Fe-doped SrTiO₃ perovskites: exploring their applications in photocatalytic dye degradation and supercapacitors

Abstract

Fe-doped SrTiO₃, SrTi_1−xFe_xO₃ (STFO, x = 0.3, 0.5, 0.7), were prepared using the solid-state reaction method and their performances in photocatalytic dye degradation and supercapacitor applications were tested. STFO samples were characterized using XRD, EDX, and XPS to confirm its cubic perovskite structure and chemical compositions. The morphology and particle size were analyzed via SEM. UV‒Vis spectroscopy reveal that Fe³⁺ could tune the bandgap and an optimized bandgap of 2.15 eV was found in STFO (x = 0.5), which is suitable for visible photocatalysts. Raman spectra could characterize the longitudinal and transverse optical modes (LO and TO), which revealed the phonon vibration of STFOs. The decolorization efficiency of the MB dye is found to be 87.71% at 220 min under visible light. The decolorization kinetics was found to be of the pseudo-first-order type with the R² value of 0.66 and the degradation rate constant of 0.02 min⁻¹. STFO (x = 0.7) was found to be the optimized supercapacitor material with the specific capacitance of 1028.45 F·g⁻¹, energy density of 0.0073 W·h·kg⁻¹, and power density of 22.74 W·kg⁻¹ at the current density of 0.22 A·g⁻¹. This study is anticipated to encourage exploring more potential lead-free perovskite materials with high dielectricity and low cost for photocatalytic and energy storage applications.

Graphical abstract

Keywords

perovskite / doped SrTiO ₃ / XPS / photocatalysis / supercapacitor

References

[1] Choi M, Posadas A B, Rodriguez C A, . Structural, optical, and electrical properties of strained La-doped SrTiO₃ films.Journal of Applied Physics, 2014, 116(4): 043705

[2] Wang J, Li N, Tang Y H, . Visible light photocatalytic performance of Y−Fe co-doped with SrTiO₃ perovskite powder.International Journal of Electrochemical Science, 2022, 17(8): 22081

[3] Phoon B L, Lai C W, Juan J C, . A review of synthesis and morphology of SrTiO₃ for energy and other applications.International Journal of Energy Research, 2019, 43(10): 5151–5174

[4] Kundu S, Clavel M, Biswas P, . Lead-free epitaxial ferroelectric material integration on semiconducting (100) Nb-doped SrTiO₃ for low-power non-volatile memory and efficient ultraviolet ray detection.Scientific Reports, 2015, 5: 12415

[5] Shafique H, Aldaghfag S A, Kashif M, . Magnetic and optical characteristics of Fe doped SrTiO₃ perovskite compound: a first principle study.Chalcogenide Letters, 2021, 18(10): 589–599

[6] Caviglia A D, Gariglio S, Reyren N, . Electric field control of the LaAlO₃/SrTiO₃ interface ground state.Nature, 2008, 456(7222): 624–627

[7] Mohapatra L, Parida K . A review of solar and visible light active oxobridged materials for energy and environment.Catalysis Science & Technology, 2017, 7(11): 2153–2164

[8] Li X, Zhao H, Zhou X, . Electrical conductivity and structural stability of La-doped SrTiO₃ with A-site deficiency as anode materials for solid oxide fuel cells.International Journal of Hydrogen Energy, 2010, 35(15): 7913–7918

[9] Kato K, Jiang J, Sakata Y, . Effect of Na-doping on electron decay kinetics in SrTiO₃ photocatalyst.ChemCatChem, 2019, 11(24): 6349–6354

[10] Hussain T, Junaid M, Qayyum H A . Preparation of Ba-doped SrTiO₃ photocatalyst by sol–gel method for hydrogen generation.Chemical Physics Letters, 2020, 754: 137741

[11] Viruthagiri G, Praveen P, Mugundan S, . Synthesis and characterization of pure and nickel doped SrTiO₃ nanoparticles via solid state reaction route.Indian Journal of Advanced Chemical Sciences, 2013, 1(3): 132–138

[12] Karaphun A, Hunpratub S, Phokha S, . Effect of Co cations and oxygen vacancy on optical and magnetic properties of SrTi_1−xCo_xO₃ nanoparticles prepared by the hydrothermal method.Journal of Materials Science: Materials in Electronics, 2017, 28(11): 8294–8303

[13] Bae S W, Borse P H, Lee J S . Dopant dependent band gap tailoring of hydrothermally prepared cubic SrTi_xM_1−xO₃ (M = Ru, Rh, Ir, Pt, Pd) nanoparticles as visible light photocatalysts.Applied Physics Letters, 2008, 92(10): 104107

[14] Zhou X, Shi J, Li C . Effect of metal doping on electronic structure and visible light absorption of SrTiO₃ and NaTaO₃ (metal = Mn, Fe, and Co).The Journal of Physical Chemistry C, 2011, 115(16): 8305–8311

[15] Abbas H A, Jamil T S . Nano sized Fe doped strontium titanate for photocatalytic degradation of dibutyl phthalate under visible light.Advanced Materials Letters, 2016, 7(6): 467–471

[16] Li P, Liu C B, Wu G L, . Solvothermal synthesis and visible light-driven photocatalytic degradation for tetracycline of Fe-doped SrTiO₃.RSC Advances, 2014, 4(88): 47615–47624

[17] Aravinthkumar K, Babu G A, Mohan C R . Promoting active sites of Fe³⁺ ions in SrTiO₃ nanosphere: a superior candidate for high performances of dye-sensitized solar cell and photocatalytic dye degradation.Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2023, 672: 131702

[18] Abdi M, Mahdikhah V, Sheibani S . Visible light photocatalytic performance of La–Fe co-doped SrTiO₃ perovskite powder.Optical Materials, 2020, 102: 109803

[19] Xie T H, Sun X, Lin J . Enhanced photocatalytic degradation of RhB driven by visible light-induced MMCT of Ti(IV)−O−Fe(II) formed in Fe-doped SrTiO₃.The Journal of Physical Chemistry C, 2008, 112(26): 9753–9759

[20] Deshmukh V V, Ravikumar C R, Kumar M R A, . Structure, morphology and electrochemical properties of SrTiO₃ perovskite: photocatalytic and supercapacitor applications.Environmental Chemistry and Ecotoxicology, 2021, 3: 241–248

[21] Priyadharsini C I, Marimuthu G, Pazhanivel T, . Electrochemical supercapacitor studies of Ni²⁺-doped SrTiO₃ nanoparticles by a ball milling method.Ionics, 2020, 26(7): 3591–3597

[22] Paul P C, Shah A, Singh L R, . Mn-doped SrTiO₃ and SrTiO₃–Fe₂O₃ composite perovskites: photocatalytic dye degradation and energy storage application.Journal of Materials Science: Materials in Electronics, 2023, 34(16): 1305

[23] Sharma D K, Sain S, Maity G, . Electrochemical studies on chromium doped SrTiO₃ for supercapacitor applications.Nano Trends, 2024, 6: 100036

[24] Cao Y, Li S, Zhong J, . CNT@SrTiO₃ nanocomposites synthesized by in situ reaction for a high-performance flexible supercapacitor.ACS Omega, 2024, 9(20): 22423–22435

[25] Cheng L, Liu K, Gao H, . Energy storage performance of sandwich structure composites with strawberry-like Ag@SrTiO₃ nanofillers.Chemical Engineering Journal, 2022, 435: 135064

[26] Chen H, Chen H W, Gao L B, . Energy storage properties of (Pb, Sm, La)(Zr, Sn, Ti)O₃ antiferroelectric ceramics with SrTiO₃ modified.Journal of Materials Science: Materials in Electronics, 2022, 33(10): 7718–7727

[27] Diantoro M, Ittikhad A A, Suprayogi T, . Performance of B-doped SrTiO₃/Ni sheet for supercapacitor material application.Key Engineering Materials, 2020, 851: 25–31

[28] Shahabuddin S, Numan A, Shahid M M, . Polyaniline‒SrTiO₃ nanocube based binary nanocomposite as highly stable electrode material for high performance supercapaterry.Ceramics International, 2019, 45(9): 11428–11437

[29] Balu S, Uma K, Pan G T, . Degradation of methylene blue dye in the presence of visible light using SrO₂@–Fe₂O₃ nanocomposites deposited on SnS₂ flowers.Materials, 2018, 11(6): 1030

[30] Ghaffari M, Liu T, Huang H, . Investigation of local structure effect and X-ray absorption characteristics (EXAFS) of Fe (Ti) K-edge on photocatalyst properties of SrTi_1−xFe_xO_3−δ.Materials Chemistry and Physics, 2012, 136(2−3): 347–357

[31] Nath A, Shah A, Singh L R, . Waste plastic-derived NiO–MWCNT composite as visible light photocatalyst for degradation of methylene blue dye.Nanotechnology for Environmental Engineerings, 2021, 6(3): 70

[32] Shah A, Mao Y M, Singh L R, . Waste plastic-derived FWCNT–NiMgAl composite for supercapacitor application.Carbon Letters, 2022, 32(6): 1541–1557

[33] Shah A, Senapati S, Murthy H C A, . Supercapacitor performance of NiO, NiO–MWCNT and NiO–Fe MWCNT composites.ACS Omega, 2023, 8(37): 33380–33391

[34] Van Minh N, Phuong D T T . SrTi_1−xFe_xO₃ nanoparticle: a study of structural, optical, impedance and magnetic properties.Journal of Experimental Nanoscience, 2011, 6(3): 226–237

[35] Humayun M, Xu L, Zhou L, . Exceptional co-catalyst free photocatalytic activities of B and Fe co-doped SrTiO₃ for CO₂ conversion and H₂ evolution.Nano Research, 2018, 11(12): 6391–6404

[36] Ahangari M, Mahmoodi E, Delibas N, . Application of SrFeO₃ perovskite as electrode material for supercapacitor and investigation of Co-doping effect on the B-site.Turkish Journal of Chemistry, 2022, 46(5): 1723–1732

[37] Fuentes S, Munoz P, Barraza N, . Structural characterisation of slightly Fe-doped SrTiO₃ grown via a sol–gel hydrothermal synthesis.Journal of Sol-Gel Science and Technology, 2015, 75(3): 593–601

[38] Pramanik S, Mondal S, Mandal A C, . Role of oxygen vacancies on the green photoluminescence of microwave-assisted grown ZnO nanorods.Journal of Alloys and Compounds, 2020, 849: 156684

[39] Ahmadi M, Dorraji M S S, Rasoulifard M H, . The effective role of reduced-graphene oxide in visible light photocatalytic activity of wide band gap SrTiO₃ semiconductor.Separation and Purification Technology, 2019, 228: 115771

[40] da Silva L F, Maia L J Q, Bernardi M I B, . An improved method for preparation of SrTiO₃ nanoparticles.Materials Chemistry and Physics, 2011, 125(1−2): 168–173

[41] Muhamad N F, Osman R A M, Idris M S, . Physical and electrical properties of SrTiO₃ and SrZrO₃.EPJ Web of Conferences, 2017, 162: 01052

[42] Pei Y, Zhang R, Song Y, . Emergent magnetic phase transitions in Fe doped SrTiO₃.AIP Advances, 2019, 9(12): 125302

[43] Dwij V, De B K, Tyagi S, . Fano resonance and relaxor behavior in Pr doped SrTiO₃: a Raman spectroscopic investigation.Physica B: Condensed Matter, 2021, 620: 413265

[44] Hasan T, Saha A, Khan M N I, . Structural, electrical, and magnetic properties of Ce and Fe doped SrTiO₃.AIP Advances, 2022, 12(9): 095003

[45] Xu Y B, Kang Z F, Fan Y, . Electrical properties of the YSZ/STO/YSZ−STO superlattice electrolyte film at low temperatures.Russian Journal of Physical Chemistry A: Focus on Chemistry, 2016, 90(2): 485–490

[46] Mahato D K, Molak A, Szeremeta A Z, . Effect of hetero-valence ions on structural and electrical properties of La₂Ni(Mn_0.5Ti_0.5)O₆ ceramics.Ceramics International, 2024, 50(15): 27086–27101

[47] Viernstein A, Kubicek M, Morgenbesser M, . High-temperature photochromism of Fe-doped SrTiO₃ caused by UV-induced bulk stoichiometry changes.Advanced Functional Materials, 2019, 29(23): 1900196

[48] Li R, Liu F, Zhang C, . Electrical properties of Fe-doped SrTiO₃ with B-site-deficient for SOFC anodes.Ceramics International, 2019, 45(17): 21684–21687

[49] Nath A, Mahato M . Polystyrene‒NiO‒CNT composite ball and film for photocatalytic degradation of methylene blue dye.Materials Today: Proceedings, 2022, 57: 321–327

[50] Laohana P, Tanapongpisit N, Kim S, . Particle size dependence of the electrochemical properties of SrTiO₃ supercapacitor electrodes.Journal of Solid State Electrochemistry, 2021, 25(4): 1121–1129

RIGHTS & PERMISSIONS

Higher Education Press