Journal of Coordination Chemistry

ISSN: 0095-8972 (Print) 1029-0389 (Online) Journal homepage: https://www.tandfonline.com/loi/gcoo20

Diaqua oxalato strontium(II) complex as a

precursor for facile fabrication of Ag-NPs@SrCO3,
characterization, optical properties, morphological
studies and adsorption efficiency

A.M. Nassar, A.M. Elseman, Ibrahim Hotan Alsohaimi, N. F. Alotaibi & A.

Khan

To cite this article: A.M. Nassar, A.M. Elseman, Ibrahim Hotan Alsohaimi, N. F. Alotaibi & A.
Khan (2019): Diaqua oxalato strontium(II) complex as a precursor for facile fabrication of Ag-
NPs@SrCO3, characterization, optical properties, morphological studies and adsorption efficiency,
Journal of Coordination Chemistry, DOI: 10.1080/00958972.2019.1588964

To link to this article: https://doi.org/10.1080/00958972.2019.1588964

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 Diaqua oxalato strontium(II) complex as a precursor for facile fabrication of
Ag-NPs@SrCO3, characterization, optical properties, morphological studies
and adsorption efficiency
A.M. NASSAR*1,2,†, A.M. ELSEMAN*3,†, IBRAHIM HOTAN ALSOHAIMI1, N. F. ALOTAIBI1 and A. KHAN4,5

1
Chemistry Department, College of Science, Jouf University, P.O. Box 2014, Sakaka, Saudi Arabia
2
Chemistry Department, Faculty of Science, Al-Azhar University, Nasr City, Cairo, Egypt
3
Electronic and Magnetic Materials Department, Advanced Material Division, Central Metallurgical Research
and Development Institute (CMRDI), P.O. Box 87 Helwan, 11745 Cairo, Egypt

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4
College of Environmental Science and Engineering, North China Electric Power University,

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Beijing 102206, PR China
5
Institute of Chemical Sciences University of Peshawar, Peshawar, Khyber Pakhtunkhwa, Pakistan 25120
†

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These authors contributed equally to this work

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Diaqua oxalato strontium(II) complex [Sr(C2O4)(H2O)2] was prepared via a precipitation
reaction. Thermal treatment of the as-synthesized precursor at 550 C resulted in formation of
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strontium carbonate (SrCO3) nanocrystals. A new composite of silver nanoparticles decorated
with strontium carbonate (Ag-NPs@SrCO3) was fabricated by heating a mixture of silver oxalate
and strontium carbonate in the air at 150 C for 2 h. The spectral and morphological properties of
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the materials have been confirmed using different physicochemical techniques such as X-ray
diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive X-ray
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spectroscopy (EDX), high-resolution transmission electron microscopy (HR-TEM), Fourier

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infrared spectroscopy (FT-IR) and thermal gravimetric analysis (TGA). From the Debye–
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Scherrer equation the calculated particle size of SrC2O4·2H2O, SrCO3 and Ag@SrCO3 are 62.1,
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58.7 and 58.5 nm, respectively. The SEM and TEM images indicate tetragonal structure of
[Sr(C2O4)(H2O)2] while SrCO3 and Ag-NPs@SrCO3 appeared as cubic structures. The calculated
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energy band gap of SrCO3 and Ag-NPs@SrCO3 using the Tauc equation are estimated at 5.9 eV
and 4.7 eV, respectively. The adsorption capacity of the materials is tested for the adsorption of
Congo red anionic dye and exhibited promising results. The adsorption capacity followed the
order Ag-NPs@SrCO3>SrCO3>[Sr(C2O4)(H2O)2] with efficiencies of 73.90%, 67.55% and
60.50%, respectively.

*Corresponding authors. Email: nassar_tanta@yahoo.com (A.M. Nassar); AhmedMourtada5555@yahoo.com

(A.M. Elseman)

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Graphical abstract

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Keywords: Strontium; Silver decorated; Thermal treatment; Congo red; Band gap
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1. Introduction
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Strontianite or strontium carbonate (SrCO3) has been used in large-scale applications such as a
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chemical sensors, glasses and ceramics, bioactive materials, catalysts, composites for enhancing
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catalytic properties, TV screen fabrications and in industrial production [1-7]. S. Jin et al.
considered SrCO3 as economic and environmentally friendly material (eco-friendly material) in
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the improvement of the photocatalytic activity of SrTiO3 during NO removal [8]. Some studies
have discussed the adsorption properties of SrCO3 due to its various architectures [9, 10]. There
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are several methods for preparation of strontium carbonate with different morphologies which
affect the material shape [11]. Recently, W. Zhang et al. reported the controllable synthesis of
micro-nanostructures of strontium carbonate with different morphological structures through
hydrothermal preparation [12]. Thermal decomposition of strontium oxalate also resulted in the
formation of strontium carbonate [13]. At room temperature, SrCO3 has orthorhombic structure
and converts to hexagonal shape when heated at 912 C [14].

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 Silver nanoparticles (Ag-NPs) are widely used in different applications [15, 16] such as
antibacterial agents, anticancer drugs, biomedical devices, food industry, optical, thermal and
electrical conductivity. Ag-NPs have been used in many textiles, keyboards and wound dressings
[17]. Enhanced activity of silver nanoparticles with different materials has been reported [18-20].
Recently, we reported a facile method for synthesis of Ag-NPs decorated with lead carbonate
and lead oxides; the study exhibited a remarkable enhancement of solid state electrical
conductivity of the lead compounds in the presence of decorated Ag-NPs [21].
The present study aims to fabrication of silver nanoparticles decorated with strontium

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carbonate as a new material via thermal degradation of diaqua oxalato strontium(II) complex
[Sr(C2O4)(H2O)2] and silver oxalate precursors. The spectral, thermal, optical and morphological

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properties and adsorption capacity of the materials are studied.

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2. Experimental
2.1. Materials an
The chemicals used in this study are Congo red, oxalic acid, strontium nitrate and silver nitrate
from BDH or Sigma-Aldrich Chemicals without further purifications. All aqueous solutions were
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prepared with distilled water.
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2.2. Preparation of diaqua oxalato strontium(II) complex, [Sr(C2O4)(H2O)2]

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Diaqua oxalato strontium(II) complex [Sr(C2O4)(H2O)2] was prepared using the method reported
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[13] with some modifications. Strontium nitrate (4.22 g, 0.02 mol) was dissolved in 25 mL
distilled water. Then, 25 mL of oxalic acid solution (1.9 g, 0.02 mol) was added to the previous
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solution with stirring at 75 C. After 1 h, the white precipitate formed was filtered off, washed
with hot water (3×10 ml) and then dried in air. The results of thermal gravimetric analysis of the
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obtained precipitate were consistent with the composition of SrC2O4·2H2O.

2.3. Preparation of strontium carbonate, SrCO3

Strontium carbonate was prepared using the method reported [14] with some modifications.
Thermal treatment of [Sr(C2O4)(H2O)2] in a porcelain crucible with heating rate 10 C/min for
3 h formed SrCO3 as a white powder.

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2.4. Preparation of silver oxalate, Ag2C2O4
Silver oxalate was prepared using the previously reported method [22]. AgNO3 solution (1M,
30 mL) was mixed with oxalic acid solution (0.5 M, 30 mL) and the mixture was heated at 70 C
with stirring for 1 h, then the white precipitate was filtered, washed several times with hot
distilled water and dried in air.

2.5. Fabrication of silver decorated strontianite, Ag-NPs@SrCO3

Silver decorated strontium carbonate is fabricated by mixing 1 g of silver oxalate with 3 g of

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strontium carbonate and the mixture kept at 150 C in an oven for 2 h. Ag@SrCO3 is formed as a

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grayish white powder. The synthesis mechanism of Ag@SrCO3 is shown in figure 1.

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2.6. Instruments
XRD measurements were performed using a Shimadzu X-600 (Japan). The surface morphology
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of the samples was explored using Scanning Electron Microscopy (SEM-JSM 6360 LA, Japan)
coupled with EDX. Transmission electron microscopy (TEM) and high-resolution transmission
electron microscopy (HRTEM) were performed with a JEOL-JEM-1230 microscope. Infrared
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spectra were recorded using an FT-IR affinity-1S Shimadzu; electronic spectra were obtained
using a LABOMED – spectro UV-Vis double beam-3200. The thermal stability was investigated
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by thermogravimetric analysis (TGA) using a TGA Q5000 thermal analyzer (Shimadzu

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Corporation) from 50-900 C in air flow at a heating rate of 10 C min-1. The surface elemental
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composition was recorded by X-ray photoelectron spectroscopy (XPS) on an ESCA Lab 220i-
XL electron spectrometer from VG Scientific using 300 W Al Ka radiation.
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3. Results and discussion

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3.1. X-ray powder diffraction

[Sr(C2O4)(H2O)2], SrCO3 and Ag@SrCO3 were characterized by X-ray diffraction to confirm the
structure as shown in figure 2. From XRD patterns, we calculated the crystallite size, lattice
constant and unit cell volume as described in table 1. These results were similar to the data
obtained from XRD of [Sr(C2O4)(H2O)2] to those reported by Arora et al. [13]. All the indexed
diffraction patterns could follow the body-centered tetragonal structure of SrC2O4·2H2O with
lattice parameter a = 6.47 Å, b = 6.52 Å and c = 6.493 Å (JCPDS, No. 00-020-1204). In turn, the

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SrCO3 has been indexed to a pure orthorhombic phase of strontianite with lattice constants a =
5.107 Å, b = 8.414 Å and c = 6.209 Å (data from JCPDS file number 005-0418). XRD peaks at
2θ of 20.3°, 21.10°, 25.17°, 25.80°, 29.61° and 36.52° could be attributed to the 110, 020, 111,
021, 002 and 130 crystallographic planes of orthorhombic phase. In addition, diffraction peaks of
SrCO3 broadened due to a nanosize effect, and the crystallinity and high purity were indicated by
no noticeable additional peaks. Finally, figure 2 shows the XRD pattern of Ag-NPs decorated
SrCO3 synthesized using direct reaction as described in the flow chart, figure 1. The XRD
patterns of Ag@SrCO3 revealed face-centered cubic and all the Ag-NPs had a similar diffraction

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profile. XRD peaks at 2θ of 38.18°, 44.25°, 64.72° and 77.40° could be attributed to the 111,

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200, 220 and 311 crystallographic planes of the face-centered cubic silver crystals, respectively.

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The XRD pattern clearly demonstrated that the Ag-NPs were crystalline. The main crystalline
phase was silver, and the other phases were found for SrCO3. The average crystallite sizes of

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prepared compound can be calculated using the Debye–Scherrer equation 1 [23-25],
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dRX = k /  Cos θ (1)

where dRX is the crystallite size,  is the wavelength of Cu target = 1.5406 Å, k = 0.9 is a
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correction factor to account for particle shapes,  is the Bragg angle, and  is the full width at
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half maximum (FWHM) of the most intense diffraction peak plane. From the Scherrer equation,
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the average crystallite sizes of [Sr(C2O4)(H2O)2], SrCO3 and Ag-NPs@SrCO3 are found to be
62.1, 58.7 and 58.5 nm in size (table 1), which is also in line with the TEM results discussed
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later. These data indicate that the particle sizes of the materials exist within the nano-scale range.
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Moreover, the particle surface area S in m2g-1 for the samples was determined using equation 2
[26, 27],
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𝑺 = 𝟔𝟎𝟎𝟎/𝑫𝝆 (2)

where D is the crystallite size in nm obtained from the diffraction lines of [Sr(C2O4)(H2O)2],
SrCO3 and Ag@SrCO3 and ρ is the density of the compounds. The particle surface area of the
samples is depicted in table 1. Ag-NPs@SrCO3 has the smaller size (58.5 nm) and higher value
of S; [Sr(C2O4)(H2O)2] has relatively bigger size (62.1 nm) with smaller value of S [28].

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3.2. Microstructure
The SEM micrographs of the produced [Sr(C2O4)(H2O)2] are shown in figure 3a. Irregular
precipitated particles, with random grain orientation as well as a broad particle size distribution,
still grow SrC2O4·2H2O in tetragonal structure which means that such structure was consistent
with the XRD result. Then, the strontium carbonate was prepared using thermal treatment of
[Sr(C2O4)(H2O)2] precursor. The particles started to grow and distributed well with cubic shape.
As the annealing temperature increased (figure 3b), the formed SrCO3 crystals possessed
numbers of cubic small particles. The similar trend also appeared for silver loaded strontium

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carbonate composite as evidenced in figure 3c. The effect of silver on the strontium carbonate
gave more crystal growth with large grain uniform size. These materials have been confirmed by

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EDX analysis. [Sr(C2O4)(H2O)2] and SrCO3 samples have Sr, O and C with different ratio while
the Ag-NPs@SrCO3 sample also has the presence of Ag along with Sr, O and C as shown in

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figures 3(d-f) and the elemental ratio for the different elements in the samples are given in
table 2. Figures 4(a-f) show the transmission electron micrograph (TEM) and the selected area
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electron diffraction pattern (SAED) corresponding to [Sr(C2O4)(H2O)2], SrCO3 and
Ag-NPs@SrCO3 samples, respectively. The crystals in figure 4a for [Sr(C2O4)(H2O)2] consisted
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of one cluster with body-centered tetragonal structure of 150-200 nm. SrCO3 (figure 4b)
appeared like surrounded particle cubes regular in shape with dimension of 90-100 nm. Ag-
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NPs@SrCO3 (figure 4c) was composed of the same structure as in figure 4b along with silver
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nanoparticles decorated SrCO3 surface.

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3.3. FT-IR spectra

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The infrared spectra of the prepared materials are recorded and compared with that of oxalic acid
(figure 5). The IR spectrum of oxalic acid shows νC=O as bands at 1590-1670 cm-1, indicating
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the trans configuration of two carboxylic groups [27]. The spectrum displayed a broad band as a
doublet assigned to stretching vibrations of hydroxyl groups and crystalline water molecules.
The spectrum of strontium complex exhibited a very intense broad band centered at 3455 cm-1
which is related to υOH of water molecules. The strong band at 1630 cm-1 was for υCOO stretching
mode [29]. The strong broad band of SrCO3 centered at 1453 cm-1 is assignable to asymmetric
stretching vibration of CO32-. Also, sharp bands at 600 cm-1 and 870 cm-1 are attributed to
bending in plane and bending out of plane vibrations of CO32- [30]. The IR spectrum of Ag

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doped strontianite has the same bands in the spectrum of unloaded strontianite. The presence of
silver nanoparticles on SrCO3 confirmed physical decorated form and not chemical bonds.

3.4. TGA-DSC studies

TGA and DSC curves of the materials are collected in figures 6a-c. The TG-DSC curves of the
strontium complex precursor show two steps of TG decomposition and two sharp DSC peaks.
The first decomposition step of [Sr(C2O4)(H2O)2] at 180-200 C is related to dehydration of two
coordinated water molecules with mass loss, found: 17.55% and calc: 17.01%. A strong

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exothermic peak at 195 C is due to the evaporation of water molecules. The second thermal

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degradation step (450-525 C) is assigned to elimination of one carbon monoxide with mass loss,

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found: 13.50%, calc: 13.23%. The strong endothermic peak at 480 C is ascribed to

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decomposition of anhydrous strontium oxalate to strontium carbonate and carbon monoxide [31].
The exothermic elevation following endothermic carbonate formation is attributed to the
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evolution of CO2 after disproportionation of the evolved carbon monoxide to give carbon dioxide
and carbon [32]. The residual part (69%) corresponded to formation of strontium carbonate, calc
69.75%. The TG-DSC results are consistent with the precursor structure of [Sr(C2O4)(H2O)2].
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3.5. X-ray photoelectron spectroscopy (XPS) analysis

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Ag-NPs decorated SrCO3 as composite is characterized by XPS to evaluate its structure and
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purity. The XPS spectrum has only Ag, Sr, C and O without any other contaminant species
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(figure 7a). The binding energies were observed at 133.4, 284.6, 358.8 and 533.2 eV of the Sr
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3d5/2, C 1s, Ag 3d5/2 and O 1s, respectively, which are consistent with literature values [33, 34].
Figure 7b shows Sr binding energies with a peak fit analysis of the Sr 3d5/2 and Sr 3d3/2 signals in
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mixed Gaussian-Lorentzian profiles, revealing two underlying components of the binding

energies at 133.4 eV and 135.2 eV. The binding energies of C 1s and O 1s are 532.01 and
284.8 eV, consistent with standard parameter values, confirming that SrCO3 phases are present in
the composite. The enlarged XPS spectra of C1s, Ag 3d are shown in figures 7c and 7d,
respectively. The Ag 3d spectrum has doublets for Ag 3d5/2 and Ag 3d3/2 at 368.49 eV and
374.5 eV which correspond to metallic silver [35].

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3.6. Energy band gap
The energy band gap was determined from Tuac’s equation [36],

αhν = A(hν –Eg)n (3)

where n is equal to 1/2 for allowed direct transitions and 2 for allowed indirect transitions, A is
an energy-independent constant, α is the absorption coefficient and Eg is allowed energy gap.
The plots of (αhν)2 and (αhν)1/2 versus hν are shown in figures 8a and 8b for SrCO3 and
Ag-Nps@SrCO3, respectively. The direct band gap was found by extrapolating the linear portion

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of the curve to (αhν)1/2 = 0. The curves indicated that the direct band gap values Eg are 5.9 eV
and 4.7 eV for SrCO3 and Ag-NPs@SrCO3, respectively. The lower energy band gap of

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Ag-Nps@SrCO3 than SrCO3 may be attributed to the presence of silver nanoparticles, which

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increases the HOMO and decreases the LUMO. The silver nanoparticles facilitate electronic
transitions between the HOMO–LUMO energy levels which decrease the energy band gap and
enhance the photoactivity of SrCO3 [37].
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3.7. Adsorption properties of materials
The adsorption capacity of Ag-NPs@SrCO3 is determined and compared with the adsorption
capacity for both [Sr(C2O4)(H2O)2] and SrCO3. The materials were exposed to Congo red dye as
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an application toward purifying water polluted with dyes. Congo red dye is high stable and
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harmful to the environment [38, 39]. The efficiency for removal of Congo red dye from water
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was carried out by electronic spectra. The materials were prepared in equal concentrations
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(5×10-5 M) of the dye in separate flasks; each flask was placed with 0.1 g from each material and
stirred in a water bath for 15 min. Then, filtration was accomplished for all flasks and filtrates
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collected. Figure 9 shows the electronic spectrum of Congo red solutions before and after
treatment with the adsorbents. Free adsorbent solution spectrum shows two main peaks at
346 nm and 496 nm with intensity of 0.78 and 1.08, respectively, consistent with literature [18].
The highest intensity band at 496 nm was selected to compare efficiency of eliminating Congo
red dye from solution. The efficiency of Congo red removal from solution is presented in
figure S1. Calculation of efficiency was obtained by applying equation 4,

Q = [(A0-At) /A0] ×100 (4)

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where Q is the execution efficiency, A0 is the dye initial concentration and At is the dye
concentration after 15 min. Figure S1 shows that the most effective material to remove dye from
solution is Ag-Nps@SrCO3 at 73.90%, while SrCO3 removed dye by 67.55%. The least effective
material is [Sr(C2O4)(H2O)2] with efficiency of 60.50%. Figure 10 shows the SEM image and
EDX analysis of Ag-NPs@SrCO3 after adsorption of Congo red dye. The changing morphology
of the adsorbent surface in comparison with surface morphology of free Ag-NPs@SrCO3
(figure 3c) gives good evidence for adsorption. EDX analysis of the sample in comparing with

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EDX of adsorbent indicates the presence of S and N elements from dye molecules. The

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adsorption results suggest potential application of these materials as effective adsorbents. An

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intensive investigation for all physical parameters of adsorption should be carried out.

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3.8. Mechanism of adsorption
Figure 11 shows the adsorption mechanism of Congo red on to Ag@SrCO3 composite. From the
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result of zeta potential, the surface of Ag@SrCO3 composite was positive (10 mV), indicating
high adsorption of Congo red on Ag@SrCO3 surface. The adsorption ability of Ag@SrCO3
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composite for Congo red has been assigned to electrostatic interaction between the positive
charge on the surface of Ag@SrCO3 and the negative charge of sulfonate (-SO3-) in Congo red
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anionic dye.
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4. Conclusion
We have fabricated new composite silver nanoparticles decorated with strontium carbonate.
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Ag-NPs@SrCO3 is characterized using different physicochemical techniques. The optical

properties of the composite showed semiconducting properties and an enhancement in
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comparing with the optical properties of SrCO3. The values of the direct band gap Eg are
enhanced from 5.9 eV to 4.7 eV for SrCO3 and Ag-NPs@SrCO3, respectively. The adsorption
capacity of the studied materials for Congo red dye showed the composite Ag-NPs@SrCO3
exhibited the best action. Further work using SrCO3 and Ag-NPs@SrCO3 as adsorbents in
wastewater treatment is in progress.

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Acknowledgements
The authors are thankful to Jouf University for giving permission to conduct the analysis and for
access to analytical equipment.

Conflicts of interest
The authors declare no competing financial interest.

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Table 1. Crystallite size, lattice parameters and unit cell volume of SrC2O4·2H2O, SrCO3 and
Ag@SrCO3.

Crystallite size, Surface area Lattice constant Unit cell volume,

Formed phase
Dx (nm) S (m2g-1) a (Å) b (Å) c (Å) V (Å3)

[Sr(C2O4)(H2O)2] 62.1 33.45 6.47 6.52 6.49 85.489

SrCO3 58.7 36.01 5.10 8.41 6.21 84.703
Ag@SrCO3 58.5 36.50 5.12 8.63 6.46

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Table 2. EDX elemental ratio for the [Sr(C2O4)(H2O)2], SrCO3 and Ag@SrCO3
samples.

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Element SrC2O4·2H2O SrCO3 Ag@SrCO3
C 29.92 37.48 21.57
O 56.96
an 55.71 55.55
Sr 12.91 6.69 12.72
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Ag ----- ----- 10.16
total 100 100 100
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Figure 1. Schematic diagram for the production of [Sr(C2O4)(H2O)2], SrCO3 and

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Ag-NPs@SrCO3 samples.

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 * o
Ag / *SrCO3
* o
*
** ** o * ** o o

*
* SrCO3
Intensity (a.u.)

* * *
**

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** **

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SrC2O4.2H2O

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10 20 30 40
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50 60 70 80
2 / o
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Figure 2. XRD of [Sr(C2O4)(H2O)2], SrCO3 and Ag-NPs@SrCO3.
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Figure 3. (a), (b) and (c) SEM microstructure and (d), (e) and (f) EDX for [Sr(C 2O4)(H2O)2],
SrCO3 and Ag-NPs@SrCO3 samples, respectively.

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Figure 4. (a), (b) and (c) TEM microstructure and (d), (e) and (f) SAED pattern for
[Sr(C2O4)(H2O)2], SrCO3 and Ag@SrCO3 samples, respectively.

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T%

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3500 3000 2500 2000 1500 1000 500

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wavenumber (ῡ) cm-1

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Figure 5. IR spectra of oxalic acid and prepared materials.
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Figure 6. TGA and DSC curves of (a) [Sr(C2O4)(H2O)2], (b) SrCO3 and (c) Ag-NPs@SrCO3
samples.
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Figure 7. XPS survey spectra of Ag-NPs@SrCO3 (a) full, (b) Sr 3d, (c) C 1s, (d) Ag 3d and
(e) O 1s.

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Figure 8. Optical band gap of (a) SrCO3 and (b) Ag@SrCO3.
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 2

1.8

1.6

1.4

1.2

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0.8

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0.6

cr
0.4

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0.2

0 an
195 245 295 345 395 445 495 545 595 645 695

Congo red [Sr(C2O4)(H2O)2] SrCO3 Ag@SrCO3

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Figure 9. Electronic spectra of Congo red dye before and after adsorption.
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Figure 10. SEM and EDX of Ag-NPs@SrCO3 after adsorption of Congo red dye.
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Figure 11. Mechanism of adsorption of Congo red dye on Ag@SrCO3 surface.
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