MS, Shimadzu).
In addition, transformation of glucose was carried out
using 20 mg of the catalyst in 5 mL methanol with glucose
(0.17 mmol, 30 mg). The reaction was performed at 40 °C for
15 min. The reactant and products were analyzed by high
performance liquid chromatography (HPLC; LC-2000 plus,
JACO) equipped with a differential refractive index detector
(RI-2031 plus, JASCO) using an Asahipak NH2P-50 column
(flow rate: 1.0 mL min−1, eluent: CH3CN : H2O = 4 : 1). Reten-
tion times of glucose and fructose were identified as 12.1
min and 9.5 min.
Results and discussion
Fig. 1 shows the XRD patterns of h-BN samples before and af-
ter ball-milling at several rotation speeds. Pristine h-BN
showed sharp peaks corresponding to the (100), (002), (101),
Fig. 1 X-ray diffraction patterns of pristine and ball-milled h-BN.
Catal. Sci. Technol., 2019, 9, 302–309 | 303

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(102) and (004) reflections, indicating that the h-BN before
ball-milling had high crystallinity. No apparent change was
found for BN 150 rpm, suggesting that the slow rotation
speed did not engender much impact energy. In contrast, sig-
nificant weakening of all diffraction peaks was observed for
BN 300 rpm and BN 400 rpm, indicating that ball milling at
such rotation speeds disrupted both the layer and in-plane
structures of h-BN. At rotation speeds higher than 400 rpm,
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the peaks corresponding to the in-plane modes ((100) and
(102)) continuously weakened whereas those of the layer
structures ((002) and (004)) strengthened. The increase of the
peaks corresponding to the layered structures is likely due to
agglomeration of the fine particles. Agglomeration is a well-
known phenomenon for long time milling.32,33 No peaks for
other materials such as B2O3 and BIJOH)3 were found, which
is important because these boron compounds would exhibit
activity in acid–base reactions. To verify the crystallinity of
the samples, the peak width at half maximum intensity of
the (002) plane was calculated. The values of FWHM (degree)
were 0.18 for pristine h-BN, 0.21 for BN 150 rpm, 0.8 for BN
300 rpm, 0.54 for BN 400 rpm, 0.28 for BN 500 rpm, and 0.27
for BN 600 rpm. The mean crystallite sizes of the samples
were calculated using the Scherrer equation, D = Kλ/β cos θ
where K is the Scherrer constant (0.9), λ is the wavelength of
X-ray radiation (Cu Kα, 0.15418 nm), β is the FWHM in ra-
Fig. 2 (a) BET surface areas and (b) pore size distributions of pristine
and ball-milled h-BN.
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dians, and θ is the diffraction angle of the (002) plane in de-
grees (13.3). The mean crystallite sizes were 45 nm for pris-
tine h-BN, 39 nm for BN 150 rpm, 10 nm for BN 300 rpm, 15
nm for BN 400 rpm, 29 nm for BN 500 rpm, and 31 nm for
BN 600 rpm. The broad shoulders at ∼25 and ∼42 degrees
were observed for the ball-milled samples, which are likely at-
tributed to the amorphous phase.
Fig. 2 shows the surface areas and pore size distributions
of pristine and ball-milled h-BN samples. The BET surface
area of pristine h-BN was quite low, 3 m2 g−1. The surface area
was increased to 26 m2 g−1 for BN 150 rpm. A substantial in-
crease of the surface areas were found for BN 300 and BN 400
rpm, which were 384 and 412 m2 g−1, respectively. The surface
areas were decreased to 211 m2 g−1 for BN 500 rpm and 93
m2 g−1 for BN 600 rpm. These variations were in good agree-
ment with the results of XRD. The increase of surface areas
was attributed to the disruption of the structure of h-BN, and
the decrease of the surface areas by ball-milling at high rota-
tion speeds was likely due to agglomeration of the small parti-
cles. Both micropores and mesopores were monotonically in-
creased with the increase of the BET surface areas.
Fig. 3 SEM images of pristine h-BN (a and b), BN 400 rpm (c and d)
and BN 600 rpm (e and f).
Fig. 4 FTIR spectra of pristine and ball-milled h-BN.
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Fig. 3 shows SEM images of pristine h-BN, BN 400 rpm, culated to be 55% for trigonal B–N, 30% for trigonal B–O,
and BN 600 rpm. Pristine h-BN consisted of plate-like parti- and 15% for tetrahedral B–O.
cles with 1–10 μm in size. In contrast, BN 400 rpm was com- Fig. 6 shows the XPS spectra of h-BN samples. Fig. 6(a)
posed of small particles with less than one μm in size. BN displays the B1s spectra. Pristine h-BN had a single peak cen-
600 rpm had the same morphology as BN 400 rpm. tered at 191.0 eV.43,44 The sample BN 150 rpm showed almost
Fig. 4 shows FTIR spectra for h-BN before and after ball-
milling. A strong absorption centered at 1376 cm−1 and a
weak and sharp band at 819 cm−1 were observed for pristine
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h-BN. These peaks correspond to B–N stretching and B–N

bending vibrations, respectively.34,35 No differences in the
spectra of pristine h-BN and BN 150 rpm were observed. In
contrast, apparent changes were found for the samples ball-
milled at 300 rpm and higher rotation. The bands attributed
to B–N vibrations, ∼1376 cm−1 and ∼819 cm−1 decreased and
broadened with the increase of ball milling rotation speed.
Simultaneously, the bands at 1079 cm−1 and 925 cm−1
appeared for samples BN 300–600 rpm which can be ascribed
to B–O vibrations.36,37 Also, the bands around 3400 cm−1 and
3150 cm−1 were observed which can be assigned to O–H and
N–H stretching vibrations, respectively.25,36,38 These bands
became intense with the increase of milling rotation speed.
These indicate that hydroxyl- and amino groups were formed
by ball-milling via cleavage of B–N bonds.39
Fig. 5 shows the 11B MAS NMR spectra of ball-milled h-BN
(BN 400 rpm). Three signals are observed; the first one cen-
tered at about 24 ppm with an isotropic chemical shift (δiso)
of 29.6 ppm, the second one ranging from 18 to 8 ppm with
an δiso of 18.8 ppm, and the third narrow one with an δiso of
0.8 ppm. The signal with the shift of 29.6 ppm is attributed
to trigonal boron connected with nitrogen, B–N,40 which is
dominant in h-BN. The second one with an δiso of 18.8 ppm
is ascribed to trigonal boron bonded with oxygen, B–O.41 The
appearance of this signal was in good agreement with the re-
sults of FTIR. The signal at 0.8 ppm is attributed to tetrahe-
dral boron, which might be due to the formation of B–OIJH)
on the basal plane of h-BN or amorphous boron oxide. The
appearance of the tetrahedral boron was also reported for the
ball-milled h-BN with LiOH.42 The distribution of B was cal-

Fig. 6 XPS spectra of pristine and ball-milled h-BN. (a) B1s, (b) N1s
11
Fig. 5 B MAS NMR spectra of ball-milled h-BN (BN 400 rpm). and (c) O1s.

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Table 1 Surface compositions of pristine and ball-milled h-BN calculated
from XPS
Sample N/B O/B BB–O/(BB–N + BB–O)
Pristine h-BN 0.97 0 0
BN 150 rpm 0.92 0.01 0.0
BN 300 rpm 0.84 0.13 0.10
BN 400 rpm 0.78 0.34 0.26
BN 500 rpm 0.61 0.55 0.40
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BN 600 rpm 0.62 0.49 0.30
the same spectrum as pristine h-BN. At rotation speeds of
300 rpm and higher, an additional peak centered at 193.1 eV
appeared which is ascribed to oxidized boron, B3+.43,45–47 The
oxidized boron was related to the formation of B–OH groups,
and the relative composition of oxidized boron to h-BN struc-
tural boron BB–O/(BB–N + BB–O) increased with the increase of
rotation speed. The ratios were 0 for BN 150 rpm, 0.10 for BN
300 rpm, 0.26 for BN 400 rpm, 0.40 for BN 500 rpm, and 0.30
for BN 600 rpm. The samples ball-milled at high rotation
speeds had a layered structure with low surface areas as
shown in Fig. 1 and 2, which was likely due to agglomeration.
It can be considered that the inner part of the agglomerated
particles was hard to be oxidized, resulting in the decrease of
the ratio of oxidized boron to structural boron (BB–O/(BB–N +
BB–O)) for BN 600 rpm. Fig. 6(b) shows the N1 s XPS spectra.
A single peak centered at 398.8 eV was observed for all sam-
ples. The peak weakened and broadened with the increase of
rotation speed. The broad spectra of the ball-milled h-BN
samples at high rotation speeds may involve amino groups in
addition to structural nitrogen, but difficult to be separated.
Fig. 6(c) shows the O1s XPS spectra. A single peak centered at
533.5 eV appeared for BN 300 rpm. The peak strengthened
with the increase of rotation speed.
Table 1 lists the results of N/B, O/B atomic ratios on the
h-BN surface calculated from XPS. The N/B ratio for pristine
h-BN was close to one. As the rotation speed became high,
the O/B ratio was increased from 0 to 0.55 whereas the N/B
ratio was decreased. The ratio of oxygen to oxidized boron, O/
BB–O, was 1.26 for BN 300 rpm, 1.31 for BN 400 rpm, 1.38 for
BN 500 rpm, and 1.62 for BN 600 rpm. The O/BB–O ratios were
between one and two, suggesting that the average structure is
a mixture of single and germinal hydroxyl groups, B–OH and
BIJOH)2. The increase of the O/BB–O ratios indicates the incre-
ment on the proportion of germinal hydroxyl groups via suc-
cessive cleavage of the B–N bond.
Fig. 7 shows the results of the nitroaldol reaction of nitro-
methane and benzaldehyde using ball-milled h-BN. No activ-
ity was found for BN 150 rpm. A small degree of activity for
the nitroaldol reaction was found with BN 300 rpm for which
the reaction rate was 0.69 mmol g−1 h−1. The reaction rate
was much increased for BN 400 rpm to 2.3 mmol g−1 h−1. A
similar activity was found for BN 500 rpm, and then the activ-
ity decreased for BN 600 rpm. The number of base sites in
ball-milled samples was determined by titration using
benzoic acid. No or negligible base sites were found in BN
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O/BB–O
—
—
1.26
1.31
1.38
1.62
Fig. 7 Reaction rate for nitroaldol reaction using ball-milled h-BN.
150 rpm. For the other samples, the number of base sites
was 0.31 mmol g−1 in BN 300 rpm, 0.52 mmol g−1 in BN 400
rpm, 0.83 mmol g−1 in BN 500 rpm and 0.74 mmol g−1 in BN
600 rpm. The increase of the number of base sites is in good
agreement with the FTIR results in which the intensity of the
band corresponding to the N–H bond was increased. Table 2
summarizes the reaction rates, number of base sites, and
turnover frequencies (TOFs) as well as the surface areas. The
TOF increased from 2.2 h−1 for BN 300 rpm to 4.4 h−1 for BN
400 rpm and then decreased to 2.6 h−1 for BN 500 rpm and
1.6 h−1 for BN 600 rpm. BN 400 rpm showed the highest reac-
tion rate and the highest TOF among the samples tested.
Given that TOFs for structure-sensitive reactions can vary by
106 and more,48 such differences are considered to be small
and indicated that the base sites are catalyzing the reaction.
It was found that the reaction rates were not directly corre-
lated with surface areas (see Fig. 2 and 7). The surface area of
BN 300 rpm was close to that of BN 400 rpm, but the reaction
rate over BN 300 rpm was lower than that over BN 400 rpm.
Also, the reaction rates over BN 400 rpm and BN 500 rpm
were similar, but the surface area of BN 500 rpm was half of
that of BN 400 rpm. It is concluded that the number of base
sites does not track the surface areas because of differences
in exposed surfaces. The base sites are primarily responsible
for the catalytic activity. In addition, the dependence of the
surface areas on the catalytic activity was estimated. The areal
reaction rates should be a constant if the active sites were
uniformly formed on the basal plane of h-BN. However, the
areal reaction rates were increased with the increase of the
rotation speed. The areal reaction rate was 0 μmol m−2 h−1
for BN 150 rpm, 1.8 μmol m−2 h−1 for BN 300 rpm, 5.6 μmol
m−2 h−1 for BN 400 rpm, 10 μmol m−2 h−1 for BN 500 rpm,
and 13 μmol m−2 h−1 for BN 600 rpm. This indicates that
most of the active sites were formed on the edge sites of ball-
milled h-BN. The catalytic activities of ball-milled h-BN cata-
lysts were compared with those of calcined MgO, calcined
hydrotalcite (HT), and n-butylamine. The reaction rate was
0.3 mmol g−1 h−1 for MgO, 1.8 mmol g−1 h−1 for HT, and 4.9
mmol g−1 h−1 for n-butylamine. The TOFs of MgO, HT, and
n-butylamine were much lower than that of BN 400 rpm.
Table 3 shows the results of the nitroaldol reaction using
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Table 2 Results of nitroaldol reaction of nitromethane and benzaldehyde using ball-milled h-BNa

Sample SBET/m2 g−1 Base sites/mmol g−1 Reaction rate/mmol g−1 hour−1 TOF/h−1
BN 150 rpm 26 0 0.0 0
BN 300 rpm 384 0.31 0.69 2.2
BN 400 rpm 412 0.52 2.3 4.4
BN 500 rpm 211 0.83 2.2 2.6
BN 600 rpm 93 0.74 1.2 1.6
Calcined MgOb 20 0.31 0.3 1.0
Calcined HTc
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109 2.03 1.8 0.9

n-Butylamined — 13.7 4.9 0.4
a
100 °C. b
Pretreated at 700 °C for 2 h. c Hydrotalcite (Mg/Al = 3). Pretreated at 500 °C for 2 h. d 0.05 mmol.

Table 3 Results of nitroaldol reaction of nitromethane and benzalde- formation of β-nitrostyrene by nucleophilic attack of
hyde and using ball-milled h-BN for 12 h
deprotonated nitromethane. Kinetic isotope effect experi-
Nitroaldol reactiona ments using CD3NO2 revealed that the abstraction of a pro-
Sample Conv./% Selectivity to β-nitrostyrene/% ton from nitromethane by base sites of the BN catalyst was
the rate-determining step. This is in good agreement with the
BN 150 rpm 0 0
BN 300 rpm 10 37 present study because the base sites are mainly responsible
BN 400 rpm 68 77 for the catalytic activity.
BN 500 rpm 20 50 The catalytic activity of ball-milled h-BN was further inves-
BN 600 rpm 15 29 tigated by transformation of glucose. Fig. 8 shows the results
a
Reaction conditions: benzaldehyde (0.5 mmol), nitromethane (1.25 of transformation of glucose using ball-milled h-BN catalysts
mmol), catalyst (50 mg), toluene (2 mL), 100 °C, 12 h. at 40 °C for 15 min. The ball-milled samples exhibited high
conversion with the formation of fructose whereas pristine
h-BN did not. Conventional solid bases including MgO and
ball-milled h-BN catalysts for 12 h. BN 400 rpm showed the hydrotalcite showed moderate glucose conversion with no
highest conversion (68%) with the highest selectivity to formation of fructose, suggesting that the apparent glucose
β-nitrostyrene (77%). conversion was probably due to the adsorption of glucose on
Our previous study has investigated the acid–base the solids at 40 °C. The sample BN 400 rpm showed the
bifunctionality of the ball-milled h-BN for the nitroaldol reac- highest conversion among the samples tested, which is in
tion,25,26,49 and the proposed reaction sequence is shown in good agreement with the results of the nitroaldol reaction.
Scheme 1. The reaction involves (1) the abstraction of a pro- The base-catalyzed aldose-ketose isomerization is named the
ton from nitromethane by an amino group of the BN catalyst, Lobry de Bruyn–van Ekenstein transformation in which de-
(2) formation of an imine intermediate by nucleophilic attack protonation of the α-carbonyl carbon of glucose with a base
of an amino group of the catalyst on the aldehyde group of is the first step. It can be considered that a hydroxyl group of
benzaldehyde with the aid of polarization of the carbonyl the BN catalyst would help the polarization of the carbonyl
group by a hydroxyl group of the BN catalyst,50,51 and (3) the group, which accelerates the isomerization as same as the

Fig. 8 Results of glucose transformation in methanol at 40 °C using

Scheme 1 Proposed reaction sequence of nitroaldol reaction on the ball-milled h-BN. (Reaction conditions: glucose (0.17 mmol, 30 mg),
ball-milled h-BN catalyst.20 catalyst (20 mg), methanol (5 mL), 40 °C, 15 min.)

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Paper
nitroaldol reaction. The yield of fructose of the sample BN
400 rpm was slightly lower than that of the sample BN 600
rpm, probably due to the further transformation of fructose
such as retro-aldol reaction.
Conclusions
Hexagonal boron nitride solid base catalysts were prepared
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by simple ball-milling at several rotation speeds of a commer-
cial low-surface area boron nitride. XRD revealed that ball-
milling at a rotation speed of 300 rpm or higher disrupted
the layer structure of pristine h-BN. Nitrogen-adsorption mea-
surements indicated that the surface areas were drastically
increased from 3 m2 g−1 for pristine h-BN to ca. 400 m2 g−1
for h-BN 300 rpm and h-BN 400 rpm. At a rotation speed of
400 rpm and higher the surface areas decreased likely
due to agglomeration as indicated by SEM and XRD. FTIR
and XPS measurements showed the formation of amino- and
hydroxyl groups on the surface of the ball-milled h-BN. The
number of base sites increased with the increase of ball-
milling speeds. The ball-milled h-BN exhibited catalytic activ-
ity in the nitroaldol reaction between nitromethane and benz-
aldehyde, in which h-BN 400 rpm was the most active cata-
lyst. The base sites were responsible for the activity.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was supported by a Grant-in-Aid for Challenging
Exploratory Research (No. 16K14474) and Science Research
(B) (No. 18H01785) of JSPS, Japan. A part of this work was
supported by the AIST Nanocharacterization Facility (ANCF)
platform as a program of the Nanotechnology Platform of the
Ministry of Education, Culture, Sports, Science and Technol-
ogy (MEXT), Japan.
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