Materials Research Bulletin 44 (2009) 91–94

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Materials Research Bulletin

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Crystal growth and structure determination of K2TiO3: A five coordinate titanate

H.S. Khalsa, M.D. Smith, H.-C. zur Loye *
Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC 29208, USA

A R T I C L E I N F O A B S T R A C T

Article history: Long, needle-shaped single crystals of K2TiO3 were grown out of a reactive high temperature hydroxide
Received 3 December 2007 melt. The structure was determined by single crystal X-ray diffraction and found to crystallize in
Accepted 27 March 2008 the orthorhombic Cmcm space group with a = 10.0283(2) Å, b = 6.9346(2) Å, c = 5.4534(1) Å,
Available online 9 April 2008
V = 379.242(15) Å3, and Z = 4. The structure is related to the K2SnO3 and K2ZrO3 structures, which
crystallize in the Pnma space group, and that of K2PbO3, which crystallizes in the Cmc21 space group. The
Keywords:
structure consists of chains of trans edge-sharing TiO5 rectangular pyramids with alternating apical
Oxides
directions. The chains are separated by KO7 polyhedra.
Crystal growth
ß 2008 Elsevier Ltd. All rights reserved.

1. Introduction synthesizing K2TiO3, no structural refinement has resulted from

Since the first report on the photocatalytic activity of TiO2 by
Fujishima and Honda in 1972 [1] researchers have searched
extensively for other semiconducting materials with photocata-
lytic activity. Recently, there has been a surge of interest in the
investigation of potassium titanates, and especially potassium
titanate fibers, for photocatalytic applications [2], since such fibers
represent cheap, high surface area materials that are viable for
water splitting or waste remediation applications [2,3]. In addition,
there also exists interest in the synthesis of potassium titanate
nanowires [4] and the use of fibrous potassium titanates for
material-wear and tensile-strength enhancement [5]. In the past,
considerable work has been done in the TiO2 + K2O system [2,5–
15], including the synthesis and structure determination of the di-
titanate, K2Ti2O5 [15], and hexa-titanate, K2Ti6O13 [12], while the
structures of the mono-titanate K2TiO3 and tetra-titanates K2Ti4O9
have never been solved.
Several authors have synthesized K2TiO3 by solid state and high
temperature molten salt methods [7–11,13,14], where syntheses
utilizing potassium carbonate melts produced very hygroscopic,
poor quality crystals that were of insufficient quality to allow for a
structure solution [13]. Synthesis in potassium hydroxide under
vacuum [8], and via solid-state reactions with potassium
carbonate have also been attempted [10,11]. Easteal et al. [10]
succeeded in producing phase pure K2TiO3 by solid-state synthesis,
however, no attempt at a structural refinement was performed.
Thus, to this day, while many groups have succeeded in
* Corresponding author. Tel.: +1 803 777 6916; fax: +1 803 777 8508.
E-mail address: zurloye@mail.chem.sc.edu (H.-C. zur Loye).
these synthetic efforts.
Our group has developed the use of molten hydroxide fluxes as
an effective method for the growth of single crystals of diverse
oxide materials including, for example, double perovskites of the
type Ln2BB0 O6 (Ln = La–Lu; B = alkali metal, B0 = pentavalent
platinum group metal) [16–19]. Our work has focused on utilizing
this flux method as a means of exploring the synthesis of new low
temperature oxide materials, as well as an effective method for
obtaining single crystals of the oxides. In an attempt to synthesize
early transition metal containing oxides [20], we have succeeded in
the growth of high quality crystals of K2TiO3. Herein we describe
the crystal growth and single crystal structure refinement of
K2TiO3.
2. Experimental
2.1. Crystal growth
Single crystals of K2TiO3 were grown from a high temperature
potassium hydroxide melt. Silver crucibles and silver tubes were
utilized as reaction vessels; the silver tubes were flame sealed on
one end, filled with reagents, and subsequently crimped and folded
over four times at the other end. In a typical reaction, 0.1 g TiO2
(Degussa P25) and 3 g KOH (Fisher, ACS reagent) were placed
inside a silver tube or crucible. The KOH flux contained
approximately 15% water by weight, to which an additional
200 mL H2O were added to increase the melt acidity. The silver
tubes and crucibles were heated to 600 8C at 10 8C/min and held at
that temperature for 6 h before cooling to room temperature at a
rate of 0.15 8C/min in a programmable furnace. The highly
hygroscopic crystals were extracted with methanol and stored

0025-5408/$ – see front matter ß 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.materresbull.2008.03.032
92 H.S. Khalsa et al. / Materials Research Bulletin 44 (2009) 91–94

in distilled methanol, which retarded material breakdown for

approximately 2 days.

2.2. Single crystal X-ray diffraction

Fig. 1. Optical image of a single crystal of K2TiO3.
Crystals of K2TiO3 are extremely moisture-sensitive. They turn
from dull orange to colorless and deliquesce within seconds of
exposure to air. They can be handled under inert oil for several can control the acidity/basicity of the melt. Furthermore, since the
minutes. For data collection, a dull orange bar-shaped crystal was solubility of metal cations in hydroxide melts is strongly
selected, cleaved to a reasonable size under oil, and quickly dependent on the acidity/basicity of the melt, we are able to
transferred to the diffractometer cold stream. The X-ray diffraction control the solubility of metal cations in the flux. For example, to
intensity data were measured at 150(1) K on a Bruker SMART APEX dissolve titanium effectively, a high acidity (high water content) is
diffractometer (Mo Ka radiation, l = 0.71073 Å). The data collec- needed.
tion covered 100% of reciprocal space to 2umax = 75.68, with an The use of high acidity in this synthesis achieved the growth of
average reflection redundancy of 8.8, and Rint = 0.023. The raw area transparent, colorless, well-formed single crystals of K2TiO3
detector data frames were processed with SAINT+ [21]. Final unit (Fig. 1). Sealed silver tubes were used in order to maintain the
cell parameters were determined by least-squares refinement of water content at elevated temperatures and, thus, the acidity of the
3738 reflections from the data set. An absorption correction based melt during the reaction. The acidic conditions, created through
on the multiple measurement of equivalent reflections was applied the addition of water, produced transparent and colorless crystals,
to the data with SADABS [21]. Patterson methods structure whereas changing the reaction conditions by pre-drying the melt
solution, difference Fourier calculations and full-matrix least- to reduce the acidity resulted in red crystals of the same
squares refinement against F2 were performed with SHELXTL [22]. composition. The use of an open silver crucibles had a more
The atomic coordinates were standardized with Structure Tidy severe effect on the reaction environment where the evaporation
[23,24]. of water at the elevated temperatures created extremely basic melt
conditions that resulted in poor quality, brown crystals of K2TiO3,
2.3. Energy dispersive spectroscopy confirming that an acidic melt environment is needed for the
growth of high quality titanium containing oxide crystals.
A Quanta 200 SEM with an energy dispersive spectroscopy
(EDS) attachment was used for elemental analysis. EDS was 3.2. Structure of K2TiO3
performed on crystals that had undergone partial degradation due
to the reaction with moisture in the air during the loading of the The title compound, K2TiO3, crystallizes in the space group
crystals into the instrument. EDS data confirmed the stoichiometry Cmcm, as determined by a combination of the pattern of systematic
of 2K:Ti:3O and verified the absence of extraneous elements, such absences in the intensity data and the successful solution and
as silver. refinement of the structure. Relevant crystallographic data from
the single-crystal structure refinements of K2TiO3 are compiled in
2.4. Optical microscopy Table 1, while atomic positions and selected interatomic distances
are summarized in Tables 2 and 3, respectively. The unit cell, with
Optical images were acquired on a Nikon SMZ 1500 optical
microscope with a Sony 3CCD color video camera attachment.
Table 1
Images were taken with crystals submerged in distilled methanol
Crystal data and structure refinement for K2TiO3
to prevent crystal degradation.
Empirical formula K2O3Ti
Formula weight 174.10
3. Results and discussion Temperature 150(1) K
Wavelength 0.71073 Å
3.1. Crystal growth of K2TiO3 Crystal system Orthorhombic
Space group Cmcm
Unit cell dimensions a = 10.0283(2) Å
Needle-shaped single crystals of K2TiO3 of up to 15 mm in b = 6.9346(2) Å
length were grown out of a potassium hydroxide flux. Silver c = 5.4534(1) Å
reaction vessels were used since silver is resistant to attack by Volume 379.242(15) Å3
molten hydroxides and nearly immune to the extremely caustic Z 4
Density (calculated) 3.049 Mg/m3
environment used during crystal growth. The acid–base properties
Absorption coefficient 4.280 mm1
of hydroxide fluxes are best described by the Lux-Flood definition F(0 0 0) 336
of oxo-acidity and oxo-basicity [25,26]. It is well known that water Crystal size 0.44 mm  0.22 mm  0.16 mm
auto dissociates into H3O+ and OH (Eq. (1)), and hydroxide ions in Theta range for data collection 3.57–37.798
Index ranges 15 ( h ( 17, 10 ( k ( 11, 9 ( l ( 9
melts undergo a similar dissociation process into H2O and O2
Reflections collected 5155
(Eq. (2)): Independent reflections 571 [R(int) = 0.0227]
Completeness to theta = 37.79 8 100.0%
2H2 O ? OH þ H3 Oþ (1) Absorption correction Semi-empirical from equivalents
Max. and min. transmission 1.0000 and 0.6242
Refinement method Full-matrix least-squares on F2
2OH ? H2 O þ O2 (2) Data/restraints/parameters 571/0/21
Goodness-of-fit on F2 1.187
+
The definition of acidity, based on the concentration of H3O in Final R indices [I > 2sigma(I)] R1 = 0.0169, wR2 = 0.0469
water, changes in hydroxides to the concentration of H2O in the R indices (all data) R1 = 0.0172, wR2 = 0.0470
Extinction coefficient 0.0197(16)
melt. Thus, by controlling the water content of the melt, either by
Largest diff. peak and hole 0.893 and 0.514 e Å3
adding water or by drying the flux at elevated temperatures, we
 H.S. Khalsa et al. / Materials Research Bulletin 44 (2009) 91–94 93

Table 2
Atomic coordinates (104) and equivalent isotropic displacement parameters
(Å2  103) for hsk1086a

x y z U(eq)

Ti(1) 0 847(1) 2500 7(1)

K(1) 3369(1) 1480(1) 2500 12(1)
O(1) 1262(1) 0 0 10(1)
O(2) 0 3374(2) 2500 16(1)

U(eq) is defined as one-third of the trace of the orthogonalized Uij tensor.

Table 3
Selected interatomic distances (Å) for K2TiO3
Ti(1)–O(2) 1.7525(14)
Ti(1)–O(1)  4 1.9508(5)  4
K(1)–O(2) 2.7041(11)
K(1)–O(1) 2.7161(7)  2
K(1)–O(1) 2.8205(3)  2
K(1)–O(2) 3.18117(14)  2

dimensions a = 10.0283(2) Å, b = 6.9346(2) Å, and c = 5.4534(1) Å,

contains four atomic positions: Ti1 on Wyckoff site 4c (0, y, 1/4), K1
on site 8g (x, y, 1/4), O1 on site 8e (x, 0, 0), and O2 on site 4c (0, y, 1/
4). Trial refinements of the site occupancies showed no significant
deviations from unity and bond valence sums were determined to
be 3.95 for titanium and 1.12 for potassium. All atoms were refined
with anisotropic displacement parameters. The largest peak and
hole in the final difference map are +0.89 e/Å3 and 0.51 e/Å3,
located 0.60 Å and 0.52 Å from Ti1, respectively.
The crystal structure of K2TiO3 consists of chains of trans, edge-
sharing TiO5 rectangular pyramids with alternating apical direc-
tions. The chains are oriented along the crystallographic [0 0 1]
direction. A representation of a one-dimensional chain is shown in
Fig. 3. Extended structure of K2TiO3. Red spheres: oxygen; blue spheres: potassium;
grey spheres: titanium.
Fig. 2. The chains are surrounded by KO7 polyhedra as shown in
Fig. 3. The potassium ion is seven coordinate, edge sharing with
three TiO5 polyhedra and corner sharing with a seventh apical
oxygen. The pyramids themselves are regular (Fig. 2a and b), with a
rectangular base of 2.53 Å (O1i–O1, O1ii–O1iii) by 2.73 Å (O1–O1iii,
O1i–O1ii), and four apical to basal oxygen bonds of 2.99 Å. The
titanium occupies the center of the square pyramid, 0.59 Å above

Fig. 2. (a) Ellipsoid plot of an infinite one-dimensional edge-sharing chain in K2TiO3. Displacement ellipsoids drawn at the 60% probability level. Symmetry codes: (i) = x, y,
z; (ii) = x, y, z + 1/2; (iii) = x, y, z + 1/2. O1–O10 and O100 –O100 0 = 2.53 Å; O1–O100 0 and O10 –O100 = 2.73 Å; O2–O1 = 2.99 Å. The Ti1-Ti1 distances are 2.97 Å. (b) Polyhedral
representation of one chain of TiO5 square pyramids. Red spheres: oxygen; grey spheres: titanium.
94 H.S. Khalsa et al. / Materials Research Bulletin 44 (2009) 91–94
the square base with four titanium to basal oxygen bonds of
1.9508(5) Å, and one 1.7525(14) Å to the apical oxygen.
The structure is closely related to that of K2SnO3, K2ZrO3 and
K2PbO3, however unlike the zirconium, tin, and lead analogues,
the chains in K2TiO3 are undistorted with 180 8 angles along the
base of the pyramids. In K2SnO3, K2ZrO3 and K2PbO3 the apical
oxygens in the pyramids are off-center to accommodate the larger
cations.
As noted, crystals of K2TiO3 rapidly deliquesce when in
contact with moisture and will break down within seconds when
exposed to the atmosphere. The destruction of the material was
noted as early as 1916 by Niggli [27] and was also observed for
the zirconate and stannate analogues by Gatehouse et al. [28].
The crystal degradation is thought to be caused by absorbed
water that enables the zirconium or tin to reach a more favorable
six-fold coordination environment. However, as in other two-
dimensional layered compounds where the layers can be ion-
exchanged and hydrated [29] it is possible to explain the
hygroscopic nature of K2TiO3 as resulting from the hydration of
the potassium cations in the interlayer spaces. In the case of
K2TiO3, however, there are only minimal forces available to hold
the one-dimensional chains of square pyramids together,
allowing the hydration process to degrade the material. Under
more extreme conditions, such as extended treatment in boiling
water or acid, the material will undoubtedly break down into
TiO2 as noted by Niggli [27].
4. Conclusion
The synthesis and structural characterization of K2TiO3 single
crystals has been reported for the first time. The crystal structure of
the material has been solved and found to be composed of chains of
edge sharing rectangular pyramids with titanium in an uncommon
five coordinate environment. The structure is related to that of the
known tin, zirconium, and lead analogues. The crystals form as
long needles that rapidly deliquesce, but which can be stabilized in
anhydrous methanol.
Acknowledgement
Financial support from the National Science Foundation
through grant DMR: 0450103 is gratefully acknowledged.
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