inorganic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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Rietveld refinement of the mixed boracite Fe1.59Zn1.41B7O13Br

aCentro Universitario de Ciencias Exactas e Ingenierá, Universidad de Guadalajara, Laboratorio de Materiales Avanzados del Departamento de Electrónica, Av. Revolución No. 1500, Módulo O, Planta baja, Zona Olímpica, CP 44840, Guadalajara, Jalisco, Mexico, bFacultad de Ingeniería, Universidad Autóoma de Baja California, Blvd. Benito Juarez s/n col. Insurgentes, Mexicali, Baja California, Mexico, cInstituto de Física, Universidad Nacional Autónoma de México, AP 20-364, 01000 México DF, Mexico, and dCentro de Nanociencias y Nanotecnología, Universidad Nacional, Autónoma de México, Apdo. Postal 356, CP 22800, Ensenada, Baja California, Mexico
*Correspondence e-mail: jcampa@daad-alumni.de

(Received 3 September 2009; accepted 25 October 2009; online 31 October 2009)

The structural characterization of the new iron–zinc hepta­borate bromide with composition Fe1.59Zn1.41B7O13Br, prepared by chemical transport is reported. A rigid-body model with constrained generalized coordinates was defined in order to hold the positions of the B atoms at reasonable inter­atomic distances that typically would reach unacceptable values because of the weak scattering power of boron. There are three independent sites for the B atoms of which two are tetra­hedrally coordinated. The bond-valence sum around the third B atom, located on a threefold rotation axis, was calculated considering two cases of coordination of boron with oxygens: trigonal-planar and tetrahedral. The contribution of the fourth O atom to the bond-valence sum was found to be only 0.06 v.u., indicating the presence of a very weak bond in the right position to have a distorted tetra­hedral coordination in favour of the trigonal-planar coordination for the third B atom. X-ray fluorescence (XRF) was used to determinate the Fe/Zn ratio.

Related literature

The method of preparation was based on Schmid (1965[Schmid, H. (1965). J. Phys. Chem. Solids, 26, 973-988.]). For related structures, see: Mao et al. (1991[Mao, S. Y., Mendoza-Alvarez, M. E., Depmeier, W., Kubel, F. & Schmid, H. (1991). Ferroelectrics, 115, 91-96.]); Dowty & Clark (1972[Dowty, E. & Clark, J. R. (1972). Solid State Commun. 10, 543-548.], 1973[Dowty, E. & Clark, J. R. (1973). Z. Kristallogr. Kristallgeom. Kristallphys. Kristallchem. 138, 64-99.]); Mendoza-Alvarez et al. (1985[Mendoza-Alvarez, M.-E., Yvon, K., Depmeier, W. & Schmid, H. (1985). Acta Cryst. C41, 1551-1552.]); Schindler & Hawthorne (1998[Schindler, M. & Hawthorne, F. C. (1998). Can. Mineral. 36, 1195-1201.]); Knorr et al. (2007[Knorr, K., Peters, L., Winkler, B., Milman, V. & Castellanos-Guzman, A. G. (2007). J. Phys. Condens. Mat. 19, 275207-1-275207-16.]). For properties and potential applications of boracites, see: Campa-Molina et al. (1994[Campa-Molina, J., Castellanos-Guzmán, A. G., Bárcena-Soto, M. & Reyes-Gómez, J. (1994). Solid State Commun. 89, 963-969.], 2002[Campa-Molina, J., Blanco, O., Correa-Gomez, A., Czank, M. & Castellanos-Guzman, A. G. (2002). J. Microsc. 208, 201-211.]); Dana (1951[Dana, J. D. (1951). Dana's System of Mineralogy, edited by C. Palache, H. Berman & C. Frondel. New York: Wiley.]); Mathews et al. (1997[Mathews, S., Ramesh, R., Venkatesan, T. & Benedetto, J. (1997). Science, 276, 238-240.]); Smart & Moore (1992[Smart, L. & Moore, E. (1992). Solid State Chemistry, an Introduction. London: Chapman and Hall.]). For bond-valence parameters for oxides, see: Brese & O'Keeffe (1991[Brese, N. E. & O'Keeffe, M. (1991). Acta Cryst. B47, 192-197.]).

Experimental

Crystal data
  • Fe1.59Zn1.41B7O13Br

  • Mr = 544.65

  • Trigonal, R 3c

  • a = 8.6081 (1) Å

  • c = 21.0703 (3) Å

  • V = 1352.12 (3) Å3

  • Z = 6

  • Cu Kα radiation

  • T = 300 K

  • Specimen shape: irregular

  • 20 × 20 × 0.2 mm

  • Specimen prepared at 1173 K

  • Particle morphology: irregular, pale pink

Data collection
  • Bruker D8 Advance diffractometer

  • Specimen mounting: packed powder sample container

  • Specimen mounted in reflection mode

  • Scan method: step

  • 2θmin = 8.1, 2θmax = 110.0°

  • Increment in 2θ = 0.02°

Refinement
  • Rp = 0.018

  • Rwp = 0.025

  • Rexp = 0.014

  • RB = 0.06

  • S = 1.89

  • Profile function: pseudo-Voigt modified by Thompson et al. (1987[Thompson, P., Cox, D. E. & Hastings, J. B. (1987). J. Appl. Cryst. 20, 79-83.])

  • 397 reflections

  • 18 parameters

Table 1
Selected geometric parameters (Å, °)

Zn—Br 2.680 (3)
Zn—Bri 3.412 (1)
Zn—O2ii 2.130 (4)
Zn—O3iii 2.081 (7)
Zn—O4iv 2.035 (4)
Zn—O5v 2.012 (7)
B1—O2vi 1.506 (14)
B1—O3vii 1.48 (2)
B1—O4vii 1.451 (13)
B1—O5vi 1.49 (3)
B2—O1 1.566 (3)
B2—O3viii 1.452 (8)
B2—O4 1.463 (18)
B2—O5 1.453 (17)
B3—O2 1.397 (14)
B3—O1 2.38 (3)
O2—B3—O2vii 119.9 (9)
Symmetry codes: (i) [-y+{\script{1\over 3}}, -x+{\script{2\over 3}}, z+{\script{1\over 6}}]; (ii) [-x+y+{\script{1\over 3}}, y+{\script{2\over 3}}, z+{\script{1\over 6}}]; (iii) [-y+{\script{2\over 3}}, x-y+{\script{1\over 3}}, z+{\script{1\over 3}}]; (iv) [x, x-y, z+{\script{1\over 2}}]; (v) [x-{\script{1\over 3}}, y+{\script{1\over 3}}, z+{\script{1\over 3}}]; (vi) [-y-{\script{1\over 3}}, -x+{\script{1\over 3}}, z-{\script{1\over 6}}]; (vii) -y, x-y, z; (viii) -x+y, -x, z.

Data collection: DIFFRAC/AT (Siemens, 1993[Siemens (1993). DIFFRAC/AT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); cell refinement: FULLPROF (Rodríguez-Carvajal, 2006[Rodríguez-Carvajal, J. (2006). FULLPROF. http://www.ill.eu/sites/fullprof/ php/reference.html.]; Rodriguez & Rodriguez-Carvajal, 1997[Rodríguez, V. & Rodríguez-Carvajal, J. (1997). Guide for the General Rigid Body Constraints/TLS Subroutine for Rietveld Refinements. In Short Reference Guide of the program FULLPROF. http://www.ill.eu/sites/fullprof/php/reference.html.], a strongly modified version of that described by Wiles & Young, 1981); data reduction: FULLPROF; method used to solve structure: coordinates were taken from an isotypic compound (Mao et al., 1991[Mao, S. Y., Mendoza-Alvarez, M. E., Depmeier, W., Kubel, F. & Schmid, H. (1991). Ferroelectrics, 115, 91-96.]); program(s) used to refine structure: FULLPROF; software used to prepare material for publication: DIAMOND.

Supporting information


Comment top

The new iron-zinc heptaborate bromine Fe1.59Zn1.41B7O13Br, belongs to the family of boracites with general formula Me3B7O13X, where Me could be a divalent ion and X a halogen. Boracites have attracted the attention of researchers since Häuy, who observed pyroelectricity in the mineral boracite Mg3B7O13Cl (Dana, 1951). Unusual physical properties can be cited for a given cations located in the crystalographic sites for Me and X. Depending on this, potential applications such as an optic stopper (Smart & Moore, 1992); ferroelectric non volatile memory (Mathews, et al., 1997); and infrared (IR) detection (Campa -Molina et al., 1994, 2002) have been reported and in some sense, can be modulated by the presence of some specific types of cations. The aim of this research was to synthesize a new boracite with Zn and Fe in the crystalographic sites for Me in the general formula, in order to stablish in first instance, its structural and crystal chemistry properties. They are needed for the understanding of its physical properties. The representation of the crystal structure of the Fe1.59Zn1.41B7O13Br mixed boracite appear in figure 3. Bond valence calculations were made using the recommended bond-valence parameters for oxides published by Brese & O'Keeffe (1991) and considering those coordination polyhedra whose bond valence calculations were based on distances and angles that were allowed to refine (this was partially true in some cases). Bond valence sum around Br is found to be 0.82 and 1.10, for BrZn6 and BrFe6 distorted octahedra respectively. The resulting average value is then 0.97 if a composition of 53% Fe and 47% Zn is considered for this site, which is almost equal to the expected value of 1 for Br. Around the Fe/Zn site, four O atoms and Br are coordinated. The bond valence sums that result here are 1.97 and 1.76 when the site is only occupyied by Fe and Zn respectively. The average value for 53% Fe and 47% Zn is then 1.87 with good proximity to the expected value of 2. For the B(3) atom, the contribution of the fourth oxygen atom O(1) to the bond valence sum obtained for the B(3)O3 triangle of 2.8 is increased to 2.86 (i.e. only 0.06 v. u. indicating the presence of a very weak bond in the right position for have a distorted tetrahedral coordination around the planar triangle coordination for the third boron atom B(3). This fact is also a feature for the reported boracites Fe3B7O13Cl (ICSD 60504, Mendoza-Alvarez et al., 1985), and Zn3B7O13Cl (ICSD 55444, Mao et al., 1991).

Related literature top

The method of preparation was based on Schmid (1965). For related structures, see: Mao et al. (1991); Dowty & Clark (1972, 1973); Mendoza-Alvarez et al. (1985); Schindler & Hawthorne (1998); Knorr et al. (2007). For properties and potential applications of boracites, see: Campa-Molina et al. (1994, 2002) Dana (1951); Mathews et al. (1997); Smart & Moore (1992). For bond-valence parameters for oxides, see: Brese & O'Keeffe (1991).

Experimental top

Single crystals of Fe1.59Zn1.41B7O13Br were grown by a chemical vapour transport technique, commonly called the three-crucibles method, reported by Schmid (1965). Growth takes place in a closed quartz ampoule. Chemical transport reactions were carried out by heating the ampoule at about 1173 K in a resistance-heated vertical furnace, with gradients of 850 K (above) and 650 K (below), over a period of 72 h. The reactants were placed in the following order: 1.7 g of B2O3 (which was obtained by dehydrating H3BO3) was placed in the first crucible; 0.5 g of each one of both metal oxides (ZnO and FeO) in the second crucible; and 0.8 g of each one of both divalent metal halides (FeCl2 and ZnCl2) in the third crucible. Crystals of Fe1.59Zn1.41B7O13Br as large as 2 mm in size were commonly obtained. X-ray Fluorescence (XRF) spectroscopy was used to estimate the Fe/Zn ratio. A small crystallite was irradiated using the "SANDRA" system developed at Instituto de Fisica, UNAM, equipped with a 75 W Mo X-ray tube (50 kV, 1.5 mA, XTF5011 model from Oxford Instruments) and AmpTeK Si-Pin detector. The system was calibrated using reference standard materials from NIST (SRM 2711). The average percent atomic content with standard uncertainty for each element in the sample were 53 (4) % for iron, and 47 (4) % for zinc, and give a Fe:Zn ratio of 1.13. Then the stichiometric formula is Fe1.59 (12)Zn1.41 (12)B7O13Br.

Refinement top

The characterization of powdered Fe1.59Zn1.41B7O13Br mixed boracite by conventional X-ray powder diffraction data indicated the presence of a well crystallized phase showing reflections that matched with the isostructural phase trembathite, Mg1.56Fe1.44Mn0.02B7O13Cl (PDF 01–089-6198) reported by Schindler & Hawthorne (1998). The starting structural parameters to perform a Rietveld refinement of the Fe1.59Zn1.41B7O13Br boracite were taken from the isostructural data reported for Zn3B7O13Cl (ICSD 55444) by Mao et al. (1991). The following parameters were refined: zero point, scale factor, background parameters, unit cell dimensions, half-width, pseudo-Voigt and asymmetry parameters for the peak shape; position and thermal isotropic factors. For the case of boron, the thermal isotropic factors were fixed to 0.24 Å2, which is a reasonable value for the boron atom and for obtaining a good refinement. The occupation factors for Fe and Zn atoms sharing the same position were fixed to the values of 0.53 and 0.47 respectively, obtained by a quantitative chemical analysis from X-ray fluorescence (XRF) spectroscopy. Due to the very low scattering power of boron atoms to the X-rays, one rigid body group (RBG) containing the boron atoms was defined as ilustrated in figure 1. This RBG has its centre in O(1) atom. Then, eight atoms define the complete RGB (including the centre) and are labelled as B(1), B(2), B(3), O(1), O(2), O(3), O(4) and O(5). Each atom has their spherical internal coordinates (dm, φm, θm) fixed according to the rigid character of the RBG formed by these eight atoms. The parameters χc, Θc, Φc, xo, yo, zo, that were refined in a first step are represented in fig. 1 b, c and were limited by the symmetry allowed movements for the RBG as a whole. At the end of this step, B(1)O4, B(2)O4 tetrahedra, and B(3)O3 triangle kept their interatomic angles and distances. In a second and final step of refinement the spherical internal coordinates for B(3) and O(2) were refined in such a way to allow to bring the B(3)O3 triangle closer to the O(1) atom. The RBG subroutine has been included in the program FULLPROF (Rodriguez & Rodriguez-Carvajal, 1997). The use of the RBG reduced significantly the number of positional parameters in the Rietveld refinement. The results of the refinement are shown in figure 2.

Structure description top

The new iron-zinc heptaborate bromine Fe1.59Zn1.41B7O13Br, belongs to the family of boracites with general formula Me3B7O13X, where Me could be a divalent ion and X a halogen. Boracites have attracted the attention of researchers since Häuy, who observed pyroelectricity in the mineral boracite Mg3B7O13Cl (Dana, 1951). Unusual physical properties can be cited for a given cations located in the crystalographic sites for Me and X. Depending on this, potential applications such as an optic stopper (Smart & Moore, 1992); ferroelectric non volatile memory (Mathews, et al., 1997); and infrared (IR) detection (Campa -Molina et al., 1994, 2002) have been reported and in some sense, can be modulated by the presence of some specific types of cations. The aim of this research was to synthesize a new boracite with Zn and Fe in the crystalographic sites for Me in the general formula, in order to stablish in first instance, its structural and crystal chemistry properties. They are needed for the understanding of its physical properties. The representation of the crystal structure of the Fe1.59Zn1.41B7O13Br mixed boracite appear in figure 3. Bond valence calculations were made using the recommended bond-valence parameters for oxides published by Brese & O'Keeffe (1991) and considering those coordination polyhedra whose bond valence calculations were based on distances and angles that were allowed to refine (this was partially true in some cases). Bond valence sum around Br is found to be 0.82 and 1.10, for BrZn6 and BrFe6 distorted octahedra respectively. The resulting average value is then 0.97 if a composition of 53% Fe and 47% Zn is considered for this site, which is almost equal to the expected value of 1 for Br. Around the Fe/Zn site, four O atoms and Br are coordinated. The bond valence sums that result here are 1.97 and 1.76 when the site is only occupyied by Fe and Zn respectively. The average value for 53% Fe and 47% Zn is then 1.87 with good proximity to the expected value of 2. For the B(3) atom, the contribution of the fourth oxygen atom O(1) to the bond valence sum obtained for the B(3)O3 triangle of 2.8 is increased to 2.86 (i.e. only 0.06 v. u. indicating the presence of a very weak bond in the right position for have a distorted tetrahedral coordination around the planar triangle coordination for the third boron atom B(3). This fact is also a feature for the reported boracites Fe3B7O13Cl (ICSD 60504, Mendoza-Alvarez et al., 1985), and Zn3B7O13Cl (ICSD 55444, Mao et al., 1991).

The method of preparation was based on Schmid (1965). For related structures, see: Mao et al. (1991); Dowty & Clark (1972, 1973); Mendoza-Alvarez et al. (1985); Schindler & Hawthorne (1998); Knorr et al. (2007). For properties and potential applications of boracites, see: Campa-Molina et al. (1994, 2002) Dana (1951); Mathews et al. (1997); Smart & Moore (1992). For bond-valence parameters for oxides, see: Brese & O'Keeffe (1991).

Computing details top

Data collection: please supply; cell refinement: please supply; data reduction: please supply; program(s) used to solve structure: please supply; program(s) used to refine structure: FULLPROF (Rodríguez-Carvajal, 2006; Rodriguez & Rodriguez-Carvajal, 1997, a strongly modified version of that described by Wiles & Young (1981); molecular graphics: DIAMOND (Brandenburg, 2009); software used to prepare material for publication: DIAMOND (Brandenburg, 2009).

Figures top
[Figure 1] Fig. 1. (a) Rigid body group (RBG) and the coordinate systems defined for performing the movements of the RBG as a whole, are represented in the unit cell of the Fe1.59Zn1.41B7O13Br mixed boracite. (b) Atoms belonging to the RBG: some are labelled and the remainig are related by symmetry (there is a symmetry axis C3 crossing vertically the RBG). (c) Orthogonal coordinate system to perform the rotations of the RBG and orthonormal molecular system.
[Figure 2] Fig. 2. Observed (crosses), calculated (solid line) and difference (solid line at the bottom) from the final Rietveld refinement of the X-ray powder diffraction data of Fe1.59Zn1.41B7O13Br mixed boracite at room temperature. Vertical marks correspond to the positions allowed for the Bragg reflections.
[Figure 3] Fig. 3. Structural representation of Fe1.59Zn1.41B7O13Br mixed boracite.
[Figure 4] Fig. 4. Crystal structure of Fe1.59Zn1.41B7O13Br mixed boracite
iron zinc borate bromide top
Crystal data top
Fe1.59Zn1.41B7O13BrF(000) = 1546.0
Mr = 544.65Dx = 4.013 Mg m3
Trigonal, R3cCu Kα radiation, λ = 1.54175 Å
Hall symbol: R 3 -2"cT = 300 K
a = 8.6081 (1) ÅParticle morphology: irregular
c = 21.0703 (3) Åpale pink
V = 1352.12 (3) Å3irregular, 20 × 20 mm
Z = 6Specimen preparation: Prepared at 1173 K
Data collection top
Bruker D8 Advance
diffractometer
Data collection mode: reflection
Radiation source: sealed X-ray tube, Cu KαScan method: step
Graphite monochromator2θmin = 8.117°, 2θmax = 110.011°, 2θstep = 0.020°
Specimen mounting: packed powder sample container
Refinement top
Least-squares matrix: full with fixed elements per cycle5240 data points
Rp = 0.018Profile function: pseudo-Voigt modified by Thompson et al. (1987)
Rwp = 0.02518 parameters
Rexp = 0.014Weighting scheme based on measured s.u.'s
RBragg = 0.06(Δ/σ)max = 0.02
R(F2) = 0.06Background function: linear interpolation between a set of 72 background points with refinable heights
Crystal data top
Fe1.59Zn1.41B7O13BrV = 1352.12 (3) Å3
Mr = 544.65Z = 6
Trigonal, R3cCu Kα radiation, λ = 1.54175 Å
a = 8.6081 (1) ÅT = 300 K
c = 21.0703 (3) Åirregular, 20 × 20 mm
Data collection top
Bruker D8 Advance
diffractometer
Scan method: step
Specimen mounting: packed powder sample container2θmin = 8.117°, 2θmax = 110.011°, 2θstep = 0.020°
Data collection mode: reflection
Refinement top
Rp = 0.018R(F2) = 0.06
Rwp = 0.0255240 data points
Rexp = 0.01418 parameters
RBragg = 0.06
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Br0.000000.000000.266700.0084 (9)
Zn0.1488 (8)0.3037 (3)0.3347 (2)0.0113 (8)0.47000
Fe0.1488 (8)0.3037 (3)0.3347 (2)0.0113 (8)0.53000
B10.184 (1)0.1519 (1)0.080 (1)0.00304
B20.1130 (2)0.0902 (1)0.0259 (1)0.00304
B30.000000.000000.105 (1)0.00304
O10.000000.000000.008 (1)0.0025 (9)
O20.010 (1)0.157 (2)0.107 (1)0.0025 (9)
O30.282 (1)0.274 (1)0.032 (1)0.0025 (9)
O40.206 (1)0.006 (1)0.085 (1)0.0025 (9)
O50.242 (1)0.059 (1)0.024 (1)0.0025 (9)
Geometric parameters (Å, º) top
Zn—Br2.680 (3)B1—O4vii1.451 (13)
Zn—Bri3.412 (1)B1—O5vi1.49 (3)
Zn—O2ii2.130 (4)B2—O11.566 (3)
Zn—O3iii2.081 (7)B2—O3viii1.452 (8)
Zn—O4iv2.035 (4)B2—O41.463 (18)
Zn—O5v2.012 (7)B2—O51.453 (17)
B1—O2vi1.506 (14)B3—O21.397 (14)
B1—O3vii1.48 (2)B3—O12.38 (3)
Zn—Br—Znvii94.1 (2)O2—B3—O2vii119.9 (9)
Symmetry codes: (i) y+1/3, x+2/3, z+1/6; (ii) x+y+1/3, y+2/3, z+1/6; (iii) y+2/3, xy+1/3, z+1/3; (iv) x, xy, z+1/2; (v) x1/3, y+1/3, z+1/3; (vi) y1/3, x+1/3, z1/6; (vii) y, xy, z; (viii) x+y, x, z.

Experimental details

Crystal data
Chemical formulaFe1.59Zn1.41B7O13Br
Mr544.65
Crystal system, space groupTrigonal, R3c
Temperature (K)300
a, c (Å)8.6081 (1), 21.0703 (3)
V3)1352.12 (3)
Z6
Radiation typeCu Kα, λ = 1.54175 Å
Specimen shape, size (mm)Irregular, 20 × 20
Data collection
DiffractometerBruker D8 Advance
Specimen mountingPacked powder sample container
Data collection modeReflection
Scan methodStep
2θ values (°)2θmin = 8.117 2θmax = 110.011 2θstep = 0.020
Refinement
R factors and goodness of fitRp = 0.018, Rwp = 0.025, Rexp = 0.014, RBragg = 0.06, R(F2) = 0.06, χ2 = 3.572
No. of parameters18
No. of restraints?

Computer programs: please supply, FULLPROF (Rodríguez-Carvajal, 2006; Rodriguez & Rodriguez-Carvajal, 1997, a strongly modified version of that described by Wiles & Young (1981), DIAMOND (Brandenburg, 2009).

Selected geometric parameters (Å, º) top
Zn—Br2.680 (3)B1—O4vii1.451 (13)
Zn—Bri3.412 (1)B1—O5vi1.49 (3)
Zn—O2ii2.130 (4)B2—O11.566 (3)
Zn—O3iii2.081 (7)B2—O3viii1.452 (8)
Zn—O4iv2.035 (4)B2—O41.463 (18)
Zn—O5v2.012 (7)B2—O51.453 (17)
B1—O2vi1.506 (14)B3—O21.397 (14)
B1—O3vii1.48 (2)B3—O12.38 (3)
O2—B3—O2vii119.9 (9)
Symmetry codes: (i) y+1/3, x+2/3, z+1/6; (ii) x+y+1/3, y+2/3, z+1/6; (iii) y+2/3, xy+1/3, z+1/3; (iv) x, xy, z+1/2; (v) x1/3, y+1/3, z+1/3; (vi) y1/3, x+1/3, z1/6; (vii) y, xy, z; (viii) x+y, x, z.
 

Acknowledgements

The authors wish to express their thanks to J. C. Carlos Carballo-Bastida from CiCESE-Ensenada, Mexico, for his technical assistance. M. Aguilar-Franco and J. L. Ruvalcaba from Instituto de Fisica, UNAM, Mexico, are acknowledged for their valuable support in performing the XRD and XRF experiments, respectively. Thanks are also due to the Laboratorio Central de Microscopia at Instituto de Fisica, UNAM. IR acknowledges a CONACyT fellowship to support her postdoctoral programme.

References

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