Spherical Superstructure of Boron Nitride Nanosheets Derived from Boron-Containing Metal-Organic Frameworks

Article abstract of DOI:10.1021/jacs.0c01023

The assembly of two-dimensional (2D) nanosheets into three-dimensional (3D) well-organized superstructures is one of the key topics in materials chemistry and physics, due to their potential applications in various fields. Herein, starting from the crystalline metal-organic framework (MOF) particles, a spherical superstructure consisting of metal-organic framework nanosheets (SS-MOFNSs) is synthesized via a simple solvothermal transformation process. After pyrolysis and nitrogenization in ammonia, the SS-MOFNSs are further transformed into the spherical superstructure consisting of boron nitride nanosheets (SS-BNNSs), which preserve the original spherical superstructure morphology. Taking advantage of this unique superstructure, the resulting SS-BNNSs exhibit excellent catalytic activity for selective oxidative dehydrogenation of propane to produce propylene and ethylene. The results of this work provide a novel synthetic strategy to fabricate 3D spherical superstructures consisting of 2D nanosheets for high-performance applications in catalysis, energy storage, as well as other related fields.

Full text of DOI:10.1021/jacs.0c01023

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Article
A Spherical Superstructure of Boron Nitride Nanosheets
Derived from Boron-Contained Metal-Organic Frameworks
Lei Cao, Pengcheng Dai, JING TANG, Dong Li, Ruihua Chen, Dandan Liu, Xin
Gu, Liangjun Li, Yoshio Bando, Yong Sik Ok, Xuebo Zhao, and Yusuke Yamauchi
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 28 Mar 2020
Downloaded from pubs.acs.org on March 28, 2020
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A Spherical Superstructure of Boron Nitride Nanosheets Derived
from Boron-Contained Metal-Organic Frameworks
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Lei Cao,1 Pengcheng Dai,*1 Jing Tang,2 Dong Li,3 Ruihua Chen,1 Dandan Liu,1 Xin Gu,1 Liangjun Li,1
Yoshio Bando,2,4,5,6 Yong Sik Ok,7 Xuebo Zhao*1 and Yusuke Yamauchi*2,8,9
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Institute of New Energy, College of New Energy, State Key Laboratory of Heavy Oil Processing, China University
of Petroleum (East China), Qingdao 266580, P. R. China.
Australian Institute for Bioengineering and Nanotechnology (AIBN), The University of Queensland, Brisbane,
Queensland 4072, Australia.
State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Bei Jing), Beijing 102249, P. R.
China.
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Institute of Molecular Plus, Tianjin University, Tianjin 300072, P. R. China.
Australian Institute for Innovative Materials, University of Wollongong, North Wollongong, NSW, 2500 Australia
International Center for Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science
(NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan
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Korea Biochar Research Center, APRU Sustainable Waste Management & Division of Environmental Science and
Ecological Engineering, Korea University, Seoul 02841, South Korea
School of Chemical Engineering, Faculty of Engineering, Architecture and Information Technology, The University
of Queensland, Brisbane, Queensland 4072, Australia.
Department of Plant and Environmental New Resources, Kyung Hee University, 1732 Deogyeong-daero, Giheung-
gu, Yongin-si, Gyeonggi-do 446-701, South Korea.
ABSTRACT: The assembly of two-dimensional (2D) nanosheets into three-dimensional (3D) well-organized superstructures is
one of the key topics in materials chemistry and physics, due to their potential applications in various fields. Herein, starting from
the crystalline metal-organic framework (MOF) particles, a spherical superstructure consisting of metal-organic framework
nanosheets (SS-MOFNSs) is synthesized via a simple solvothermal transformation process. After pyrolysis and nitrogenization in
ammonia, the SS-MOFNSs is further transformed into the spherical superstructure consisting of boron nitride nanosheets (SS-
BNNSs), which preserve the original spherical superstructure morphology. Taking advantage of this unique superstructure, the
resulting SS-BNNSs exhibit excellent catalytic activity for selective oxidative dehydrogenation of propane to produce propylene
and ethylene. The results of this work provide a novel synthetic strategy to fabricate 3D spherical superstructures consisting of 2D
nanosheets for high-performance applications in catalysis, energy storage, as well as other related fields.
cleavage of C-H bonds and provide a promising alternative to
meet the increasing gap between demand and supply of
INTRODUCTION
Hexagonal boron nitride (h-BN), a structural analog of
graphite, has attracted significant research interests due to its
superb thermal/chemical stabilities, high thermal conductivity,
excellent optoelectronic properties, and intrinsic electrical
insulation.1-2 Their controlled nanoarchitectures, such as 0D
nanoparticles,3-4 1D nanotubes,5-6 2D nanosheets,7-8 and 3D
nanoporous structures,9-10 are very promising for applications
in various areas including sensor,11 pollutant removal,12-13 and
thermal-conductive polymers.14-15 In addition to these
traditional properties-driven applications, h-BN has recently
been found to be a break-through catalyst for selective
oxidative dehydrogenation of propane (ODHP) to produce
propylene and ethylene,16 essential building blocks (> 250
million metric tons per year) in the production of various
chemicals.17 For instance, it was reported that h-BN could
catalyze ODHP with high propylene (79 %) and ethylene (12
%) selectivity at a propane conversion of 14 %.16 Edge
hydroxylated h-BN exhibited an enhanced propylene
selectivity (80.2 %) at a propane conversion of 20.6 %.18
These results present a new metal-free catalyst for selective
olefins.
Although outstanding ODHP performance has been
achieved by h-BN, the olefins yield is still not satisfactory for
practical applications, because the olefins selectivity at high
propane conversion is still relatively low. In general, the
olefins yield must be higher than 30% for the commercial
viability of a process.19-21 Thus, research efforts on h-BN
catalysts still have to be spent toward higher activity and
higher olefins yield. Since oxygen-containing boron sites on
the edges of h-BN are decisive for its unique catalytic function
in the ODHP reaction,22-23 maximizing the number of oxygen-
containing boron sites by nanostructural engineering may be
the most effective option to improve the catalytic activity of h-
BN.24 Constructing hierarchical 3D architectures,25-26
especially spherical organization based on 2D h-BN
nanosheets, is an effective strategy for exploring more edge
active sites, and therefore, is highly desirable for improving
the catalytic activity of h-BN. Nevertheless, although various
techniques have been reported for the synthesis of h-BN
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nanostructures with controllable size and morphology,2, 27 no
synthetic strategy has been developed for controlling the
assembly of 2D h-BN nanosheets into 3D spherical
superstructure.
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crystal structure solution. The refined atomic position,
equivalent isotropic displacement parameters, selected bond
lengths, and bond angles of SS-MOFNSs are listed in Table
S2-S4. The resulting MOF (SS-MOFNSs) is crystallized in a
trigonal space group P123 with cell parameters of a=8.6527 Å,
b=8.6527 Å, and c=15.0844 Å. Each Zn(II) metal center is
coordinated by three oxygen donor atoms from borate ions and
one nitrogen atom from 2-methylimidazole, leading to a four-
coordinated pyramid geometry. Zn(II) ions and borate ions
formed 2D graphene-like layers (denoted as ZnBO layers)
consisting of irregular hexagon circles, as shown in Figure 2b.
Each irregular hexagon circle is formed of one B atom, two Zn
atoms, and three O atoms. The N atoms of 2-methylimidazole
are connected by two Zn(II) ions in a monodentate form,
which can link the 2D ZnBO layers along the z-axis in series
and formed a 3D structure (Figure 2c, Figure S3).
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The main target of this study is to synthesize a spherical
superstructure of hexagonal boron nitride nanosheets (SS-
BNNSs). Using metal-organic frameworks (MOFs) as self-
sacrificial templates has recently been proved to be a
promising strategy to prepare spherical superstructures.28 The
MOFs are a kind of emerging materials of metal ions coupled
with organic linkers.29-31 The thermal transformation of MOFs
is an efficient strategy to produce carbon and carbon-based
materials,32-33 metal oxides,34-36 metal chalcogenides,37-38 metal
phosphides and metal carbides with controlled morphology.39-
42 Up to now, there is no precedent that MOFs can produce h-
BN materials due to the less existence of MOFs materials
containing abundant boron atoms. In this work, we newly
design a new kind of boron-containing MOFs with a novel
spherical superstructure composed of nanosheets (SS-
MOFNSs), which can be easily transformed to SS-BNNSs by
nitrogenization under an ammonia atmosphere (Figure 1). The
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The morphology of SS-MOFNSs was investigated by field
emission scanning electron microscopy (SEM). As shown in
Figure 2d, the as-prepared SS-MOFNSs exhibit a 3D spherical
superstructure (7-10 μm in diameter) with massive 2D MOF
nanosheets (~60 nm in thickness) ordered along the three
directions (Figure 2e). The Brunauer-Emmett-Teller (BET)
surface areas and pore volumes of SS-MOFNSs are 24.4 m2 g-
as-prepared
SS-BNNSs
with
preserved
spherical
superstructure afford an olefins yield of 40.2% (propylene
27.8% and ethylene 12.4%), which is the highest in ODHP
using h-BN-based catalysts.
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and 0.13 cm3 g-1, respectively (Figure 2f), which are much
lower than those of the starting ZIF-8 NPs (1799 m2 g-1, 0.94
cm3 g-1) (Figure S4), probably due to the different pore
structures of SS-MOFNSs and ZIF-8. Figure S5 shows the
TGA data of SS-MOFNSs. The first weak weight-loss can be
attributed to the loss of minute quantities of guest molecules,
and the second weight-loss is mainly the loss of methyl in 2-
methylmidazole. The last rapid weight-loss step corresponds
to the decomposition of organic ligands. The whole weight-
loss is about 30.6%, which agrees with the theoretical mass
ratio of organic ligands (29.9%). The FT-IR and XPS results
also agree with the crystal structure of SS-MOFNSs (Figure
S6-S7).
RESULTS AND DISCUSSION
Figure 1 illustrates the synthetic process for SS-MOFNSs and
SS-BNNSs. In general, zeolitic imidazolate framework-8
(ZIF-8) nanoparticles (Figure S1) were chosen as the precursor
to produce SS-MOFNSs. Through
a
solvothermal
transformation process at 150 ºC, ZIF-8 nanoparticles reacted
with boric acid and formed SS-MOFNSs. Annealing SS-
MOFNSs at 1000 ºC under an ammonia atmosphere,
preserving their original morphology, gave rise to the
formation of SS-BNNSs with 2D h-BN nanosheets assembled
into 3D spherical superstructure.
Figure 1. Schematic illustration of the creation of SS-MOFNSs
and SS-BNNSs.
Figure 2. (a) Final Rietveld refinement profile of SS-MOFNSs.
(b) The crystal structure of ZnBO layer. (c) The whole crystal
structure of SS-MOFNSs. (d-e) SEM images of SS-MOFNSs
with different magnification. All the scale bars are 1 μm. (f)
Nitrogen adsorption-desorption isotherm of SS-MOFNSs. The
inset shows the corresponding pore size distribution.
The XRD pattern of as-achieved SS-MOFNSs is entirely
different from that of ZIF-8 (Figure S2), indicating the
formation of a new MOF, whose composition is determined to
be Zn2(BO3)1(C4N2H5)1 by elemental analysis (Table S1). The
structure of this boron-containing MOFs can be successfully
determined from the powder X-ray diffraction data. As shown
in Figure 2a, the Rietveld refinement is in good agreement
with the experimental XRD result with the profile factor of
Rp=3.1%, Rwp=3.8%, and GOF =1.793, which validates the
To understand the formation mechanism of SS-MOFNSs,
we studied the transformation processes by temperature- and
time-dependent control experiments (Figures S8-S9). At 110
ºC, the product maintains the original crystal structure of ZIF-
8 (Figure S8a), showing the original nanoparticle morphology.
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Figure 3. (a) XRD pattern of SS-BNNSs. (b-c) SEM images of
However, some of the particles start to crack into small
irregular particles (Figure S9a), indicating that ZIF-8 particles
are partially decomposed. At 120 ºC, the new phase appears.
The SEM image (Figure S9b) reveals that all the ZIF-8
particles break down into small particles, and a small amount
of 2D nanosheets appear. When the temperature increases to
130 ºC, ZIF-8 particles are mostly converted to the new crystal
phase, although the ZIF-8 peaks and the intermediate peaks
still exist. Correspondingly, 2D nanosheets are found to be the
main product, and few ZIF-8 particles can be observed from
the SEM image (Figure S9c). The ZIF-8 particles completely
disappear at temperatures higher than 140 ºC (Figure S9d),
leaving only spherical superstructure consisted of 2D
nanosheets (Figure S9d). At 150 ºC, the XRD peaks derived
from only the new phase of SS-MOFNSs can be observed
(Figure S8a). The above temperature-dependent control
experiments reveal that boric acid, due to its acidic nature, can
etch ZIF-8 particles43, resulting in the slow decomposition of
ZIF-8 particles when the temperature is above 110 ºC. The
boric acid reacts with the dissolved zinc ions and 2-
methylimidazole, generating the new crystal phase from 120
ºC.
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SS-BNNSs with different magnification. All the scale bars are 1
μm. (d-e) TEM images of SS-BNNSs with different
magnification. (f) Nitrogen adsorption-desorption isotherm of the
SS-BNNSs. The inset shows the corresponding pore size
distribution.
Annealing of SS-MOFNSs at 1000 ºC under dynamic
ammonia atmosphere for 6 h produced the well-defined SS-
BNNSs. The XRD results in Figure 3a reveals the formation
of a highly crystallized h-BN structure. The diffraction peaks
at 2θ = 25.7º and 42.1º corresponds to the (002) and (100)
planes of h-BN, respectively. No peaks corresponding to Zn
and Zn-related compounds can be observed, which reveals that
Zn is entirely absent from SS-BNNSs. SEM image illustrates
that SS-BNNSs preserve the original morphology of SS-
MOFNSs with 2D h-BN nanosheets assembled into a 3D
spherical superstructure (Figure 3b). The diameter of SS-
BNNSs is 7-10 μm (Figure S12), consistent with that of SS-
MOFNSs. However, the thickness of nanosheets decreases 25-
30 nm (Figure 3c), which is attributed to the decomposition of
organic ligands. Some pores appear on the BN nanosheets
(white circle in Figure 3c), verifying the departure of the
volatile components. The transmission electron microscopy
(TEM) images (Figure S13) confirm that the interior of SS-
BNNSs possesses a porous structure. HRTEM image indicates
that dozens of h-BN (002) layers within the nanosheets, with
an interlayer crystal lattice spacing of 0.35 nm corresponding
to the (002) crystal planes of h-BN (Figure 3e).44-45 The N2
adsorption-desorption isotherm (Figure 3f) indicates that SS-
BNNSs have similar type-IV isotherms with that of SS-
MOFNSs, but possess a much higher BET surface area of 476
m2 g-1 and pore volume of 1.87 cm3 g-1. The pore size
distribution of SS-BNNSs contains abundant mesopores in the
range of 5-40 nm. Such open mesopores of SS-BNNSs
provide effective channels for gas diffusion, which is
advantageous for the contact between reactant gases and active
sites on the catalysts. The SEM elemental mapping (Figure
S14) reveals the uniform distribution of boron, nitrogen, and
oxygen.
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Figures S8b and S10 illustrate the XRD patterns and SEM
images of products obtained with different reaction times at
150 ºC. The appearance of the new crystal phase starts at a
reaction time of 3 h, resulting in the crack of nanoparticles and
the generation of small irregular particles consisting of 2D
nanosheets (Figure S10a). When the reaction time reaches 7 h,
the new crystal phase becomes the main phase, showing the
co-existence of flower-like superstructures and detached
nanosheets (Figure S10c). When the reaction time reaches at
10 h (Figure S10d), the sample displays uniform spherical
superstructures. The time-dependent control experiments show
individual MOFNSs are firstly formed in the morphology of
detached nanosheets during the reaction. The detached
nanosheets are assembled into small irregular superstructures,
and then uniform spherical superstructures with the extension
of the reaction time. In brief, the above investigation indicates
that the formation of SS-MOFNSs is a stepwise transformation
process. The slow dissolution of ZIF-8 particles provides a
continuous supply of low-concentration zinc ions and 2-
methylimidazole, which react with boric acid at a slow growth
rate and lead to the formation of MOFNSs. On the contrary,
directly heating zinc nitrate hexahydrate, 2-methylimidazole,
and boric acid in methanol yield nanosheets with random
shapes and sizes (Figure S11), which could be attributed to the
rapid nucleation of MOF in high reactant concentration.
Figure 4. (a) XPS survey spectrum of SS-BNNSs. (b-d) XPS
spectra of N 1s, B 1s, and O 1s, respectively. (e) The FT-IR
spectrum of SS-BNNSs. (f) TGA curve of SS-BNNSs under the
air atmosphere.
XPS data provides the specific contents and the detailed
chemical states of the elements on the surface of SS-BNNSs.
The XPS survey spectrum (Figure 4a) shows that SS-BNNSs
mainly contains boron, nitrogen, oxygen, and some C
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impurity, whose contents are listed in Table S5. The content of
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stability test (Figure S18), indicating excellent chemical
stability of SS-BNNSs and ignorable coke deposition.
Comparison of the physical and chemical properties of SS-
BNNSs before (fresh) and after (spent) ODHP test also shed
light on the stability of SS-BNNSs catalyst. The SEM images
(Figure S19) revealed that the diameter of SS-BNNSs is 7~10
μm, and the thickness of h-BN nanosheets is still 25~30 nm,
indicating that SS-BNNSs keep the original morphology after
the ODHP test. The XRD pattern of the SS-BNNSs-Spent
(Figure S20) shows diffraction peaks ascribed to the (002) and
(100) planes of h-BN, consistent with that of the fresh sample,
revealing the permanent crystal structure. After the ODHP
test, the SS-BNNSs still have a BET surface area of 439 m2 g-1
and a pore volume of 1.77 cm3 g-1 (Figure S21), proving the
excellent mechanical stability. The surface properties of SS-
BNNSs-spent were characterized by XPS (Figure S22). The
XPS survey spectrum of SS-BNNSs-Spent exhibits no
significant change compared with that of the SS-BNNSs-Fresh
(Figure 4a-d). The carbon content of SS-BNNSs-Spent is only
0.66 at.% (Table S7), illustrating ignorable coke deposition
during the ODHP process. The N 1s, B 1s, and O 1s spectra of
SS-BNNSs-Spent are nearly the same with those of fresh SS-
BNNSs, suggesting the unchanged surface properties. Based
on all the characterizations mentioned above, it is evident that
SS-BNNSs exhibit outstanding stability during the long-term
and high-temperature test, demonstrating the potential for
industrial application. What is more, almost the same catalytic
performance is successfully obtained, when the SS-BNNSs-
Spent sample is employed for the second run of the ODHP
reaction, which revealed the outstanding repeatability of SS-
BNNSs (Figure S23).
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oxygen reached 4.03 at.%, indicating massive oxygen species
on the surface of SS-BNNSs. The N 1s spectrum (Figure 4b) is
fitted as N-B3 (398.1 eV) and HN-B2 (400.0 eV) species.7, 46
The B 1s spectrum (Figure 4c) can be fitted into two peaks at
190.4 eV and 191.9 eV, arising from the signal of B in B-N,
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and B-OH bonds, respectively.7,
The peaks in the O 1s
spectrum (Figure 4d) can be perfectly fitted into B-OH species
(532.6 eV).18, 47-48 The C impurity can be attributed to the C
dopants in BN or the adsorbed organic pollutants (Figure
S15a). Fourier transform infrared (FT-IR) analysis was also
carried out to identify the functional groups of SS-BNNSs
further. As illustrated in Figure 4e, the peaks at ~ 3400 cm-1
and ~ 1170 cm-1 correspond to the stretching vibration of OH
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and B-O, which also confirms the existence of B-OH
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species.16,
These results reveal that SS-BNNSs contain
massive oxygen-containing boron species on the surface
(Figure S15b), which have been reported as useful active sites
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for the ODHP reaction.18,
TGA data under the air
atmosphere revealed the excellent oxidation resistance of SS-
BNNSs. As shown in Figure 4f, SS-BNNSs exhibit no weight-
loss even though the temperature went up to 800 °C. A little
upward trend occurring from 800 °C is resulted from the
oxidation of BN to produce the corresponding oxides (B2O3).50
The superior anti-oxidation ability under high temperature
makes SS-BNNSs a valuable catalyst for the ODHP reaction.
Once prepared, SS-BNNSs is readily used as a catalyst for
ODHP without any further activation. The catalytic reaction
was carried out in a fixed-bed microreactor (Figure S16).
Figure 5a shows the ODHP catalytic performance of SS-
BNNSs as a function of reaction temperature (450-515 °C).
The conversion of propane was around 5 % at 450 °C, while
the selectivities of propylene and ethylene were 89 % and 5 %,
respectively. When the reaction temperature rises to 490 °C,
the propane conversion increase to 21 %, and the selectivity of
propylene and ethylene is 78% and 10%, which surpasses the
performance of other previously published h-BN materials at
the same reaction temperature (Table S6). At 510 °C, the
conversion of propane has risen to 58 %, and the propylene
selectivity is still around 48 %, yielding the maximum
propylene yield of 27.8% (Figure 5b). Meanwhile, the
ethylene selectivity increases to 21%, providing an ethylene
yield of 12.4%. Thus, the overall olefins yield is 40.2%, which
is the highest olefins yield achieved by h-BN based catalysts
so far (Table S6). The olefins yield continues to grow as the
reaction temperature increases, but the propylene yield starts
to reduce due to the cracking of propylene into ethylene at
high temperature. It is more attractive that the CO2 selectivity
is less than 2% throughout the whole process, and the
byproducts are mainly ethylene and CO, which are both
valuable feedstocks for a vast array of chemicals.51-52 Weight
hourly space velocity (WHSV) affects the propane conversion
and propylene selectivity as well (Figure S17a), and the
reaction order of reaction gas (2.23 for propane and 0.77 for
O2, Figure S17b) is in good agreement with the previous
reports.16, 18
Figure 5. (a) Propane conversion and product selectivity as a
function of reaction temperature over SS-BNNSs. (b) The olefins
yield as a function of propane conversion. (c) Stability test of SS-
BNNSs for ODHP at 490 °C. (d) Comparison of propane
conversion and product selectivity among the different catalysts at
490 °C. (e) Comparison of olefins yield between SS-BNNSs, C-
BNNSs, and P-BNFs. (f) Reaction rate as a function of reaction
temperature over SS-BNNSs, C-BNNSs, and P-BNFs.
The assembly of 2D BN nanosheets into 3D ordered
architectures not only inherits the exceptional properties of
their building blocks, but also exhibit certain unconventional
advantages caused by the unique 3D structures, thus rendering
them attractive candidates for various applications.53-54 For
instance, 3D porous BN nanosheets reported by Li et al.
exhibited much higher absorption capacities for organic
pollutants than 2D BN nanosheets.55 The unique 3D porous
structure made of BN nanosheets with high-density adsorption
sites are believed to play a key role in the excellent pollutant
The long-term stability of SS-BNNSs for ODHP was
conducted at 490 °C for 100 hours (Figure 5c). The propane
conversion is 20 ± 1% during the test, and the selectivity of
propylene and ethylene stays at around 78 ± 1% and 10 ± 1%,
respectively. The almost unchanged olefins selectivity reveals
the outstanding stability of SS-BNNSs as a catalyst for ODHP.
The carbon balance kept at 100 ± 3% during the long-term
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capture performance. Yang et al. synthesized 3D
active sites on the surface.13, 49 In contrast, the surface area of
SS-BNNSs is mainly contributed by the mesopores with the
pore sizes in the range of 5-40 nm (Figure 3f), which means
that the reactant can quickly diffuse in the pores of SS-BNNSs
and reaches the active sites easily.57-62 Moreover, the unique
3D spherical superstructure explores most of the edge active
sites of BNNSs to the top surface of SS-BNNSs. It allows
effective contact between the reaction gases and the active
sites without going inside the pores, which benefited the
catalytic activity. Figure 5f shows the Arrhenius plot of all the
samples, which gives the apparent activation energies (Ea).63 It
is found that the Ea of SS-BNNSs was 175.3 kJ mol-1, which
is much lower than that of C-BNNSs (202.9 kJ mol-1), P-BNFs
(195.7 kJ mol-1) and other previously reported h-BN
catalysts,16, 18, 64 further proving the high catalytic activity of
SS-BNNSs. It is notable that template-methods for preparing
h-BN have the disadvantage of the possible existence of other
elements.65-66 For instance, our XPS results indicate there are
some carbon atoms (1.07 at.%) in SS-BNNSs. The impurities
might affect the catalytic activity greatly.67 Future research
efforts will be directed toward understanding the contribution
of the impurities on the catalytic performance.
1
functionalized flower-like boron nitride nanosheets
(FBNNSs), which exhibited much higher NH3 and CO2
adsorption properties than 2D BN nanosheets.56 The excellent
adsorption properties are attributed to the efficient contact
surface area and the high number of adsorption. To shed light
on the structural advantage of SS-BNNSs, we compared the
ODHP performance of SS-BNNSs with commercial h-BN
nanosheets (C-BNNSs) and porous h-BN fibers (P-BNFs,
Figure S24). Prior to the ODHP tests, C-BNNSs and P-BNFs
need an activation process to arm B-OH species on the surface
and achieve the optimized catalytic performance (Figure
S25a).49 However, having massive oxygen-containing boron
species on the surface, SS-BNNSs can be used directly as a
catalyst for ODHP without any activation (Figure S25b). As
shown in Figure S26a, the unique structural design of SS-
BNNSs result in much higher propane conversion than C-
BNNSs. For example, at the same reaction temperature of 490
°C, SS-BNNSs obtain a propane conversion of 20.8%, while
the propane conversion of C-BNNSs is only 12.7% (Figure
5d). What is more, the propylene selectivity (78.1%) and
ethylene selectivity (10.2%) of SS-BNNSs are also higher than
those of C-BNNSs (76.2% for propylene and 8.3% for
ethylene). Such high propane conversion and olefins
selectivity of SS-BNNSs result in much higher olefins yield
than that of C-BNNSs (Figure 5e and Figure S26b-c). The
enhanced catalytic activity is attributed to the high surface area
and massive active sites of SS-BNNSs. As shown in Figure
S27a, C-BNNSs exhibit a surface area of 23 m2 g-1, which is
much lower than that of SS-BNNSs (439 m2 g-1). The in situ
DRIFTS results prove that the oxygen-containing boron sites
on SS-BNNSs are the active sites for ODHP (Figure S28). The
integral areas of –OH species (~3400 cm-1 in the FT-IR
spectra) can be used to quantify the number of active sites.24, 49,
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CONCLUSION
In summary, we have successfully synthesized a 3D spherical
superstructure composed of 2D anisotropic MOF nanosheets
via a solvothermal transformation of ZIF-8 nanoparticles. The
boron-contained SS-MOFNSs can preserve the original
morphology during the nitrogenization in ammonia, providing
a 3D spherical superstructure of h-BN nanosheets rich in
oxygen-containing boron active sites. The SS-BNNSs can be
applied as an effective catalyst for ODHP without any further
activation and achieve much-enhanced propane conversion
and olefin selectivity compared with C-BNNSs and P-BNFs.
57
As shown in Figure S29, the intensity of –OH vibrational
Moreover, an excellent olefins yield of 40.2% (propylene
27.8% and ethylene 12.4%) is achieved using SS-BNNSs as a
catalyst, surpassing all the previously reported h-BN catalysts.
This newly developed method not only opens up a new route
to prepare 3D spherical superstructure of nanosheets for
catalysis and other related fields, but also provides an idea to
improve the ODH performance through structural engineering.
stretches of SS-BNNSs is much higher than that of C-BNNSs,
indicating that high surface area of SS-BNNSs results in more
active sites than C-BNNSs.
In addition to the surface area, the pore size distribution
may also play an important part in the ODHP performance. To
get insight into the effect of the pore size distribution, we
compared the ODHP performance of SS-BNNSs and high-
surface-area porous h-BN fibers (P-BNFs). The surface area of
P-BNFs is much higher (838 m2 g-1, Figure S27b) than that of
SS-BNNSs (439 m2 g-1), but the ODHP performance of P-
BNFs is much lower than that of SS-BNNSs (Figure 5e and
Figure S26). For instance, the propane conversion of P-BNFs
is only 13.7% at 490 °C (Figure 5d), much lower than that of
SS-BNNSs (20.8%) at the same reaction temperature. The
propylene selectivity (77.7%) and ethylene selectivity (8.5%)
of P-BNFs are also lower than those of SS-BNNSs (78.1% for
propylene and 10.2% for ethylene). Accordingly, P-BNFs
exhibit lower overall olefins yield than SS-BNNSs (Figure
5e). The mismatch between the surface area and the ODHP
performance of P-BNFs can be explained by the unbefitting
pore size distribution. Although P-BNFs has a high surface
area, the surface area is mainly contributed by the micropores
with pore sizes around 1 nm (Figure S27b). Such small
micropores seriously block the diffusion of the reaction gases
and limit the exposure of active sites. As shown in Figure S29,
the integral areas of -OH species on P-BNFs is much lower
than that of SS-BNNSs, even though P-BNFs have a higher
surface area and are activated in the reaction condition to arm
ASSOCIATED CONTENT
Supporting Information.
The Supporting_Information is available free of charge via the
Internet at http://pubs.acs.org.
The experimental details, supporting figures and tables. (PDF)
Crystallographic data (CIF)
AUTHOR INFORMATION
Corresponding Author
*Pengcheng Dai: dpcapple@upc.edu.cn
*Xuebo Zhao: zhaoxuebo@upc.edu.cn
*Yusuke Yamauchi: y.yamauchi@uq.edu.au
Author Contributions
L.C. and P.D. contributed equally to this work.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
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composite by the guided assembly of boron nitride nanosheets for
flexible and stretchable electronics. Adv. Funct. Mater. 2019, 29 (37),
1902575.
This work was supported by the National Natural Science
Foundation of China (51702365), the Key Research and
Development Plan of Shandong Province (2019GGX102056,
2018GGX104018), the Special Project Fund of “Taishan
Scholars” of Shandong Province (NO.ts201511017), the
Fundamental Research Funds for the Central Universities
(16CX05006A, 19CX05002A), New Faculty Start-up funding in
China University of Petroleum (East China) (YJ201501029). Dr.
J. Tang and Professor Y. Yamauchi are the recipients of
Discovery Early Career Researcher Award (DE190101410) and
Future Fellow (FT150100479), respectively, funded by the
Australian Research Council (ARC).
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5
6
ACS Paragon Plus Environment