Spherical Mesoporous Metal Oxides with Tunable Orientation Enabled by Growth Kinetics Control

Article abstract of DOI:10.1021/jacs.0c07938

Recent advances in spherical mesoporous metal oxides (SMMOs) have demonstrated their enormous potential in a large variety of research fields. However, a direct creation of these materials with precise control on their key shape features, particularly pore architectures, remains a major challenge as compared to the widely explored counterpart of silica. Here, using Al2O3 as an example, we identified that deposition kinetics in solution played an essential role in the construction of different SMMOs. Specifically, a controlled Al3+ precipitation is critical to maintaining the electrostatic interaction between the inorganic precursors and the molecular templates, thereby achieving a designable assembly of these two components toward uniform mesoporous Al2O3-based nanospheres. We demonstrated that such a synthesis strategy is not only able to precisely control the channel orientations from concentric to radial and dendritic, a synthesis capability impeded so far for SMMOs, but is readily applicable to other metal oxides. Our study showed that the growth-kinetics control is a simple but powerful synthesis protocol and opened up a multifunctional platform to achieve systematic design of SMMOs for their future applications.

Full text of DOI:10.1021/jacs.0c07938

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Spherical Mesoporous Metal Oxides with Tunable Orientation
Enabled by Growth Kinetics Control
Wei Zhang, Bin Li, Yong-Gang Sun, An-Min Cao,* and Li-Jun Wan*
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ABSTRACT: Recent advances in spherical mesoporous metal oxides (SMMOs) have demonstrated their enormous potential in a
large variety of research fields. However, a direct creation of these materials with precise control on their key shape features,
particularly pore architectures, remains a major challenge as compared to the widely explored counterpart of silica. Here, using Al O3
2
as an example, we identified that deposition kinetics in solution played an essential role in the construction of different SMMOs.
Specifically, a controlled Al3 precipitation is critical to maintaining the electrostatic interaction between the inorganic precursors
and the molecular templates, thereby achieving a designable assembly of these two components toward uniform mesoporous Al O -
+
2
3
based nanospheres. We demonstrated that such a synthesis strategy is not only able to precisely control the channel orientations
from concentric to radial and dendritic, a synthesis capability impeded so far for SMMOs, but is readily applicable to other metal
oxides. Our study showed that the growth-kinetics control is a simple but powerful synthesis protocol and opened up a
multifunctional platform to achieve systematic design of SMMOs for their future applications.
esoporous oxides have drawn considerable interest due
to their attractive physical and chemical properties,
which promised enormous potential for their applications in
form a stable interface for the assembly process, not to
mention a good morphological control into highly favored
nanospheres, a shape of particular interest in mesoporous
structures which tends to require minimum energy for its
formation while maintaining complicated inner pore architec-
M
different fields such as sensors, catalysis, biology, energy
1
−11
storage, and conversion.
In this regard, tremendous
research efforts have been devoted to the creation of
mesoporous materials with delicate control on the structures,
particularly pore geometry and morphology, as well as
30−34
tures.
Current routes to build SMMOs mainly rely on hard-
template-based protocols by using mesoporous SiO nano-
1
2−19
2
composition.
mesoporous SiO2.
Stober process, which features a hydrolysis and condensation
One of the most successful materials is
spheres as the mold; a delicately controlled nanocasting
2
0−23
Taking advantage of the modified
process is needed to replicate the shape of SiO for
2
̈
35−39
constructing SMMOs.
Such a synthesis showed the
reaction for the formation of spherical SiO , researchers have
2
capability in shape control but is known for its shortcomings,
such as time-consuming, high cost, low yield, and environ-
mental risk caused during the template removal. Recently,
Zhao et al. identified a similar growth behavior of resorcinol
developed a flexible capability to produce mesoporous SiO
2
24−26
nanospheres at the assistance of different surfactants.
A
large variety of mesoporous SiO was constructed with desired
2
characteristics in pore size and particle morphology, which is
essential for not only ensuring optimized application perform-
ance but also achieving new and foundational knowledge on
the designing principles of mesoporous materials.
Despite the extensive achievements in the flexible creation of
mesoporous SiO2 nanospheres, it remains a significant
challenge to transfer the knowledge to the synthesis of a
non-siliceous counterpart, particularly spherical mesoporous
metal oxides (SMMOs) as addressed in this contribution.
Generally speaking, the successful construction of mesoporous
40
formaldehyde (RF) resin; thereby, mesoporous polymeric
RF nanospheres were successfully created through a soft-
templating route, highlighting the importance of well-tamed
growth behaviors for a controlled formation of spherical
particles. Unfortunately, for mesopore metal oxides, the widely
used soft-templating routes, particularly the solvent-induced
self-assembly process, were capable of creating mesopores but
41−48
have achieved scarce success in building SMMOs.
It is in
high demand that a synthetic protocol be developed to not
only provide flexible and versatile tools to form SMMOs with
SiO relies on a coordinated interaction of two involved
objects: the micellar template and gradually formed siliceous
2
species. The Stober reaction was capable of slowly producing
̈
Received: July 23, 2020
negative-charged inorganic oligomers, which would be electro-
statically attracted to the preexisting cationic surfactants to
form an inorganic/organic interface, whose cooperative
27−29
assembly led to the formation of mesoporous structure.
Different from SiO , the hydrolysis of metal precursors is
2
usually much faster, whose quick precipitation makes it hard to
©
XXXX American Chemical Society
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J. Am. Chem. Soc. XXXX, XXX, XXX−XXX
A

Journal of the American Chemical Society
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Communication
good control on the particle morphology but also be capable of
49,50
effectively regulating the pore architectures.
Herein, we demonstrated a synthesis route that is simple but
efficient to build various SMMOs with good control over their
pore orientations. Using Al O3 as a model system, we
2
demonstrated the possibility of modulating the hydrolysis
and precipitation of Al3 through a formamide decomposition
induced process, which provides an ideal tool to control the
growth kinetics of the inorganic species, whose slow formation
facilitates the favored interface assembly with the cationic
surfactants, successfully leading to the formation of uniform
Al O -based nanospheres with embedded mesopores (Al O -
+
2
3
2
3
SMMO). By controlling the reaction parameters such as
concentration and additives, it is convenient to systematically
modulate the pore configurations of the prepared Al O -
2
3
SMMO from radial orientation, to dendritic morphology, and
concentric patterns. Such a synthesis route could be readily
extended to constructing various SMMOs such as Cr O ,
2
3
CeO , La O , and Y O or hybrid compounds of Ce La O .
2
2
3
2
3
x
y
z
Our study opened up a reliable and versatile synthetic platform
to achieve systematic design of SMMOs for their future
applications.
To prepare Al O -SMMO, sodium dodecyl sulfonate (SDS)
2
3
51−54
is selected as the soft template
with Al(NO ) as the
3 3
aluminum source and additives were added to control the
organic−inorganic interaction, like the aluminum chelating
agent sodium salicylate (NaSal) (Figure S1). Different from
previously reported processes, we found the use of formamide
as a unique precipitant was critical for the growth and
morphological control of mesoporous particles. The product
existed as spherical particles of uniform size according to
scanning electron microscopy (SEM, Figures 1a and S2), and
the size is tailorable (Figure S3). Transmission electron
microscopy (TEM) proved the existence of radially oriented
mesochannels throughout the entire particles (Figure 1b). The
morphology, pore size, and channel orientation can be
systematically tuned (Figure S4), when using additives to
adjust the organic−inorganic interactions. For example,
dendritic Al O -SMMO nanospheres were produced in the
Figure 1. (a) SEM image of Al O -SMMO. (b−e) TEM images of
2
2
3
Al
O -SMMO with tunable morphology and channel orientation, (b)
3
radial orientation, (c) dendritic Al O -SMMO, (d) spheres, and (e)
2
3
hemispheres with a concentric pattern. (f) TEM image of Au@Al O -
2
3
SMMO with the radially oriented channels.
(
XRD, Figure S10) and high-resolution TEM (HRTEM,
Figure S11) indicate the amorphous property of the wall.
To study the underlying mechanism for the formation of
Al O -SMMO, negative-stained TEM was performed to
2
3
investigate the morphology of micelles. In conventional
synthesis, SDS tends to aggregate as cylinder-like micelles in
2
3
presence of sulfate (Figures 1c and S5), which might be
because of the competitive interaction among SDS, NaSal, and
3
+
the presence of Al (Figure S12), which is well described by
1
1
3
+
packing parameters (g) within the range of /
3
< g < /
2
sulfate with Al . While the additive was replaced with the
zwitterionic surfactant lauryl sulfobetaine, Al O -SMMO
g = v
0
2
3
spheres with concentrically oriented mesochannels were
fabricated (Figure 1d). Further adjusting the concentration
would produce Al O -SMMO hemispheres (Figure 1e), which
al0
(
1)
where v and l denote the volume and length of surfactants,
0
0
2
3
respectively, and a is the effective surface area of the
hydrophobic headgroup. For a certain surfactant, g is
determined by a, which is governed by headgroup interactions
is probably attributed to the in situ generated interface-
directed coassembly process similar to the previous report
55,56
(Figures S6 and S7).
Also, this method can be applied to
57
according to Tanford’s model,
constructing a mesoporous shell, e.g., Au@Al O -SMMO
2
3
(
Figure 1f).
1/2
iα y
j z
The d-spacing of Al O -SMMO was ∼2.9 nm with a
a = j z
2
3
k σ {
(2)
mesochannel diameter of ∼1.5 nm according to the high-
magnification TEM (Figure 2a). The chemical composition of
this mesoporous product was analyzed by elemental mapping
in scanning TEM (STEM) (Figures 2b and S8). Both Al and
O distributed evenly in each particle, confirming the formation
of Al O -SMMO, verified by the X-ray photoelectron spec-
where σ and α represent the interfacial tension and headgroup
repulsion parameters of surfactants, respectively. After
introducing NaSal, the strong coordination reduced the
attractive force between the inorganic salt and the soft
template, resulting in the increased α and the decreased g.
2
3
troscopy (XPS) (Figure S9). The mesoporous nature of Al O -
Accordingly, the cylindrical-like aggregates were transferred to
2
3
1
SMMO was confirmed by two-dimensional small-angle X-ray
scattering images (2D SAXS) (Figure 2c), and the strong peak
at a q value of ∼0.21 in the 1D SAXS pattern (Figure 2d),
which is consistent with TEM results. X-ray powder diffraction
spherical geometry (0 < g < / ) (Figure 2e). After gradual co-
3
deposition, radially oriented or dendritic Al O -SMMO
2
3
formed. When zwitterionic surfactant was added, the newly
emerged cationic group decreased the repulsive interaction
B
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Communication
concentration of hydroxide ions corresponding to a pH value
slightly higher than 3.9 (Figure S15), which provides an
3
+
optimal medium for gradual deposition of Al according to
59
the previous report. Driven by the minimum surface energy,
this controlled growth kinetics laid a good foundation for the
synthesis of homogeneously dispersed spheres, considering the
lowest surface-to-volume ratio (Figure S16). The gradual
formation of size-suitable positively charged inorganic building
blocks maintained electrostatic attraction with negative soft
templates, promoting the decent assembly and co-deposition
for constructing Al O -SMMO. For urea, the deposition speed
2
3
3
+
of Al is greatly boosted, making it hard to produce uniform
spheres, but regular channels are maintained because of the
electrostatic attraction between positive alumina oligomers and
negative surfactants, considering that the pH value is lower
than the isoelectric point (IEP) of alumina oligomers. When
ammonia is used and the pH value increases higher than IEP,
the zeta potential of alumina oligomers turns negative (Figure
S17) and the repulsive force between inorganic building blocks
and soft templates leads to the failure of the coassembly
process, resulting in macrophase separation. Based on all of the
above observations, we proposed a kinetics-controlled process
for the formation of SMMOs with tunable pore architectures
(
Figure 3).
Figure 2. (a) TEM image of Al O -SMMO. (b) STEM image and
2
3
elemental mapping of Al and O for Al O -SMMO. (c) 2D SAXS
2
3
image and (d) 1D SAXS pattern of Al O -SMMO. (e, f) Negative-
2
3
3
+
stain TEM images of micelles in the presence of Al for the synthesis
of Al O -SMMO with radial and concentric channels. (e) A scattering
2
3
of black dots indicates the spherical micelles. (f) Multilamellar
vesicles.
between SDS molecules, resulting in the formation of lamellar
1
structures ( / < g < 1) (Figure 2f). After precipitation,
2
concentrically aligned Al O -SMMO spheres and hemispheres
2
3
were produced.
Our control experiments identified that the use of
formamide was critical to modulating the structural features
of SMMOs, whose formation showed a close relationship to
the growth kinetics of the inorganic species. First, fast
precipitation should be prevented in the pursuit of SMMOs.
The use of ammonia or sodium hydroxide turned out to
produce only messy species without either mesopores or the
spherical shape (Figure S13). When urea was used to achieve
Figure 3. Schematic illustration of the formation process of Al O -
SMMO with tunable pore orientation prepared by kinetics controlled
growth.
2
3
forced hydrolysis of Al3 through its slow decomposition, the
particles remained irregular in shape, but mesopores started to
form (Figure S14), showing its beneficial contribution to the
cooperative assembly on the organic−inorganic interface.
Given the clear impact of the precipitation speed as well as
the fact that the target spherical particles represent a low
energy system, we surmised that control on the growth kinetics
to an even slower condition was beneficial for the creation of
SMMOs. A quick calculation showed that a pH value of
+
58
Impressively, this concept to construct controllable Al O -
2
3
SMMO can be extended to other non-siliceous oxides. Taking
concentric-ring patterns as an example, various mesoporous
metal oxides can be fabricated via a similar process, such as
Cr O , CeO , La O , and Y O (Figures 4a−c, S18, S19, and
2
3
2
2
3
2
3
S20), when suitable precipitants were utilized corresponding to
the K value. Besides, composite oxides with desirable channel
sp
orientation can also be prepared via our approach. Using
bimetallic oxide Ce La O as a proof-of-concept material, the
3
+
around 3.9 was needed for the precipitation of 1.6 mM Al ,
where the ionic products in solution reach the solubility
x
y
z
STEM elemental mapping of La and Ce dispersed evenly on
the particles, demonstrating the homogeneous distribution of
bimetallic oxides (Figure 4d−h, S21). Notably, these
mesostructures exhibit poor thermal stability and soft
templates can be partly removed, well consistent with previous
reports (Figure 4i). While this was not explored in this work, a
constant (K ) of aluminum hydroxide. As for urea, its
sp
decomposition product has a high pH of ∼6.4, a value much
higher than what is needed for the Al3 deposition.
+
When formamide was used as a precipitant, the decom-
position product endowed the solution with a suitable
C
https://dx.doi.org/10.1021/jacs.0c07938
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Sciences (CAS), Beijing 100190, P. R. China; University of
Chinese Academy of Sciences, Beijing 100049, China;
orcid.org/0000-0001-9280-4337; Email: anmin_cao@
iccas.ac.cn
Li-Jun Wan − CAS Key Laboratory of Molecular Nanostructure
and Nanotechnology, and Beijing National Laboratory for
Molecular Sciences, Institute of Chemistry, Chinese Academy of
Sciences (CAS), Beijing 100190, P. R. China; University of
Chinese Academy of Sciences, Beijing 100049, China;
orcid.org/0000-0002-0656-0936; Email: wanlijun@
iccas.ac.cn
Authors
Wei Zhang − CAS Key Laboratory of Molecular Nanostructure
and Nanotechnology, and Beijing National Laboratory for
Molecular Sciences, Institute of Chemistry, Chinese Academy of
Sciences (CAS), Beijing 100190, P. R. China; University of
Chinese Academy of Sciences, Beijing 100049, China
Bin Li − College of Materials Science and Engineering, Qingdao
University of Science and Technology, Qingdao 266042, China
Yong-Gang Sun − CAS Key Laboratory of Molecular
Nanostructure and Nanotechnology, and Beijing National
Laboratory for Molecular Sciences, Institute of Chemistry,
Chinese Academy of Sciences (CAS), Beijing 100190, P. R.
China
Complete contact information is available at:
https://pubs.acs.org/10.1021/jacs.0c07938
Figure 4. (a−d) TEM images of other SMMOs including (a) CeO ,
2
(
b) La O , (c) Y O , and (d) bimetallic oxide Ce La O . (e) STEM
Notes
2
3
2
3
x
y
z
image and (f−h) elemental mapping of Ce, La, and O for Ce La O .
The authors declare no competing financial interest.
x
y
z
(
i) Nitrogen adsorption−desorption isotherms and pore-size
distribution of mesoporous La O (inset).
2
3
ACKNOWLEDGMENTS
■
This work was supported by the Key Research Program of
Frontier Sciences, CAS (ZDBS-LY-SLH020), Beijing National
Laboratory for Molecular Sciences (BNLMS-CXXM-202010),
the Beijing Natural Science Foundation (L182050), and the
National Natural Science Foundation of China (Grant No.
focus of future studies will be to address this issue with a softer
post-treatment method.
In summary, using Al O3 as a model system, we
2
demonstrated a kinetics-controlled process to realize the
construction of SMMOs with tailorable shape and pore
orientation, from radial stacking, to concentric alignment, to
hemispheres, to dendritic morphology. The success lies in the
precisely controlled hydrolysis speed of metal ions and
systematically tuned organic−inorganic interaction. In addi-
tion, this approach can be well extended to the construction of
other SMMOs, e.g., Cr O , Y O , CeO , La O , and composite
51672282).
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