DOI: 10.1002/slct.

201700372 Full Papers

z Energy Technology & Environmental Science

Room-Temperature Hydrolysis of Potassium Titanyl

Oxalate and Water-Assisted Crystallization for TiO2 with
High Photocatalytic Activity
Lu–Lu Lai,[a] Wei Wen,[b] and Jin-Ming Wu*[a]

The commonly adopted approach to synthesize nanostructured immersing duration in hot water for up to 72 h. The low-
TiO2 starting from titanates demands a hydrothermal environ- temperature crystallized TiO2 powders possessed abundant
ment to achieve the titanate precursor, and a subsequent high surface hydroxyl groups (~ 38 %), high specific surface area (~
temperature calcination to fulfill the decomposition of titanates 126 m2/g) and pore volume (~ 0.50 cm3/g). When utilized to
and crystallization of TiO2. In this report, hydrogen titanate assist photodegradation of rhodamine B in water under UV
aggregates were achieved by a room-temperature hydrolysis of light illumination, the reaction rate constant was twice that of
a potassium titanyl oxalate in an aqueous H2O2 solution. The the commercial P25 TiO2 nanoparticles. The high photocatalytic
subsequent immersion in water at 80 8C induced the crystal- activity is contributed to the abundant surface hydroxyl groups,
lization of TiO2 with a mixture of anatase nanoparticles and high specific surface area, and the appropriate mixture of
rutile nanorods. The anatase fraction increased with increasing anatase nanoparticles and rutile nanorods (~ 84:16 in weight).

Introduction
realized later in 2002.[12] The hot water treatment was also
Titanium dioxide (TiO2) is a photocatalyst attracted the most applied to synthesize mesoporous anatase TiO2 nanorods from
attention[1, 2] . The photocatalytic activity of TiO2 is affected by titanium glycolate nanorods,[13] mesoporous nanowires from as-
multi-factors of crystalline phases,[3] morphologies,[4] dopants,[5] anodized amorphous nanotubes,[14] and porous anatase from
and surface deficiencies,[6] etc. Various synthetic techniques sol-gel derived amorphous titania.[15] Starting from hydro-
have been developed to achieve TiO2 with a high activity. thermally synthesized titanate nanowires, crystallized TiO2 with
Among them, the two-step routes of decomposing hydrogen controlled phases and nanostructures has been achieved by
titanates to crystallized TiO2 enables morphology control and immersing in various acidic aqueous solutions at 60–70 8C for 7
facile doping, which are beneficial to the improvement in days.[16]
photocatalytic activity.[7] The titanates are often synthesized via In this work, we report the synthesis of hydrogen titanates
hydrothermal/solvothermal routes and most of them involve via the room temperature hydrolysis of potassium titanyl
the utilization of high temperature and high pressure,[8] which oxalate, K2TiO(C2O4)2, in the presence of H2O2 and HNO3. On
demand for high energy consumption and bring about safety contrary to the commonly adopted hydrothermal technique,[8]
concerns when scaled-up. the synthetic route developed herein demands no external
Thermal treatment at high temperatures is usually em- energy input, which is energy-efficient and simple. TiO2 with a
ployed to achieve the transformation of titanate to TiO2.[7b] mixture of anatase nanoparticles and rutile nanorods were
However, grain growth[9] and the loss of hydroxyl groups gained by a subsequent hot water treatment at 80 8C for 72 h,
accompany the calcination.[10] Therefore, alternative routes like which achieved crystallization of TiO2 and retained the
hot water treatments have been investigated to achieve beneficial surface hydroxyl groups at the same time. The
transformations of titanates to TiO2 crystallites. In 1999, positive effects arising from the hot water treatment, as well as
Yanagisawa et al. applied a hydrothermal technique to achieve the mixed phase and morphology, were studied in detail. When
the crystallization of amorphous titania.[11] Crystallization of utilized to assist photodegradation of rhodamine B in water
amorphous titania gel in hot water in an open atmosphere was under the UV light, the TiO2 powder exhibited an exceptional
high activity, which doubled that of the commercial Degussa
P25 TiO2 nanoparticles.
[a] Dr. L.–L. Lai, Prof.Dr. J.-M. Wu
State Key Laboratory of Silicon Materials and School of Materials Science
and Engineering, Zhejiang University Results and Discussion
Hangzhou, 310037, P. R. China
E-mail: [email protected] Figure 1a shows the field emission scanning electron micro-
[b] Dr. W. Wen
scopy (FESEM) morphology of the precipitates collected after
College of Mechanical and Electrical Engineering, Hainan University
Haikou, 570228, P.R. China the room temperature hydrolysis of K2TiO (C2O4)2 for 72 h.
Supporting information for this article is available on the WWW under Aggregates of spindle-like nanoparticles can be seen. The
https://doi.org/10.1002/slct.201700372 average length and width of the primary nanoparticles are ca.

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located at 447 cm1 that can be attributed to rutile TiO2 can
also be found,[20] which is in accordance with the XRD result.
The transmission electron microscopy (TEM) images of
powders after the hot water treatment are shown in Figure 3a

Figure 1. FESEM images of room temperature precipitated powder (a), that

after crystallization in water at 80 8C for 72 h (b) or calcination in air at 450 8C
for 1 h (c). The insets show the corresponding low magnification FESEM
images.

40 nm and 15 nm, respectively. The subsequent calcination in

air at 450 8C for 1 h does not change the morphology
(Figure 1c). Figure 1b demonstrates that, when the aggregates
were subjected to the hot water treatment at 80 8C for 72 h,
the morphology changed significantly. Nanorods and nano-
particles co-assembled the aggregates. The average length and
width of the nanorods are ca. 160 nm and 50 nm, respectively;
whilst the average dimension of nanoparticles is ca. 40 nm.
Figure 2 illustrates the X-ray diffraction (XRD) patterns and
corresponding Raman spectra of the room temperature

Figure 3. TEM (a, b) and HRTEM (c, d) images of the powders after
crystallization in water at 80 8C for 72 h; (b) TEM image of the marked region
in (a); HRTEM images of nanorod (c) and nanoparticle (d). The inset shows
the corresponding SAED pattern.

and b. Powders assembled by nanorods and nanoparticles can

be clearly observed. The average length and width of the
nanorods estimated from the TEM image are 150 nm and
50 nm, respectively, which is in accordance with the SEM
observation. The corresponding selected area electron-diffrac-
Figure 2. XRD patterns (A) and Raman spectra (B) of room temperature
precipitated powders (a), that after crystallization in water at 80 8C for 72 h tion (SAED) pattern demonstrates a heterogeneous structure
(b) or calcination in air at 450 8C for 1 h (c). consisted of anatase and rutile. Figure 3c and d display the
corresponding high resolution TEM (HRTEM) image of the
nanorod and nanoparticle, respectively. The internal porosity
and single-crystallinity of nanorod are revealed by the HRTEM
precipitated powder, that after hot water treatment or that image (Figure 3c), which clearly displays mesopores inside the
after calcination. The peaks of the room temperature precip- single crystallite. The formation of such mesopores can be
itates can be indexed to hydrogen titanate H2Ti2O5·H2O (JCPDS contributed to the non-classical particle-mediated crystalliza-
card no. 47–0124). The corresponding Raman spectrum displays tion pathway, that is, the oriented attachment (OA) mecha-
broad bands which can be ascribed to the active modes of nism.[21] Two sets of lattice fringe of ca. 0.33 nm and 0.25 nm
titanates.[17] The subsequent water treatment led to the with an angle of ca. 68 8 can be discerned, which correspond
formation of a mixture of well crystallized anatase (JCPDS card to the (110) and (101) crystal planes of rutile TiO2, respectively.
no. 21–1272) and rutile (JCPDS card no. 21–1276). The weight The SAED pattern further confirms the single crystallinity of the
ratio of anatase to rutile is calculated to be 84:16, utilizing the rutile nanorod (inset in Figure 3c). The HRTEM image of the
X-ray intensities of the (101) peaks of anatase and rutile,[18] nanoparticle demonstrates lattice with a neighboring distance
respectively. On the contrary, calcination in air decomposed of 0.35 nm, which corresponds to the (101) plane of anatase
titanate to anatase only. The Raman spectra of both water- TiO2 (Figure 3d).
treated powder and calcined powder exhibit peaks located at To shed light on the low temperature water-assisted
145, 197, 399, 516, 636 cm1, which could be indexed to crystallization procedure, the phase and morphology evolution
anatase TiO2.[19] For the hot water-treated powder, another peak upon the hot water treatment duration were investigated

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(Figure 4 and S1). After 24 h of reaction, no diffraction peak is composed of one Ti atom coordinated by two [C2O4]2 ions
corresponding to hydrogen titanate can be discerned. On the and bonded by two O atoms. Under the ambient temperature,
K2TiO(C2O4)2 hydrolyzed in the aqueous H2O2 solution and [C2
O4]2 would be replaced by O22 from H2O2 to form peroxo-
complexes, which is further evidenced by the deep orange
color of the solution. K + ions were exchanged by H + ions,
which were provided by nitric acid in the reactants, and thus
released to the solution. As a result, hydrogen titanate was
achieved. Nitric acid was also used to control the pH value of
the solution and thus the hydrolysis rate of K2TiO(C2O4)2.
At the initial stage of the hot water treatment, the room
temperature precipitated hydrogen titanate dissolved and
precipitated back to the solution in forms of both anatase
nanoparticles and rutile TiO2 nanorods. During the hot water
treatment, water molecules catalyzed the rearrangement of the
Figure 4. XRD patterns (A) and Raman spectra (B) of the powders after
crystallization in water at 80 8C for various durations: (a) 0 h; (b) 24 h; (c) 48 h; TiO6 octahedra by adsorption to the surface and increased the
(d) 72. rate of crystallization.[11] In our previous work, for titanates
achieved using a higher hydrolysis temperature (40 8C), an
intermediate proton exchange process was indispensable to
contrary, the XRD peaks corresponding to anatase and rutile eliminate K-related impurities before the final calcination to
appeared. The weight ratio of anatase to rutile was estimated obtain pure TiO2.[7c] In the current investigation, phase pure
to be 52:48 (Figure 4 A). When the reaction time reached 48 h, TiO2 could be achieved by direct decomposition of the titanate
the weight percentage of anatase increased to 58:42. With the thanks to the room temperature hydrolysis, which is supposed
prolonged reaction time to 72 h, the ratio of anatase to rutile to weaken the bonding between K + ions and hydrogen
further increased to 84:16. The change in phase composition is titanates. Instead of nanoparticles as in the case of anatase,
well supported by the corresponding Raman spectra, as nanorods were achieved for the rutile phase, which can be
illustrated in Figure 4B. The peaks indexed to titanate almost ascribed to the remarkable difference in the growing rate and
vanished at the reaction time of 24 h, and peaks corresponding surface energy.[22] The order of growth rate of rutile is V < 110 > <
to anatase and rutile appeared. For the 24 h hot-water treated V < 100 > < V < 101 > < V < 001 > < V < 111 >, and {110}, {100} and
product, the XRD pattern shows no peaks corresponding to {101} facets are easily exposed.[22a] The anisotropic morphology
titanate yet the Raman spectrum does. This can be attributed of rutile is also related to the oriented attachment process.[22b]
to the difference in the sensitivity. The amount of titanate is The gradual increase in the anatase fraction with the prolonged
too small to be detected by XRD, which is negligible when hot water treatment deserves a further study; however, it is
calculating the phase composition utilizing the XRD intensity. speculated that during the room temperature hydrolysis,
Further increasing the water treatment duration to 48 and 72 h, amorphous TiO2 also precipitated because of the relatively high
the peaks of titanate totally disappeared while the peaks Ti(IV) concentrations at the early stage. The crystallization of
related to anatase and rutile remained unchanged. The the amorphous TiO2 demands more time which gradually
morphology evolution demonstrated by the corresponding increased the XRD intensity of peaks corresponding to anatase;
FESEM images in Figure S1 reveals that, except nanoparticles, whilst the amount of rutile remained unchanged. This led to
nanorods appeared at the reaction time of 24 h, the amount of the increased anatase/rutile ratio upon the prolonged hot
which remained nearly unchanged with the further prolonged water treatment duration (Figure 4a). It is also possible that the
reaction time to 48 h and 72 h. hydrolyzed product is inhomogeneous so that a part of the
Based on the results above-mentioned, the formation products tend to transform to rutile and the rest follows the
mechanism of the TiO2 aggregates by the present room amorphous-recrystallization process to anatase.
temperature hydrolysis and subsequent hot water treatment is The N2 adsorption-desorption isotherms of the powders
shown in Scheme 1. It is noted that each K2TiO(C2O4)2 molecule after the hot water treatment or calcination in air are shown in
Figure 5a and the calculated data are listed in Table 1. An IV
type isotherm with a H3 type hysteresis loop can be discerned
for both powders. The specific surface area of powders after
the hot water treatment is 126.2 m2·g1, much higher than the
calcined product (61.7 m2·g1). Figure 5b illustrates the corre-
sponding pore size distribution curves. The average pore size
defined for the hot water-treated powder and calcined powder
is 15.96 nm and 13.98 nm, respectively; whilst they display
Scheme 1. A schematic image demonstrating the formation mechanism of apparently different pore size distributions (Figure 5b). The
TiO2 during the hot water treatment. calcined powder shows pores ranging from 4–10 nm and 10–
100 nm whilst the hot water-treated powder possesses pores

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Figure 5. The N2 adsorption-desorption isotherms (a) and the pore size

distribution curves (b) of the powders after crystallization in water at 80 8C
for 72 h (hot water treatment), followed by a final calcination in air at 450 8C
for 1 h (hot water-treatment!calcination), or directly calcinated in air at 450
8C for 1 h (calcination).

Figure 6. Diffuse reflectance UV-Vis spectra of the powder after crystallization

in water at 80 8C for 72 or calcination in air at 450 8C for 1 h. That of
commercial Degussa P25 TiO2 nanoparticles was also included for reference.
ranging from 1–4 nm and 10–100 nm. The pore volume for hot
water-treated and calcined powder is calculated to be
0.503 cm3·g1 and 0.216 cm3·g1, respectively. These results
demonstrate that, when compared with calcination, the hot Figure 7 exhibits the high-resolution Ti 2p and O 1 s XPS
water treatment can achieve high specific surface area and spectra of the powder after hot water treatment or calcination,
pore volume, which is beneficial for photocatalytic reactions.
When subjected to an additional calcination in air at 450 8C for
1 h, the specific surface area of the hot water-treated powder
decreased to 68.6 m2·g1 and the pore volume reduced slightly
to 0.487 cm3·g1, which can be contributed to the elimination
of deficiencies upon the final calcination. It is noted that the
pore texture remains almost the same.
As illustrated by the diffuse reflectance UV-Vis spectra in
Figure 6, the powders after hot water treatment exhibited
enhanced absorbance over the UV light region and an
absorption tail in visible light region, which merited from the
mixed morphology of nanorods and nanoparticles, and the
deficiencies originating from the low-temperature crystalliza-
Figure 7. High-resolution XPS spectra of (A) Ti 2p and (B) O 1 s for the
tion, as will be disclosed by the X-ray photoelectron spectra
powder that after crystallization in water at 80 8C for 72 (a) or calcination in
(XPS) later. The absorption edge estimated for hot water- air at 450 8C for 1 h (b) and the water treated powder with a further
treated powder, calcined powder, and commercial Degussa P25 calcination in air at 450 8C for 1 h (c).
TiO2 is 398, 390 and 402 nm, respectively. As listed in Table 1,
the corresponding band gaps are 3.11, 3.18 and 3.08 eV,
respectively. It is not surprising that the band gap decreased
with increasing rutile fraction, because the band gap of bulk and hot water-treated powder with a further calcination in air
anatase and rutile is 3.2 and 3.0 eV[23], respectively. at 450 8C for 1 h. For all the powders, the XPS spectrum of Ti
2p exhibits two peaks corresponding to Ti 2p1/2 and Ti 2p3/2

Table 1. Morphologies, band gap values, surface analysis data and reaction rate constant of room temperature precipitates followed with different
crystallization routes. The data of P25 is derived from reference and also listed below.

Crystallization -OH ratio Phase composition Morphology Band gap BET Specific surface area m2 g-1 Pore volume k
route Anatase to Rutile eV cm3 g-1 min-1

Hot water–treatment 0.38 84:16 Nanorod + 3.11 126.2 0.503 0.17

nanoparticle
Hot water–treatment 0.19 83:17 Nanorod + / 68.6 0.487 0.021
!calcination nanoparticle
Calcination 0.28 100:0 Nanoparticle 3.18 61.7 0.216 0.014
P25 / 80:20 [30] Nanoparticle 3.08 63 [30] / 0.086

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with a split of 5.7 eV, which is characteristic of Ti4 +.[24] The O 1 s
spectra can be fitted into two peaks, with the peak at lower
binding energy (BE) indexed to lattice oxygen and the higher
BE assigned to the hydroxyl groups (-OH).[25] The ratio of the
integrated area of two peaks can be used to compare the
amount of -OH possessed by the powders underwent different
crystallization processes.[26] The ratio of the peak area of -OH for
the powder after hot water treatment is 0.38, remarkably
higher than 0.28 defined for the powder after calcination. The
ratio decreases from 0.38 to 0.19 by a further calcination
process for the hot water-treated powder. These results
demonstrate that low temperature water-assisted crystallization
process guarantees high percentage of surface hydroxyl
groups. The calcination at 450 8C removes them effectively.
The photocatalytic activity of the powder after hot water Figure 9. The cycling performance of the powder after crystallization in water
treatment or calcination was evaluated by photodegradations at 80 8C for 72. Initial rhodamine B concentration: 0.01 mM; catalyst load:
of rhodamine B in water under the illumination of UV light and 0.5 g·L1; UV light intensity: 5.3 mW·cm2.
the results are displayed in Figure 8a. It should be noted that,

slightly reduced removal ability is attributed to the catalyst loss

after each cycle resulted from the recovery process through
centrifugation.
The superior photocatalytic performance of the hot water-
treated powder when compared with the calcined one may
firstly be attributed to the remarkably higher specific surface
area merited from the hot water-assisted crystallization process
(126 vs. 62 m2·g1), which provides more active sites for the
target molecules. Moreover, the abundant surface hydroxyl
groups inherited from the hot water-assisted crystallization
process further contributes to the photodegradation reac-
Figure 8. (a) Photodegradation curves of rhodamine B in water in the tion.[28, 29] The positive effect of hydroxyl groups is confirmed by
presence of P25, the powder after crystallization in water at 80 8C for 72 (hot subjecting the hot water-treated powder to a further calcina-
water treatment) or calcination in air at 450 8C for 1 h (calcination), under the tion in air at 450 8C for 1 h. The subsequent calcination of the
UV light illumination. (b) The fitting results assuming a pseudo-first-order
hot water-treated powder altered neither the phase composi-
reaction. Initial rhodamine B concentration: 0.01 mM; catalyst load: 0.5 g·L1;
UV light intensity: 5.3 mW·cm2. tion (Figure S2) nor the morphology (Figure S3); however, the
ratio of hydroxyl groups greatly reduced from 38% to 19%
(Figure 6). The photocatalytic activity of both powders is
compared and the result is displayed in Figure 10. After the
because UV light only is utilized as light source here, the visible
light induced photosensitization procedure of rhodamine B
dyes in the presence of TiO2 can be neglected.[27] Under the
identical condition, the TiO2 powder crystallized with the
assistance of water exhibited much higher activity than the
calcined powder and P25. The dye molecules were nearly
degraded with the assistance of the water-treated powder
within 15 min whilst it took 30 min for P25 to achieve the
similar degradation rate. Only 30% rhodamine B molecules
could be degraded for calcined powder within 30 min. All the
degradation procedures can be fitted well by a pseudo-first
order kinetic (Figure 8b).[28] As summarized in Table 1, the hot
water-treated powder exhibited a reaction rate constant of Figure 10. (a) Photodegradation curves of rhodamine B in water in the
0.17 min1, which almost doubled that of P25 nanoparticles presence of the powders after crystallization in water at 80 8C for 72 h, with
(0.086 min1) and more than 12 folds that of the calcined and without the subsequent calcination at 450 8C for 1 h. (b) The fitting
results assuming a pseudo-first-order reaction. Initial rhodamine B concen-
powder (0.014 min1). The stability of the powder after the hot
tration: 0.01 mM; catalyst load: 0.5 g·L1; UV light intensity: 5.3 mW·cm2.
water treatment was confirmed by the repetitively photo-
degradation of rhodamine B in water under the UV light
illumination for up to 5 cycles, as demonstrated in Figure 9. The

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subsequent calcination, the hot water-treated powder exhib- the hot water-treated powders before and after a subsequent
ited much reduced efficiency when compared with the fresh calcination.
one. Under the identical condition, the reaction rate constant
decreased from 0.17 to 0.021 min1 (Table 1). Considering that
Acknowledgements
the specific surface area reduced just from 126.2 to 68.6 m2·g1,
this demonstrates clearly the crucial role of the surface hydroxyl We are grateful for financial support from the National Natural
groups. Science Foundation of China (No. 51502065) and State Key
As summarized in Table 1, the hot water-treated powder Laboratory of Silicon Materials (No. SKL2016-12).
followed by the subsequent calcination exhibited a rate
constant higher than that of the powder obtained by directly
Conflict of Interest
calcinating the as-precipitated titanate, which are spindle-like
nanoparticles assembled aggregates of phase pure anatase The authors declare no conflict of interest.
(Figure 1c). The higher activity could thus be assigned to the
synergistic effect arising from the mixed phase and morphol- Keywords: Photocatalysis · potassium titanyl oxalate · room-
ogy. It is argued that TiO2 with appropriate phase composition temperature hydrolysis · titanium dioxide · water-assisted
of anatase and rutile can lead to enhanced photocatalytic crystallization
performance because of the phase junction effect.[30] The
morphology of the coexistence of nanorods and nanoparticles
may also contribute to the improved efficiency by allowing
[1] M. R. Hoffmann, S. T. Martin, W. Y Choi, D. W. Bahnemann, Chem. Rev.
multiple reflections and permitting the opportunity for the 1995, 95, 69–96.
light to be more efficiently used. It is noted that the weight [2] X. B. Chen, S. S. Mao, Chem. Rev. 2007, 107, 2891–2959.
ratio of anatase to rutile derived for the hot water-treated TiO2 [3] a) Z. Ding, G. Q. Lu, P. F. Greenfield, J. Phys. Chem. B 2000, 104, 4815–
4820; b) A. Testino, I. R. Bellobono, V. Buscaglia, C. Canevali, M. D.
is near to that of commercial Degussa P25 TiO2 nanoparticles
Arienzo, S. Polizzi, R. Scotti, F. Morazzoni, J. Am. Chem. Soc. 2007, 129,
(Table 1). 3564–3575.
The doubled reaction rate constant for the present hot [4] T. R. Gordon, M. Cargnello, T. Paik, F. Mangolini, R. T. Weber, P. Fornasiero,
water-treated powder when compared with P25 nanoparticles C. B. Murray, J. Am. Chem. Soc. 2012, 134, 6751–6761.
[5] a) G. Liu, Y. N. Zhao, C. H. Sun, F. Li, G. Q. Lu, H. M. Cheng, Angew. Chem.
can be attributed to the much higher specific surface area (126
Int. Ed. 2008, 47, 4516–4520; b) C. L. Muhich, J. Y. Westcott, T. Fuerst,
vs. 62 m2·g1),[31] higher pore volume, more surface hydroxyl A. W. Weimer, C. B. Musgrave, J. Phys. Chem. C 2014, 118, 27415–27427.
groups, and the enhanced absorbance throughout the UV light [6] U. I. Gaya, A. H. Abdullah, J. Photochem. Photobiol., C 2008, 9, 1–12.
region. Considering also the fact that the micrometer-sized [7] a) F. Shao, J. Sun, L. Gao, S. W. Yang, J. Mater. Chem. 2012, 22, 6824–
6830; b) T. Z. Xu, H. Zheng, P. Y. Zhang, W. Lin, Y. Sekiguchi, J. Mater.
aggregates facilitate the catalyst-recovery from the slurry
Chem. A 2015, 3, 19115–19122; c) L. L. Lai, W. Wen, J. M. Wu,
system when compared with nanoparticles,[32] the synthetic CrystEngComm 2016, 18, 5195–5201.
technique developed herein may find practical applications in [8] a) Y. V. Kolen’ko, K. A. Kovnir, A. I. Gavrilov, A. V. Garshev, J. Grantti, O. I.
wastewater remediation. Lebedev, B. R. Churagulov, G. V. Tendeloo, M. Yoshimura, J. Phys. Chem. B
2006, 110, 4030–4038; b) N. Ttreault, E. Horvth, T. Moehl, J. Brillet, R.
Smajda, S. Bungener, N. Cai, P. Wang, S. M. Zakeeruddin, L. Forro, A.
Conclusion Magrez, M. Gratzel, ACS Nano 2010, 4, 7644–7650; c) Z. H. Zhao, J. Tian,
Y. H. Sang, A. Cabot, H. Liu, Adv. Mater. 2015, 27, 2557–2582.
Hydrogen titanate aggregates were synthesized through the [9] a) Z. T. Jiang, Y. M. Zuo, Anal. Chem. 2000, 73, 686–688; b) Y. Q. Wang,
S. G. Chen, X. H. Tang, O. Palchik, A. Zaban, Y. Koltypin, A. Gedanken, J.
room temperature hydrolysis of K2TiO (C2O4)2 in the solution
Mater. Chem. 2011, 11, 521–526.
containing HNO3 and H2O2. The dissolution of the titanate in [10] J. Sun, J. M. Wu, Sci. Adv. Mater. 2013, 5, 549–556.
hot water and the subsequent precipitation achieved TiO2 with [11] K. Yanagisawa, J. Ovenstone, J. Phys. Chem. B 1999, 103, 7781–7787.
mixed phase and morphology, that is, anatase nanoparticles [12] J. M. Wu, S. Hayakawa, K. Tsuru, A. Osaka, J. Ceram. Soc. Jpn. 2002, 110,
78–80.
and rutile nanorods. The anatase fraction increased gradually
[13] S. Priya, J. Robichaud, M. C. Methot, S. Balaji, J. M. Ehrman, B. L. Su, Y.
with increasing hot water treatment duration. Merited from the Djaoued, J. Mater. Sci. 2009, 44, 6470–6483.
water-assisted crystallization, the hot water-treated TiO2 pow- [14] D. A. Wang, L. F. Liu, F. X. Zhang, K. Tao, E. Pippel, K. Domen, Nano Lett.
der exhibited an extremely high photocatalytic activity, which 2011, 11, 3649–3655.
[15] N. Li, Q. Zhang, J. B. Joo, Z. D. Lu, M. Dahl, Y. Gan, Y. D. Yin, Nanoscale
doubled that of P25 nanoparticles, when utilized to assist the
2016, 8, 9113–9117.
photodegradation of rhodamine B in water under the UV light [16] Z. S. Hong, Y. X. Xu, Y. B. Liu, M. D. Wei, Chem. - Eur. J. 2012, 18, 10753–
illumination. The excellent photocatalytic activity can be 10760.
attributed to the mixed phase and morphology, high specific [17] a) H. W. Liu, Z. F. Zheng, D. J. Yang, E. Waclawik, X. B. Ke, H. Y. Zhu, S.
Palmer, R. L. Frost, J. Raman Spectrosc. 2010, 41, 1601–1605; b) W. B. Hu,
surface area, large pore volume, and abundant surface hydroxyl
L. P. Li, G. S. Li, Y. Liu, R. L. Withers, Sci. Rep. 2014, 4, 6582; c) S. W. Liu,
groups. J. Q. Xia, J. G. Yu, ACS Appl. Mater. Interfaces, 2015, 7, 8166–8175.
[18] R. A. Spurr, H, Myers, Anal. Chem. 1957, 29, 760–762.
[19] T. Ohsaka, F. Izumu, Y. Fujiki, J. Raman Spectrosc. 1978, 7, 321–324.
Supporting Information Summary [20] M. Ocana, J. G. Ramos, C. J. Serna, J. Am. Ceram. Soc. 1992, 75, 2010–
2012.
The experimental details, the morphology evolution during the [21] a) H. Colfen, M. Antonietti, Angew. Chem. Int. Ed. 2005, 44, 5576–5591;
hot water treatment, the FESEM images and XRD patterns for b) L. L. Lai, W. Wen, J. M. Wu, Ceram. Int. 2015, 41, 12317–12322.

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 Full Papers
[22] a) J. K. Oh, J. K. Lee, H. S. Kim, S. B. Han, K. W. Park, Chem. Mater. 2010, [30] a) Z. Y. Liu, X. T. Zhang, S. Nishimoto, M. Jin, D. A. Tryk, T. Murakami, A.
22, 1114–1118; b) C. Ribeiro, C. Vila, D. B. Stroppa, V. R. Mastelaro, J. Fujishima, Langmuir 2007, 23, 10916–10919; b) T. Xia, N. Li, Y. L. Zhang,
Bettini, E. Longo and E. R. Leite, J. Phys. Chem. C 2007, 111, 5871–5875. M. B. Kruger, J. Murowchick, A. Selloni, X. B. Chen, ACS Appl. Mater.
[23] Y. C. Lan, Y. L. Lu, Z. F. Ren, Nano Energy 2013, 2, 1031–1045. Interfaces 2013, 5, 9883–9890.
[24] J. M. Wu, H. X. Xue, J. Am. Ceram. Soc. 2009, 92, 2139–2143. [31] D. G. Gong, V. P. Subramaniam, J. G. Highfield, Y. X. Tang, Y. K. Lai, Z.
[25] Y. S. Luo, J. S. Luo, W. W. Zhou, X. Y. Qi, H. Zhang, Y. W. Yu, C. M. Li, H. J. Chen, ACS Catal. 2011, 1, 864–871.
Fan, T. Yu, J. Mater. Chem. A 2013, 1, 273–281. [32] J. M. Wu, X. M. Song, M. Yan, J. Hazard. Mater. 2011, 194, 338–344.
[26] W. M. Seong, D. H. Kim, I. J. Park, G. D. Park, K. Kang, S. Lee, K. S. Hong, J.
Phys. Chem. C 2015, 119, 13297–13305.
[27] T. X. Wu, G. M. Liu, J. C. Zhao, J. Phys. Chem. B 1998, 102, 5845–5851.
[28] J. M. Wu, T. W. Zhang, J. Photochem. Photobiol., A 2004, 162, 171–177. Submitted: February 21, 2017
[29] a) Y. Shiraishi, N. Saito, T. Hirai, J. Am. Chem. Soc. 2005, 127, 12820– Revised: June 9, 2017
12822; b) J. M. Wu, Environ. Sci. Technol. 2007, 41, 1723–1728. Accepted: June 12, 2017

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