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Enhanced Photocatalytic Water Splitting of SrTiO3 Perovskite through Cobalt

Doping: Experimental and Theoretical DFT Understanding

Article in Inorganic Chemistry · August 2023

DOI: 10.1021/acs.inorgchem.3c01758

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pubs.acs.org/IC Article

1 Enhanced Photocatalytic Water Splitting of SrTiO3 Perovskite

2 through Cobalt Doping: Experimental and Theoretical DFT

3 Understanding

4 Mohammed Lamhani,* Zakaria Chchiyai, Abdelali Elomrani, Bouchaib Manoun,

5 and Abdellatif Hasnaoui

Cite This: https://doi.org/10.1021/acs.inorgchem.3c01758 Read Online

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sı Supporting Information

6 ABSTRACT: Throughout extensive research endeavors, SrTiO3 has

7 emerged as a promising photocatalytic material for utilizing solar energy
8 and facilitating hydrogen production via water splitting. Yet, the pursuit of
9 enhanced efficiency and amplified hydrogen generation has prompted
10 researchers to delve into the realm of advanced doping strategies. In this
11 work, using experimental characteristics and DFT calculations, we studied the
12 effect of cobalt substitution on the structural, electronic, optical, and magnetic
13 properties as well as the photocatalytic activity of SrTi1−xCoxO3−δ (x = 0,
14 0.125, 0.25, 0.375, and 0.5) perovskites. The samples were successfully
15 prepared by using the solid-state reaction method. Based on X-ray diffraction
16 and the Rietveld refinement method, the elaborated samples were shown to
17 preserve the absorption range up to the visible region. Moreover, the position
18 of band edge levels after cobalt doping becomes more appropriate for water splitting. Our findings report that all cobalt-doped
19 compounds exhibit good photocatalytic activities and could be used as suitable photocatalyst materials for hydrogen production.

1. INTRODUCTION Strontium titanate-type perovskite, SrTiO3 (STO), has been 45

20 The simultaneous production of hydrogen (H2) and oxygen recognized as a semiconductor material with the estimated 46

21 (O2) can be achieved and sustained by the photocatalytic direct band gaps of 3.2517 and 2.98 eV18 derived by 47

22 water-splitting process,1,2 in which the substances of photo- experimental and theoretical investigations, respectively. It 48
23 catalysis capture light and generate charge carriers. These has also excellent structural stability, resistivity to photo- 49
24 charges migrate to the surface to promote the chemical corrosion, and tunability of the electronic structure.15 Due to 50
25 reaction that occurs at the surface.3 In addition, certain criteria these motivating properties, STO is considered as an attractive 51
26 must be fulfilled for the photocatalysis substance to be candidate for the photocatalytic degradation of pollutant 52
27 qualified as a successful material for the water-splitting organic molecules.19 Unfortunately, the wide band gap of 53
28 process, outlined as follows: (i) structural stability, (ii) STO limits its photocatalytic applicability exclusively to the 54
29 sufficient band gap (1.23 eV < Eg ∼2.0 eV), and (iii) relative UV domain of the solar spectrum.20 The challenge and trend 55
30 band-edge energy levels suitable for water splitting.4−6 in lowering the band gap (3.25 eV) of the STO material has 56
31 Besides, other criteria including sunlight absorption, capture been the subject of extensive research in the field of hydrogen 57
32 and recombination of electrons, holes stimulated by radiation, production from water splitting, which could be achieved 58
33 and so forth (for more details, see refs 7−910) are secondary
through doping, heterostructures, grain boundaries, chemistry 59
34 conditions to enhance the photocatalytic activity for water
defects, and band engineering.21−2324252627282930 In particular, 60
35 splitting. Among the widely developed and extensively
doping in the form of substitution or co-substitution in the A- 61
36 investigated photocatalytic systems, we can find metal−
37 organic frameworks (MOFs) 3 and perovskite oxides or/and B-site is an unmatched approach to boost the 62

38 (ABO3).7,11,12
39 Recently, perovskite materials (e.g., SrTiO3, BaTiO3, and Received: May 29, 2023
40 CaTiO3) with the general formula ABO3 have received a lot of
41 attention in the field of advanced photocatalysis.3,13,14 These
42 materials have undergone extensive research as photocatalysis
43 materials owing to their high structural stability, low toxicity,
44 high production yield, and low manufacturing cost.15,16

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63 photocatalytic activity of materials since it alters the chemical labeled as STO (undoped), STCO1, STCO2, STCO3, and 126
64 and physical properties of the materials.31−33 STCO4 for the compositions x = 0, 0.125, 0.25, 0.375, and 127
65 Over the past years, it has been demonstrated that the 0.50, respectively. Moreover, their crystal structure, optical 128
66 transition-metal (Fe, Mn, V, Cu, Ni, etc.) substitution in the properties, electronic structure, and photocatalytic activity are 129
67 Ti-site enhances significantly the photocatalytic performance reported and discussed in detail. In Section 2, we present the 130
68 of STO.15,34−363738 For example, Wu et al.19 prepared a series experimental and computational tools used to characterize the 131
69 of Mn4+ (3−7% Mn)-doped STO perovskites by the perovskites under investigation. In Section 3, the obtained 132
70 hydrothermal synthesis method. They found that the band experimental and theoretical results of pristine and cobalt- 133
71 gap reduces from 3.2 to 2.76 eV with the increase in Mn doped SrTiO3 are discussed in detail with a focus on the 134
72 amount, and the light absorption onset shifted toward the crystal and band structures, optical characteristics, and 135
73 visible region, concluding that the energy band tuning of STO photocatalytic activity. 136
74 by Mn doping is responsible for the high photocatalytic
75 activity. In another study, Wang et al.39 investigated Ce-/N- 2. METHODS
76 codoped SrTiO3 and found that the introduction of Ce and N
2.1. Material Synthesis. Powders of SrTi1−xCoxO3−δ (STCO) 137
77 decreases the band gap of STO to 2.45 eV, improving the perovskite compounds (x = 0, 0.125, 0.25, 0.375, and 0.50) were 138
78 photocatalytic performance of the STO material. prepared by the solid-state reaction method57 using highly pure 139
79 Moreover, using DFT modeling, Bentour et al.40 explored powders of strontium nitrate (Sigma-Aldrich, 99.9%), titanium(IV) 140
80 the effect of Se and Te doping at the O-site, and they revealed dioxide (Sigma-Aldrich, 99,9%), and cobalt(II) chloride hexahydrate 141
81 that the band gap decreases with Se and Te doping, which (Sigma-Aldrich, 99.5%) according to the stoichiometry, as shown in 142
82 significantly improves the performance of SrTiO3 for photo- the following reaction: 143
83 catalytic water separation. Mikuła et al.41 investigated the
84 energy stability, electronic structure, and structural properties Sr(NO3)2 + (1 x)TiO2 + xCoCl 2·6H 2O
85 of Cr incorporation in STO. Their results demonstrated that SrTi1 xCox O3 + 2NO2 + 6x H 2O + xCl 2 (1) 144
86 the effective mass of the hole is greatly increased, followed by
87 an enhancement in the band gap upon Cr substitution in the The stoichiometric powders were mixed in an agate mortar with 145
88 Ti-site. Afterward, Kumar et al.27 reported the influence of the addition of acetone for 2 h to obtain homogeneous mixtures. The 146
89 Mn- and N-codoping at the Sr- and O-sites of the STO mixtures were then treated in an oven overnight at a temperature of 147
90 material, respectively. Their results show that Mn−N-codoped 120 °C, causing the chemical elements indicated by the upward 148
91 STO is a potential candidate for photocatalytic activity under arrow to evaporate. To obtain pure phases with good crystallinity, the 149
92 visible light compared to pristine STO. obtained powders were progressively ground and calcined in air at 150
93 Recently, codoping of the STO material with Bi3+/Fe3+ ions 500, 700, and 900 °C/12 h in an alumina crucible. The calcined 151
powders were reground for 30 min to make the mixtures more 152
94 has led to an improvement of photocatalytic hydrogen
homogeneous. Finally, the powders were calcined at the temperature 153
95 production under full-range UV and visible light irradiation.42 of 1050 °C for 16 h. 154
96 It has been also reported that doping with A = Na, K, Ca, Bi, 2.2. Material Characterizations. Using a Bruker D2 PHASER 155
97 Sb, Pb, Ag, and so forth, and/or B = Ru, Rh, Ir, N, and Ag diffractometer, the purity and phase structure of the samples were 156
98 atoms, is an effective method to improve the visible light investigated by X-ray diffraction (XRD). Incident X-ray radiation was 157
99 activity of the STO material.43−45464748 Moreover, several a mixture of CuKα1 (λ = 1.5406 Å) and CuKα2 (λ = 1.5444 Å). Data 158
100 studies have reported that doping STO with rare earth were collected with a step size for signal collection of 0.01° in the 2θ 159
101 elements (such as RE = La, Ce, Pr, and Nd) can increase the range from 10 to 80° with a collection time of 1 s at each step. The 160
102 photocatalytic activity in visible light.3,49,50 XRD data were examined by the Rietveld method using WinPLOTR 161
software integrated into the Full-prof program. A JEOL LSM- 162
103 Cobalt doping was recently used to enhance the photo- IT500HRLA microscope equipped with an EDX detector was 163
104 catalytic activity of common photocatalyst oxides including employed to evaluate the microstructure and purity of the elaborated 164
105 ZnO, TiO2, and LaMnO3.51−53 For example, the introduction perovskites. To study their optical characteristics, the optical 165
106 of cobalt into LaMnO3 (at the Mn site) increases the absorption and diffuse reflection measurements of the ceramic 166
107 photocatalytic activity as a result of surface enrichment by B- compounds were identified by using a LAMBDA 1050-UV/visible 167
108 cations with higher oxidation states, Mn4+ and Co3+.54 (PerkinElmer) spectrophotometer in the wavelength range 250−800 168
109 Moreover, doping with cobalt demonstrates a good onset nm. 169
110 potential for oxygen reduction and higher current density 2.3. Density Functional Theory Calculations. Herein, spin- 170

111 compared to other transition-metal doping like Mn, Ni, Fe, polarized calculations with a ferromagnetic state were performed 171
using the norm-conserving pseudopotentials (NCPPs),58,59 as 172
112 and Cr.55 implemented in Quantum ESPRESSO (QE) package.60,61 We used 173
113 Recently, Mishra and his group found that 3% of cobalt generalized gradient approximation (GGA) for the exchange− 174
114 doping into SrTiO3 possesses the best charge transfer and correlation functional with the PBEsol parametrization62 with 175
115 recombination capability.56 Motivated by the above reports Sr(4s,4p,5s), Ti(3p,4s,3d), Co(3p,4s,3d), and O(2s,2p) valence 176
116 and due to the lack of study for cobalt-doped STO material, states. 80 and 800 Ry were utilized as the wave function energy 177
117 we choose to investigate experimentally and theoretically and charge density cutoff, respectively. The k-point mesh of the 178
118 cobalt doping at the Ti-site of STO material as a strategy to Brillouin zone sampling for the supercell was fixed at 6 × 6 × 6 based 179
119 enhance its optical properties and photocatalytic activity. In on the Monkhorst−Pack scheme.63 All simulations were run with 180

120 this work, a series of perovskites of cobalt-doped strontium fully relaxed structures, and the convergence criteria for energy and 181
force were set to 10−6 and 10−3 eV/Å, respectively. In order to adjust 182
121 titanate SrTi1−xCoxO3−δ (x = 0, 0.125, 0.25, 0.375, and 0.5) the band gap value determined by GGA, we employed the DFT + U 183
122 were experimentally prepared via a solid-state reaction formalism64−66 to increase the precision of the description of the 184
123 method. Moreover, the same compositions were theoretically localized d or f electrons. The Hubbard correction was applied to the 185
124 modeled using DFT simulations. In terms of the chemical Ti- and Co-3d states with the empirical U values of 4.82 and 5 186
125 composition of SrTi1−xCoxO3−δ (STCO), the samples were eV,22,67 respectively. When doping is involved, the used crystal 187

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Figure 1. Crystal structure of SrTi1−xCoxO3−δ compounds; (a) x = 0, (b) x = 0.125, (c) x = 0.25, (d) x = 0.375, and (e) x = 0.5.

Figure 2. (a) X-ray powder diffraction patterns of the as-prepared samples of SrTi1−xCoxO3−δ (0 ≤ x ≤ 0.5) with different Cobalt contents. (b)
An enlarged view of the (110) diffraction peak.

f1 188 structure was the 40 atom 2 × 2 × 2 supercell with cubic symmetry, 0.5, the peak shifts to a higher diffraction angle. This indicates 201
f1 189 as shown in Figure 1. that the shift of intense peaks could be related to the effect of 202
cobalt substitution. Since the ionic radius of Co is smaller (r = 203
3. RESULTS AND DISCUSSION 0.545 Å) than that of Ti (r = 0.605 Å), this could have 204
190 3.1. Structural Properties: XRD Analysis and Rietveld resulted in a reduction of the lattice parameters, and 205
191 Refinement. The XRD profiles of the cobalt-doped single thereafter, the Rietveld refinement will be used to verify the 206
192 perovskite oxides SrTi1−xCoxO3−δ (x = 0, 0.125, 0.25, 0.375, effect of cobalt substitution. 207
f2 193 and 0.5) are shown in Figure 2a. In comparison to the pristine Afterward, we performed the Rietveld refinement (de- 208
194 STO (x = 0), all compositions have identical sharp diffraction scribed in the Supporting Information)68 on the X-ray 209
195 patterns that can be well indexed by using Pm3̅m cubic diffraction data using the Full-Prof program to provide 210
196 symmetry, suggesting the appearance of a single ABO3-type different structural parameters such as unit cell, symmetry, 211
197 perovskite phase. However, no impurity peak was observed in and atomic positions. The structural refinements were carried 212
198 all samples. Moreover, Figure 2b shows an enlarged view of out with the cubic structure in the Pm3̅m symmetry for 213
199 the strongest diffraction peak (110) at about 2θ ∼ 32°, and it different concentrations of Co dopant in the Ti-site using an 214
200 is observed that with increasing cobalt substitution up to x = initial model of STO.69 In this model, the Sr, Ti/Co, and O 215

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Figure 3. Refined powder X-ray diffraction patterns for SrTi1−xCoxO3−δ perovskites: (a) x = 0, (b) x = 0.125, (c) x = 0.25, (d) x = 0.375, and (e)
x = 0.5. Red open circles indicate the observed XRD data, and black solid lines indicate the calculated XRD patterns with the Rietveld method.
The lower curve is the difference between the observed and calculated XRD patterns. The calculated positions of the Bragg reflections are marked
by vertical markers.

Table 1. Refined Lattice Parameter (a), Cell Volume, and the Different Reliability Factors Obtained from the XRD Patterns
for the Prepared SrTi1−xCoxO3−δ (0 ≤ x ≤ 0.5) Samples
sample a (Å) V (Å3) Rexp RB RF Rp RWP χ2
0 3.9059 (0) 59.591 (1) 4.35 2.61 1.73 5.11 7.00 1.59
0.125 3.9006 (2) 59.347 (5) 6.36 2.01 1.47 4.97 6.73 1.12
0.25 3.8982 (3) 59.236 (8) 5.51 3.11 2.36 4.61 5.88 1.14
0.375 3.8975 (4) 59.205 (2) 4.85 3.67 2.90 4.54 5.73 1.40
0.50 3.8941 (7) 59.050 (9) 4.35 3.91 2.65 4.23 5.39 1.53

216 atoms are placed at the 1a (0, 0, 0), 1b (1/2, 1/2, 1/2), and reliability factors are used to assess the quality of the 222
f3 217 3c (1/2, 1/2, 0) sites, respectively. Figure 3 shows excellent structural refinements. The refined structural parameters of 223
218 agreement between the observed and refined XRD patterns the cubic unit cell and various reliability factors are given in 224
219 for all the selected compositions of the SrTi1−xCoxO3−δ (0 ≤ x Table 1. From this table, it is observed that the different RF, 225 t1
220 ≤ 0.5) perovskite series using the Pm3̅m cubic structure. RB, RP, RWP, and Rexp reliability factors show small values, 226
221 During Rietveld refinement, RF, RB, RP, RWP, and Rexp revealing the success of the realized structural refinements. 227

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Figure 4. Variation of the lattice parameter a (a) and cell volume V (b) with Co amount obtained from Rietveld refinement (exp), GGA, and
GGA + U for the SrTi1−xCoxO3−δ (0 ≤ x ≤ 0.5) solid solution.

Table 2. Lattice Parameters for the Perovskite Materials SrTi1−xCoxO3−δ (0 ≤ x ≤ 0.5) Calculated by GGA, GGA + U, and
Experimental Methods (All the Values are in Å)
this work literature
x exp GGA GGA + U exp71,72 GGA20 GGA + U20
0 3.9059 3.8898 3.8934 3.9052 3.9124 3.9124
0.125 3.9006 3.8736 3.9093 3.9012 3.9012
0.25 3.8982 3.8471 3.8749
0.375 3.8975 3.8242 3.8502
0.5 3.8941 3.7996 3.8232 3.8869

228 To illustrate the effect of cobalt concentration on the average particle size of 0.47 μm, but subsequent doping with 247
229 structural parameters, their variation with the cobalt the cobalt amount changes the morphology to ice-cube-like 248
f4 230 concentration is plotted in Figure 4a,b. From these figures, formations. Figure S1 displays the histograms of the grain size 249
231 the lattice parameter ‘a’ and the volume obtained from distribution of the prepared SrTi1−xCoxO3−δ polycrystalline 250
232 Rietveld refinement show a decrease as a function of cobalt samples. The influence of cobalt doping on the grain size of 251
233 concentration, which is due to the simple substitution of Ti4+ STCO materials is shown in Figure 5f. In this figure, it can be 252
234 (r = 0.605 Å) cations by Co3+ (r = 0.545 Å) cations. In Table noticed that the grain size exhibits a decrease from 0.47 to 253
235 S1, we list the results of Rietveld refinement such as the 0.39 μm as the cobalt concentration increases from 0 to x = 254
236 Wyckoff positions, fractional atomic coordinates, isotropic 0.5. Figure S2 shows the EDX spectra of the prepared 255
237 thermal parameters, and occupancy of different atoms for the samples, which confirm that each sample contained only Sr, 256
238 synthesized SrTi1−xCoxO3−δ (x = 0, 0.125, 0.25, 0.375, and Ti, Co, and O elements without any additional elements. The 257
t2t3 239 0.5) perovskite compounds with the Pm3̅m space group. percentage weights and atomic proportion of these elements 258
for each composition are summarized in Table S2. 259
Table 3. Ti−O and Co−O Bond Lengths of Optimized Co- 3.3. DFT Calculations. The first-principles calculations of 260
doped SrTiO3 Structures, Calculated Based on Experience the optimization were conducted using the experimental 261
Using GGA and GGA + U Methods (All the Values are in crystal structure. The Site-Occupancy Disorder code (SOD) is 262
Å) used to generate all possible configurations.70 First, we 263

GGA GGA + U exp substituted different titanium concentrations of 0, 12.5, 25, 264

x Ti−O Co−O Ti−O Co−O Ti−O Co−O

37.5, and 50% with cobalt in the pristine SrTiO3. To acquire a 265
detailed overview, starting from x > 0.125, too many candidate 266
0 1.9449 1.9495 1.9530
configurations for the substitution of cobalt atoms can be 267
0.125 1.9296 1.8919 1.9408 1.9271 1.9503 1.9503
suggested. We, therefore, have explored three, four, and six 268
0.25 1.9236 1.8842 1.9407 1.9282 1.9491 1.9491
0.375 1.9071 1.8711 1.9324 1.9209 1.9488 1.9488
configurations for x = 0.25, 0.375, and 0.5, respectively. For all 269

0.50 1.9374 1.8623 1.9401 1.8541 1.9470 1.9470

configurations, the formation energy (Ef) of the investigated 270
SrTi1−xCoxO3−δ (x = 0, 0.125, 0.25, 0.375, and 0.5) materials 271
is calculated from first-principles calculations, as depicted in 272
240 3.2. Morphology and Purity: SEM and EDX. A Table S3. The most stable configuration for each concen- 273
241 scanning electron microscope was used to check and analyze tration is identified by the lowest formation energy, Ef, and is 274
242 the morphology of the prepared cobalt-doped strontium subsequently used for further analysis. The effect of cobalt 275
243 titanate SrTi1−xCoxO3−δ (x = 0, 0.125, 0.25, 0.375, and 0.50) doping on the formation energy of SrTi1−xCoxO3−δ (x = 0, 276
f5 244 samples. We report in Figure 5a−e the morphology images of 0.125, 0.25, 0.375, and 0.5) materials is depicted in Figure 6. 277 f6
245 differently prepared SrTi1−xCoxO3−δ perovskites. The micro- As a result, the cobalt doping in the STO perovskite leads to a 278
246 graph of pure STO shows nearly spherical grains with an reduction in the formation energy of the system. 279

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Figure 5. Scanning electron microscopy images of SrTi1−xCoxO3−δ samples collected in secondary electron mode; (a) x = 0, (b) x = 0.125, (c) x
= 0.25, (d) x = 0.375, and (e) x = 0.5. (f) Average grain size as a function of cobalt fraction x for the SrTi1−xCoxO3−δ perovskite series.

280 Table 2 summarizes the structural parameters for experimental structural parameters as well as with the 287
281 SrTi1−xCoxO3−δ materials with 0 ≤ x ≤ 0.5. Consistent with theoretical and experimental values from the literature 288
282 previous assumptions based on the larger ionic radii of (Table 2), with the GGA + U method demonstrating the 289
283 tetravalent Ti4+ compared to Co3+, we observe a decrease in best agreement. In addition, we find that the Ti−O bonds are 290
284 lattice parameters as the cobalt concentration increases for consistently longer than the Co−O bonds across all of the 291
285 both computational methods (GGA and GGA + U). materials studied, as presented in Table 3. These results 292
286 Importantly, our computed results agree well with the provide valuable insights into the structural properties of 293

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Figure 6. Formation energy plotted as a function of the cobalt Figure 7. Magnetic moment of the SrTi1−xCoxO3−δ materials with
fraction x for the SrTi1−xCoxO3−δ perovskite materials. different cobalt concentrations (0 ≤ x ≤ 0.5).

294 SrTi1−xCoxO3−δ materials and have important implications for Clearly, from the band structure of STCO shown in Figure 335
295 their potential applications in various fields. 8a,b, it is observed that STO is a direct semiconductor with a 336
296 Figure 4a,b also illustrates how the lattice ‘a’ and volume ‘V’ band gap of 1.88 and 2.97 eV for GGA and GGA + U, 337
297 parameters change as a function of the cobalt content respectively. For the pristine STO, the electronic band 338
298 determined by DFT and experience. The DFT results show structure determined by GGA + U is consistent with our 339
299 the same trend as that of the experiment, showing the lattice experimental results, which is 3.27 eV for the direct band gap. 340
300 parameter and volume of the doped samples to be lower than For additional comparisons, our results found by GGA + U 341
301 those of the pristine samples. and experiment agree well with several findings in the 342
302 3.4. Magnetic and Electronic Structures. The influence literature.19,20,49,73,74 After the incorporation of cobalt, the 343
303 of cobalt doping on the magnetic and electronic characteristics band gap energy decreased gradually from 1.88/2.97 to 0.92/ 344
304 estimated using the GGA and GGA + U methods is explored 1.53 eV using the GGA/GGA + U method, respectively. 345
305 in this section. At 0 K, GGA and GGA + U compute that the Moreover, for the compositions STO, STCO3, and STCO4, 346
306 pristine STO structure is paramagnetic. The structure changes the forbidden band is of a direct type that occurred at Γ point, 347
307 from paramagnetic (PM) to ferromagnetic (FM) after doping whereas the indirect forbidden band is observed at the M/R- 348
308 (i.e., x = 0.125), while the experiment shows that the Γ/X direction for the compositions STCO1 and STCO2. 349
309 magnetic transition is observed at x = 0.375 from PM to Essentially, DFT + U offers accurate estimations of electronic 350
310 antiferromagnetic (AFM), according to ref 72. This difference characteristics that are congruent with the experimental data 351
311 between the DFT and the experiment can be due to the (see Section 3.5). 352
312 difference in the measurement temperature. In addition, the The PDOSs of various concentrations of cobalt doped at 353
313 variation of the magnetic moment of the cobalt ions, the Ti-site in STO with a ferromagnetic configuration are 354
314 calculated by GGA and GGA + U, as a function of presented in Figure 9 to illustrate the effect of doping on the 355
f7 315 concentration x is presented in Figure 7. It is observed that electronic properties of the pristine (STO). Contributions to 356
316 after doping, the magnetic moment does not change or spin-up and spin-down are shown separately (top and bottom, 357
317 changes a little, and the GGA + U approach offers more respectively). For composition x = 0, the valence band (VB) is 358
318 accurate findings than the GGA method compared to the predominantly composed of 2p-O states, while the conduction 359
319 experimental findings reported in the literature.72 band (CB) is mainly composed of 3d-Ti states that remain 360
320 On the other hand, Table S4 lists the magnetic moments of insulated with a band gap, revealing a semiconductor nature. 361
321 all ions calculated by GGA and GGA + U. We observe that After doping, the behavior of the states (2p-O and 3d-Ti) that 362
322 the GGA method gives magnetic moments lower than 1 μB, contribute to the conduction and valence bands almost exactly 363
323 resulting in a low-spin configuration of Co4+ (t52ge0g) ion. matches that of pure SrTiO3, in which the 3d-states of cobalt 364
324 Furthermore, the Hubbard correction (GGA + U) provides a cations are observed at energies between ∼0.5 and 2 eV and 365
325 magnetic moment close to 3 μB in all systems (Table S4). As a change slimly with the amount of cobalt. 366
326 result, the ground state of the Co4+ ion doped in SrTiO3 For further analysis of the PDOSs (Figure 9b), around the 367
327 appears to be an intermediate spin state (t42ge1g). This agrees Fermi level down to 1 eV, there is an apparent peak that 368
328 well with the experimentally observed range of magnetic corresponds to the Co and O antibinding states that gradually 369
329 moments from 2.67 to 2.48 μB for x = 0.05 to 0.50, increases with the doping amount. This hybridization between 370
330 respectively.72 Summary of these moments are given in Table Co-3d and O-2p takes place between 2 and 3.5 eV,75 as seen 371
331 S4 (Supporting Information). in the bismuth−strontium cobaltite ([Bi0.87SrO2]2[CoO2]1.82). 372
332 The calculated electronic structures and the corresponding For all systems, we also see a second peak appearing at about 373
333 partial density of states (PDOSs) of cobalt-doped strontium 2 eV, suggesting that the O-2p and Ti-3d orbitals have 374
f8f9 334 titanate (STCO) are shown in Figures 8 and 9, respectively. hybridized. In addition to this, in ABO3-type perovskites, the 375

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Figure 8. Band structure of SrTi1−xCoxO3−δ (0 ≤ x ≤ 0.5) perovskites calculated by using GGA (a) and GGA + U (b). The Fermi level is
adjusted to zero. The high-symmetry points are labeled by Γ (0, 0, 0), X (0.5, 0, 0), M (0.5, 0.5, 0), and R (0.5, 0.5, 0.5). The maximum value of
the valence band and the minimum value of the conduction band are shown by the blue and red dots of GGA and GGA + U, respectively.

Figure 9. Electronic DOSs of SrTi1−xCoxO3−δ materials with different Co concentrations (0 ≤ x ≤ 0.5) obtained with (a) GGA and (b) GGA +
U. The Fermi level is set to zero.

376 transition metal exhibits hybridization with O-2p like V or Ni gap energy of the SrTiO3 material, is also experimentally 380
377 recently reported in SrTiO3.35,45 investigated. Utilizing UV−visible absorption spectra, the 381
378 3.5. UV−vis Spectroscopy. Herein, the effect of cobalt optical band gap energies of cobalt-doped STO perovskites 382
379 doping on the optical properties, such as absorption and band were examined. In the wavelength range of 250−800 nm, the 383

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384 UV−vis absorption spectra for the STCO samples were (1 R )2

f10 385 captured at room temperature, as displayed in Figure 10. F (R ) =
S 2R (2) 400

where F(R) denotes the Kubelka−Munk function, α is the 401

absorption coefficient, and R is the diffuse reflectance (DR). 402
For direct allowed transitions, the optical band gap of each 403
synthesized compound was calculated based on the Tauc 404
method according to the following equation26 405

h = A( h Eg )2 (3) 406

where (hν) is the incident photon energy, A is a constant, and 407

Eg is the optical band gap energy. For each composition, the 408
Tauc plots of (αhν)2 versus photon energy (hν) are depicted 409
in Figure 11a−e. In these figures, the band gap values of the 410 f11
STCO materials, computed as the slope of the linear part, are 411
shown. Pristine STO has a band gap energy of 3.27 eV, which 412
agrees with the other values in the literature.76,77 The impact 413
of the cobalt concentration on the band gap energy of the 414
SrTi1−xCoxO3−δ materials is displayed in Figure 12. It is clear 415 f12
that with the increasing cobalt substitution in STO, Eg 416
Figure 10. Absorbance spectra of the prepared SrTi1−xCoxO3−δ (x =
generally decreases from 3.27 to 1.56 eV. Meanwhile, as was 417
0, 0.125, 0.25, 0.375, and 0.50) perovskite samples measured at room
temperature in UV and visible light regions. previously mentioned, this is compatible with the first- 418
principles modeling for cobalt-doped STO materials. This 419
result is generally in agreement with previous investigations on 420

386 Based on the UV−visible absorption spectrum, the sample cobalt-doped STO that employed other different amounts (x 421

387 STO (x = 0) exhibits two UV absorption bands at roughly = 0.10, 0.20, 0.30, 0.40, and 0.50).76 422

388 280 and 345 nm, although no visible bands could be found. 3.6. Photocatalytic Activity. The photon energy received 423
389 As the concentration of cobalt increases, the absorption edge by a semiconductor material (suspended in water) during the 424
390 shifts away from the UV light and moves toward the visible photocatalytic fractionation process can excite electrons from 425
391 range. All cobalt-doped STO samples exhibit a maximum the valence band (VB) into the conduction band (CB), 426
392 absorbance in the optical range from 350 to 800 nm, including leaving excited holes in the VB. Following their migration to 427
393 the whole visible range, which suggests good absorption of the photocatalyst surface, the photogenerated electron−hole 428
394 solar light for all cobalt-doped samples. Thus, enhancement of pairs subsequently start redox reactions with the water 429
395 the optical properties of STO materials is achieved through molecules that have been adsorbed in the active sites, as 430
396 cobalt doping. presented in Figure 13a. In global water splitting, the 431 f13
397 Using the Kubelka−Munk function, the UV−vis diffuse semiconductor photocatalysts are used to decompose H2O 432
398 reflectance spectra have been transformed into absorbance molecules to H2 and O2 simultaneously, according to eqs 433
399 spectra using the following formula69: 4−6.8,78,79 434

Figure 11. Tauc curves of (αhν)2 as a function of energy hν for the SrTi1−xCoxO3−δ series: (a) x = 0, (b) x = 0.125, (c) x = 0.25, (d) x = 0.375,
and (e) x = 0.5.

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Based on the optical band gap energy (Eg), the energy levels 451
of VBM and CBM of pristine and cobalt-doped SrTiO3 452
materials can be calculated via the following relations81: 453

1
E VBM = STCO Ee + Eg
2 (7) 454

ECBM = E VBM Eg (8) 455

where Ee = 4.5 eV denotes the total energy of a free electron, 456

and χSTCO denotes the electronegativity of pure and cobalt- 457
doped STO materials, which is calculated by the formula 458
below69: 459

1 x x 3 1/5
STCO =[ Sr Ti Co O ] (9) 460

where χSTCO represents the absolute electronegativity for each 461

composition in the perovskite series SrTi1−xCoxO3−δ (0 ≤ x ≤ 462
0.50), and χSr, χTi, χCo, and χO are the electronegativities of Sr, 463
Figure 12. Evolution of the optical band gap energy as a function of Ti, Co, and O elements, respectively. Besides, the electro- 464
cobalt substitution in SrTi1−xCoxO3−δ perovskites. negativity values of various elements were obtained from 465
Bartolotti.82 466
+ 1+ From Figure 13b, we get a clear indication that pure SrTiO3 467
H 2O + 2h 2H + O2
435 2 (4) is suitable for water-splitting application since its computed 468
CBM (−1.163 eV) is lower than the reduction potential (H+/ 469

436 2H+ + 2e H2 (5) H2), and VBM (2.107 eV) is higher than the oxidation 470
potential (O2/H2O), in agreement with the values reported in 471
1 the literature (ECBM = −0.49 eV vs NHE, and EVBM = 2.71 eV 472
H 2O H 2 + O2 vs NHE).83 When Co is incorporated at the Ti-site of the 473
437 2 (6)
STO material, we notice that the CBM and VBM edges 474
438 Moreover, Figure 13b illustrates the calculated valence and approach the reduction and oxidation potentials, respectively. 475
439 conduction band-edge positions of the cobalt-substituted STO However, the water redox levels are still sandwiched between 476
440 perovskites, which give an in-depth vision of the performance the CBM and VBM, indicating an improvement in the 477
441 of the photocatalytic activity for elaborated perovskites. In the performance of photocatalytic water splitting through the 478
442 photocatalytic water-splitting process, a semiconductor ma- addition of cobalt ions. Our results indicate that cobalt doping 479
443 terial with a band gap energy larger than 1.23 eV is required. is an effective strategy to improve the splitting of water like 480
444 The redox levels of water must also be sandwiched between other reported elements, as shown in Table S5. Overall, 481
445 the conduction band minimum (CBM) and valence band cobalt-doped compounds meet the criteria for the water- 482
446 maximum (VBM), i.e., the CBM should be lower than the splitting process in terms of the energy band gaps and the 483
447 reduction potential of H+/H2 (0 eV vs normal hydrogen band-edge (CBM and VBM) positions, which are reported to 484
448 electrode NHE), and the VBM should be higher than the be significantly lower than those of the pristine STO structure. 485
449 oxidation potential of O2/H2O (1.23 eV vs normal hydrogen Thereby, these compounds are suitable and promising 486
450 electrode NHE) simultaneously.80 candidates for the water-splitting application. 487

Figure 13. (a) Schematic representation for the photocatalytic water-splitting process and (b) VBM and CBM positions of pristine and cobalt-
doped SrTiO3 materials relative to the NHE potential.

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4. CONCLUSIONS https://pubs.acs.org/10.1021/acs.inorgchem.3c01758 546

488 The effect of cobalt doping on the crystal structure and

489 morphological, magnetic, electronic, and photocatalytic Notes 547
490 properties of the SrTiO 3 matrix has been examined The authors declare no competing financial interest. 548
experimentally and theoretically. The SrTi1−xCoxO3−δ (x =
■
491
492 0, 0.125, 0.25, 0.375, and 0.5) perovskite oxides were ACKNOWLEDGMENTS 549
493 successfully synthesized by the solid-state method, with
494 calcination at 1050 °C. Based on the XRD patterns and the This research was supported through computational resources 550

495 Rietveld refinement method, the cobalt-doped compounds of HPC-MARWAN provided by the National Center for 551

496 show a Pm3̅m cubic crystal structure similar to the pristine Scientific and Technical Research (CNRST), Rabat, Morocco. 552

497
498
499
material, SrTiO3. The SEM results indicate the dimensions in
grain size from 0.47 to 0.39 μm as a function of cobalt
content, x = 0 to 0.5. Compared to the pristine SrTiO3, the
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524 Khouribga, Morocco; orcid.org/0000-0002-9442-8950; and Future Perspectives. Catal. Today 2019, 327, 47−63. 584
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533 Mathematics and Environment Sciences (LS2ME), Sultane (12) Ahmadi, M.; Seyed Dorraji, M. S.; Rasoulifard, M. H.; Amani- 595
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537 Instrumentation, S3M, Hassan First University of Settat, (13) Soltani, T.; Zhu, X.; Yamamoto, A.; Singh, S. P.; Fudo, E.; 599
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539 Nano-engineering Department, University Mohammed VI Oxide Cocatalyst on the Photocatalytic Activity of Ag Loaded 601
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541 Abdellatif Hasnaoui − FPK, Laboratory of Materials, Catal. B Environ. 2021, 286, No. 119899. 603
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