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Crystengcomm: Accepted Manuscript
Crystengcomm: Accepted Manuscript
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CrystEngComm
Accepted Manuscript
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Y. M. Jin, H. Q. Zhang, Y. Su and H. Yang, CrystEngComm, 2015, DOI: 10.1039/C5CE00804B.
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HIGHLIGHT
1. Introduction
Titanium dioxide has been widely applied as pigments,
sunscreens, paints, ointments and many other commercial
products due to its high optical refractive ability, chemically
stability and low toxicity. During recent decades, it has also
been one of the most important and fundamental materials,
especially in the field of energy and environmental
applications. This was initialled in 1972, that Fujishima and
Honda published the finding of photocatalytic splitting of water
by a TiO2 electrode under ultraviolet (UV) light, which offers a
promising way for clean, low-cost and environmentally friendly
production of hydrogen fuel from solar energy.1 Since then,
TiO2 has been extensively studied and remained as one of the
most important candidates used as photovoltaic devices,
photocatalysis, photodegradation, energy storage and
electrochromic devices.2-11
In addition to these success, approaches of TiO2 in
biomedical applications are exciting and, have made it a
promising material for health care, especially cancer treatment.
12-17
For instance, based on its excellent photocatalytic activity,
photoexcited TiO2 demonstrates the capability to kill cancer
cells effectively, and it can also be applied as a nucleic acid
endonuclease, which is of vital importance to genetic
engineering.
Undoubtedly, the unique physicochemical properties are not
only impacted by the intrinsic characteristics, but also by
crystal shape, size, doping and polymorph. Because of the
significant impact of crystal shape distributions, general
methodologies for the prediction, measurement, and techniques, modeling, and simulation have led to an improved
improvement of crystal shape are highly desired for product understanding of TiO2 crystal growth. The growth of crystals
and process design. These topics have been studied for a long generally have two controlling factors: thermodynamics and
period, recent breakthroughs in theoretical and experimental kinetics, which jointly determine the geometries of the
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systemically studied. And it was also found that the thickness dominated by well-faceted {001} facets. This synthesis
of the as-synthesized TiO2 nanosheets is dependent on the involves the hydrothermal treatment of the mixed solution of
concentration of HF.36 By a judicious tuning of its titanium(IV) butoxide, isobutyl alcohol, HF and deionized
concentration, {001} facets dominated anatase TiO2 nanosheets water.41 The formation of unique structure was ascribed to the
with the thickness of 1.6 nm were prepared, that is, only two presence of isobutyl alcohol as the reaction media, which might
layers of crystal units along the [001] crystallographic direction change the growth behaviour of anatase TiO2 nanosheet units
can be integrated into the entire matrix. As a complementary, and its mutual interactions as well. Besides, isolated micro-
the crystal growth behaviour of the {001} facets dominated sized TiO2 nanosheets wholly exposed with high-energy {001}
anatase crystals were also probed under the hydrothermal and {100} facets were synthesized through a solvothermal
condition.37 Within only deionized water, anatase TiO2 route, wherein titanium tetrafluoride was transferred to titanium
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nanosheets can grow into larger single crystals with a truncated oxydifluoride (TiOF2) first and then anatase TiO2 in the
bipyramidal shape through an oriented attachment process presence of the HF and 1-butanol as the capping agent and
along the [001] crystallographic direction, driven by the solvent.42, 43 The as-prepared anatase TiO2 nanosheets show a
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react with Ti4+ and form yellow peroxotitanium acid, which can
retard the hydrolysis and influence the surface energy. Further
study by Wu et al. demonstrated 11% of exposed {110} facets
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anatase TiO2 with large percentage {105} facets is based on a crystals dominated by {101} facets show a superior
flow field by tuning reaction kinetics.53 But regarding the photocatalytic activity in decomposing methylene blue to those
thermodynamic control we exemplified here, it will discussed with {301} facets. Also by the titanate route, Wang et al.
in the following part. By employing a new titanium precursor, synthesized spindled shaped anatase TiO2 crystals with exposed
titanium disilicide, Yang et al. have described a Si doped {401} facets (Fig. 7b).56 When urea was added, the spindle
anatase TiO2 crystals bound by high-index {201} and high- shaped crystals would evolve into truncated tetragonal
energy {001} facets.54 Such crystals enabled the visible-light bipyramidal particles. This can be explained as that the
induced photocatalytic H2 production, and combined the {110} hydroxyl ions would preferentially adsorb onto anatase {100}
and {001} features, offer similar high reactivity to perfect facets and thus limit the crystal growth along the a and b axes.
{001} but are more stable. Si-doped anatase TiO2 with {101} As expected, electrochemical performance analyses verified
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and {001} facets were also prepared via the control of reaction that the electrochemical performance of TiO2 can be ranked as
parameters which only presented about half catalytic activity {401} > {101} and {001} > {101} facets. Xie et al. has
compared with the anatase TiO2 crystals with high-index facets. investigated other agents including ethanol,
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3. Biomedical applications
disease diagnosis65, 66 and drug monitor.67, 68 Thus we will
To date, the shape engineering of anatase TiO2 has achieve highlight the strength of shape engineering of anatase TiO2
great advancement in physicochemical applications especially crystals in biomedical applications which may be as a candidate
photocatalysis and solar cells, which has been intensively tool for the further advances in this field.
reviewed.109 In addition, TiO2 based materials also enable many Anatase TiO2 have been utilized for electrochemical
biomedical applications, such as photodynamic therapy for detection of dopamine,69 tryptophan,70 aripiprazole,71 uric
cancer, drug delivery system, cell imaging, biosensors for acid,72 ascorbic acid,73 glucose,74 O6-benzylguanine,75 6-
biological assay and genetic engineering.64 Through the studies Phosphate aminopurine,76 adenine77 and guanine.77 Surface
of crystal shape engineering in this field are at the initial stage, characteristic is an crucial parameter for the selection and
these tailored anatase TiO2 crystals have many success in development of the sensing materials. Based on different
functional activities for different purposes, these
electrochemical biosensors of anatase TiO2 with facets can be
classified into two types: disease diagnosis and drug monitor.
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surface that effectively improved charge transport at the using appropriate capping agents while the kinetics controlled
interface. These results demonstrated that nano-p-n junction technique can make it. The key problem in the kinetics route is
heterostructures based on TiO2 nanobelts might serve as how to model and design the flow or liquid field, and then
promising candidates for biosensing applications of anticancer optimize the experimental parameters and improve the crystal
drugs that will be of significance in cancer diagnosis, treatment yields. As comparison, the bio-inspired method would be more
and molecular biology research. attractive in view of the unique crystalline structures stemmed
from nature. For example, the skeleton of a brittlerstar is
3.3 Toxicity composed of a single calcite crystal with regular inner pores
which is derived from the biological organism. State-of-the-art,
However, the cytotoxicity and genotoxicity of TiO2 have also mesoporous single crystal structure can only be synthesized by
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caused wide concerns by researchers in recent years.113-120 The a complicated methods with multiple steps,121 which reversely
toxic effects of anatase TiO2 are not only associated with the emphasize the importance of learning and simulating from the
particle size, but also closely related to the surface reactivity of natural biomineralization.
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