Abstract
Cerium, nitrogen, and sulfur ions were doped into SrTiO3 (STO) lattice by sol–gel method. PXRD results confirm the cubic perovskite structure for all the doped samples. Higher Ce dopant concentration leads to the formation of CeO2 as a separate phase. X-ray density calculations show the solid to be of omission solid solution type material. A red shift in the absorption towards the visible region for all the doped samples was due to the formation of various mid-band gap states. FTIR technique confirms the presence of bidentately coordinated SO42− ions on the surface of doped samples. The XPS technique confirms the presence of Ce3+, Ce4+, S6+ and two different types of nitrogen. The surface acidity of the doped catalyst increases by the presence of SO42− and OH− ions favoring efficient trapping of photogenerated electrons. The upward shift in the position of VB of doped samples by almost 0.26 eV reduces the band gap of CeNS-STO samples as confirmed by the VB XPS technique. The lower PL intensity and higher magnitude of photocurrent for Ce0.48N0.19S0.44–SrTiO3 (CeNS-STO (2)) sample corresponds to higher separation efficiency of photogenerated electron-hole pairs. The enhanced photocatalytic activity of CeNS-STO (2) sample under both UV/solar light may be attributed to the synergistic effect between the three dopants Ce4+, N3−, and S6+ narrow band gap, decreased crystallite size, mesoporous structure, and high surface area. Intermediate products were identified by HPLC analysis and a possible degradation reaction mechanism was proposed.
Highlights
-
Ce4+, N3−, and S6+ ions were incorporated into SrTiO3 lattice.
-
X-ray density values of doped samples were found to decrease with the increase in the dopant concentration.
-
The observed lift in the VB edge by 0.26 eV is due to the N dopant at different lattice sites.
-
S6+ ion on the surface of catalysts gets oxidized to highly electron withdrawing SO42− species.
-
The ease of conversion of Ce3+ ↔ Ce4+ facilitates electron trapping and detrapping process.
Similar content being viewed by others
References
Puangpetch T, Sreethawong T, Yoshikawa S, Chavadej S (2008) Synthesis and photocatalytic activity in methyl orange degradation of mesoporous- assembled SrTiO3 nanocrystals prepared by sol gel method with the aid of structure-directing surfactant. J Mol Catal A: Chem 287:70–79
Zheng Z, Huang B, Qin X, Zhang X, Dai Y (2011) Facile synthesis of SrTiO3 hollow microspheres built as assembly of nanocubes and their associated photocatalytic activity. J Colloid Interface Sci 358:68–72
Wu G, Li P, Xu D, Luo B, Hong Y, Shi W, Liu C (2015) Hydrothermal synthesis and visible-light-driven photocatalytic degradation for tetracycline of Mn-doped SrTiO3 nanocubes. Appl Surf Sci 333:39–47
Yu He, Yan S, Li Z, Yu T, Zou Z (2012) Efficient visible-light-driven photocatalytic H2 production over Cr/N-codoped SrTiO3. Int J Hydrog Energy 37:12120–12127
Wang J, Yin S, Komatsu M, Zhang Q, Saito F, Sato T (2004) Photo-oxidation properties of nitrogen doped SrTiO3 made by mechanical activation. Appl Catal B Environ 52:11–21
Karunakaran C, Gomathisankar P (2013) Solvothermal Synthesis of CeO2−TiO2 Nanocomposite for Visible Light Photocatalytic Detoxification of Cyanide. Sustain Chem Eng 1:1555–1563
Djaja N, Saleh R (2013) Characteristics and photocatalytics activities of Ce-doped ZnO nanoparticles. Mater Sci Appl 4:145–152
Xiao G, Huang X, Liao X, Shi B (2013) One-pot facile synthesis of cerium-doped TiO2 mesoporous nanofibers using collagen fiber as the biotemplate and its application in visible light photocatalysis. J Phys Chem C 117:9739–9746
Amana N, Satapathy PK, Mishra T, Mahato M, Das NN (2012) Synthesis and photocatalytic activity of mesoporous cerium doped TiO2 as visible light sensitive photocatalyst Mater Res Bull 47:179–183
Masui T, Fujiwara K, Machida K-i, Adachi G-y (1997) Characterization of cerium(IV) oxide ultrafine particles prepared using reversed micelles. Chem Mater 9:2197–2204
Silva AMT, Silva CG, Drazic G, Faria JL (2009) Ce-doped TiO2 for photocatalytic degradation of chlorophenol. Catal Today 144:13–18
Yan N, Zhu Z, Zhang J, Zhao Z, Liu Q (2012) Preparation and properties of Ce-doped TiO2 photocatalyst. Mater Res Bull 47:1869–1873
S and car K, Yang G, Jiang Z, Shi H, Xiao T, Yan Z (2010) Preparation of highly visible-light active N-doped TiO2 photocatalyst. J Mater Chem 20:5301–5309
Gomathi Devi L, Kavitha R (2014) Enhanced photocatalytic activity of sulfur doped TiO2 for the decomposition of phenol: A new insight into the bulk and surface modification. Mater Chem Phys 143:1300–1308
Chao-hail W, Xin-hu’ T, Jie-rong L, Shu-ying T (2007) Preparation, characterization and photocatalytic activities of boron and cerium-codoped Ti02. J Environ Sci 19:90–96
Song S, Xu L, He Z, Chen J, Xiao X, Yan B (2007) Mechanism of the Photocatalytic Degradation of C.I. Reactive Black 5 at pH 12.0 Using SrTiO3/CeO2 as the Catalyst. Environ Sci Technol 41:5846–5853
Sulaeman U, Yin S, Suehiro T, Sato T (2009) Solvothermal synthesis of SrTiO3-LnTiO2N solid solution and their visible light responsive photocatalytic properties. Mater Sci Eng 1:012017
Zhangb C, Jia Y, Jing Y, Yao Y (2015) New insights into assessing the favorable cooping dopants with various co-doped cases for the band gap engineering of SrTiO3, Int J Hydrogen Energy 40:1343–1351
Wei W, Dai Y, Guo M, Yu L, Jin H, Han S, Huang B (2010) Codoping synergistic effects in N-doped SrTiO3 for higher energy conversion efficiency. Phys Chem Chem Phys 12:7612–7619
Yu He, Yan S, Li Z, Yu T, Zou Z (2012) Efficient visible-light-driven photocatalytic H2 production over Cr/N-codoped SrTiO3. Int J Hydrog Energy 37:12120–12127
Cheng X, Yu X, Xing Z (2012) One-step synthesis of Fe–N–S-tri-doped TiO2 catalyst and its enhanced visible light photocatalytic activity. Mater Res Bull 47:3804–3809
Gomathi Devi L, Anitha BG (2018) Exploration of vectorial charge transfer mechanism in TiO2/SrTiO3 composite under UV light illumination for the degradation of 4-Nitrophenol: A comparative study with TiO2 and SrTiO3. Surf Interface 11:48–56
Gomathi Devi L, ArunaKumari ML, Anitha BG, Shyamala R, Poornima G (2016) Photocatalytic evaluation of Hemin (chloro(protoporhyinato)iron(III)) anchored ZnO hetero-aggregate system under UV/solar light irradiation: A surface modification method. Surf Interface 1–3:52–58
Leonid V Azroff, Introduction to Solids, Tata McGraw-Hill publishing company, New Delhi, T M H Edition 10th reprint (1990); Anthony R. West, Solid State Chemistry and its Applications, John Wiley and Sons, reprint June (1987) Singapore edition.
Liu C, Tang X, Mo C, Qiang Z (2008) Characterization and activity of visible-light-driven TiO2 photocatalyst codoped with nitrogen and cerium. J Solid State Chem 181:913–919
Lu M, Zhang Y, Wang Y, Jiang M, Yao X (2016) Insight into several factors that affect the conversion between antioxidant and oxidant activities of nanoceria. ACS Appl Mater Interfaces 8:23580–23590
Choudhury B, Borah B, Choudhury A (2012) Extending photocatalytic activity of TiO2 nanoparticles to visible region of illumination by doping of cerium. Photochem Photobiol 88:257–264
Ye T, Huang W, Zeng L, Li M, Shi J(2017) CeO2-x platelet from monometallic cerium layered double hydroxides and its photocatalytic reduction of CO2 Appl Catal, B 17(S0926-3373):30264-3
Wang Y, Wang Y, Meng Y, Ding H, Shan Y (2008) A highly efficient visible-light-activated photocatalyst based on bismuth- and sulfur-codoped TiO2. J Phys Chem C 112:6620–6626
Jung SM, Grange P (2002) TiO2–SiO2 mixed oxide modified with H2SO4: II. Acid properties and their SCR reactivity. Appl Catal A: Gen 228(1–2):65–73
Bae E, Choi W (2003) Highly enhanced photoreductive degradation of perchlorinated compounds on dye-sensitized metal/TiO2 under visible light. Environ Sci Technol 37:147–152
Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouquerol J, Siemieniewska T (1985) International union of pure and applied chemistry. Pure Appl Chem 57(4):603–619
lPelaez M, de la Cruz AA, Stathatos E, Falaras P, Dionysiou DD (2009) Visible light-activated N-F-codoped TiO2 nanoparticles for the photocatalytic degradation of microcystin-LR in water. Catal Today 144:19–205
Chen X, Burda C (2004) Photoelectron spectroscopic investigation of nitrogen-doped titania nanoparticles. J Phys Chem B 108:15446–15449
Krishna Reddy J, Suresh G, Hymavathi CH, Durga Kumari V, Subrahmanyam M (2009) Ce (III) species supported zeolites as novel photocatalysts for hydrogen production from water. Catal Today 141:89–93
Kavitha R, Gomathi Devi L (2014) Synergistic effect between carbon dopant in titania lattice and surface carbonaceous species for enhancing the visible light photocatalysis. J Environ Chem Eng 2:857–867
Xue W, Zhang G, Xu X, Yang X, Liu C, Xu Y (2011) Preparation of titania nanotubes doped with cerium and their photocatalytic activity for glyphosate. Chem Eng J 167:397–402
Zhanga Y, Donga K, Liua Z, Wanga H, Maa S, Zhanga A, Lia M, Yua L, Yan L (2017) Sulfurized hematite for photo-Fenton catalysis. Prog Mater Sci Natl: Mater Int 27:443–451
Li F-T, Zhao Y, Hao Y-J, Wang X-J, Liu R-H, Zhao D-S, Chen D-M (2012) N-doped P25 TiO2–amorphous Al2O3 composites: One-step solution combustion preparation and enhanced visible-light photocatalytic activity J Hazard Mater 239–240:118–127
Cong Y, Zhang J, Chen F, Masakazu (2007) Synthesis and characterization of nitrogen-doped TiO2 nanophotocatalyst with high visible light activity anpo. J Phys Chem C 111:6976–6982
Yang X, Cao C, Erickson L, Hohn K, Maghirang R, Klabunde K (2009) Photo-catalytic degradation of Rhodamine B on C-, S-, N-, and Fe-doped TiO2 under visible-light irradiation. Appl Catal B Environ 91:657–662
Pleskov YV (1981) Conversion of luminous energy into electrical and chemical energy in photoelectrochemical cells with semiconductor electrodes (review). J Sov Electrochem 17(1):1–25
Palmisano L, Augugliaro V, Sclafani A, Schiavello M (1988) Activity of chromium-ion-doped titania for the dinitrogen photoreduction to ammonia and for the phenol photodegradation. J Phys Chem 92:6710–6713
Xue W, Zhang G, Xu X, Yang X, Liu C, Xu Y (2011) Preparation of titania nanotubes doped with cerium and their photocatalytic activity for glyphosate. Chem Eng J 167:397–402
Gomathi Devi L, Girish Kumar S (2011) Influence of physicochemical–electronic properties of transition metal ion doped polycrystalline titania on the photocatalytic degradation of Indigo Carmine and 4-nitrophenol under UV/solar light. Appl Surf Sci 257:2779–2790
Sobczyński A, Duczmal L, Zmudziński W (2004) Phenol destruction by photocatalysis on TiO2: an attempt to solve the reaction mechanism J Mol Catal A: Chem 213:225–230
Acknowledgements
Authors acknowledge the financial assistance from University Grants Commission for DSA-SAP project.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Additional information
Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Rights and permissions
About this article
Cite this article
Devi, L.G., Anitha, B.G. Effective band gap engineering by the incorporation of Ce, N and S dopant ions into the SrTiO3 lattice: exploration of photocatalytic activity under UV/solar light. J Sol-Gel Sci Technol 94, 50–66 (2020). https://doi.org/10.1007/s10971-019-05074-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10971-019-05074-4