Series of Sc/V co-doped rutile TiO2 with different Sc/V ratio was synthesized. Samples were characterized by XRD, SEM, XPS, BET, EPR, diffuse reflectance spectroscopy and Kelvin probe methods. EPR spectroscopy reveals a simultaneous increase of V4+ and Ti3+ as vanadium content grows. At the same time, an increase of vanadium concentration in co-doped samples results in stronger absorption in visible light range. However, a photocatalytic activity dependence on the co-dopant ratio demonstrates “volcano” plot behavior with maximum at 75/25 Sc/V ratio, while the work function dependence on Sc/V ratio demonstrates a negative correlation with photocatalytic activity resulting in a minimal value of work function at the same optimal ratio of co-dopant content. The analysis of the experimental results infers that alteration of Sc/V co-doping ratio leads to redistribution between shallow traps, which are not effective in charge carrier recombination, and deep traps, which act as effective recombination centers, with maximal shallow traps concentration corresponding to the optimal Sc/V ratio equal to 75/25, yielding the lowest recombination efficiency and therefore, the highest photocatalytic activity. Redistribution of defect states induced by co-doping should be distinguished as a primary factor of alteration of photocatalytic activity in co-doped TiO2. Presented results demonstrate that photoactivity of co-doped titania cannot be considered as result of either independent action of dopants or their additive effect.
This is a preview of subscription content, access via your institution.
Buy single article
Instant access to the full article PDF.
Tax calculation will be finalised during checkout.
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
Tax calculation will be finalised during checkout.
Ghosh S, Das AP (2015) Modified titanium oxide (TiO2) nanocomposites and its array of applications: a review. Toxicol Environ Chem. https://doi.org/10.1080/02772248.2015.1052204
Wang Z, Cai W, Hong X et al (2005) Photocatalytic degradation of phenol in aqueous nitrogen-doped TiO2 suspensions with various light sources. Appl Catal B Environ 57:223–231. https://doi.org/10.1016/j.apcatb.2004.11.008
Grabowska E, Zaleska A, Sobczak JW et al (2009) Boron-doped TiO2: characteristics and photoactivity under visible light. Procedia Chem 1:1553–1559
Inturi SNR, Boningari T, Suidan M, Smirniotis PG (2014) Visible-light-induced photodegradation of gas phase acetonitrile using aerosol-made transition metal (V, Cr, Fe, Co, Mn, Mo, Ni, Cu, Y, Ce, and Zr) doped TiO2. Appl Catal B Environ 144:333–342. https://doi.org/10.1016/j.apcatb.2013.07.032
Choi J, Park H, Hoffmann MR (2010) Effects of single metal-ion doping on the visible-light photoreactivity of TiO2. J Phys Chem C 114:783–792. https://doi.org/10.1021/jp908088x
Zheng Y, Wang W (2014) Electrospun nanofibers of Er3+-doped TiO2 with photocatalytic activity beyond the absorption edge. J Solid State Chem 210:206–212. https://doi.org/10.1016/j.jssc.2013.11.029
Anpo M, Takeuchi M (2003) The design and development of highly reactive titanium oxide photocatalysts operating under visible light irradiation. J Catal 216:505–516. https://doi.org/10.1016/S0021-9517(02)00104-5
Bloh JZ, Dillert R, Bahnemann DW (2012) Designing optimal metal-doped photocatalysts: correlation between photocatalytic activity, doping ratio, and particle size. J Phys Chem C 116:25558–25562. https://doi.org/10.1021/jp307313z
Kuznetsov VN, Serpone N (2006) Visible light absorption by various titanium dioxide specimens. J Phys Chem B 110:25203
Emeline AV, Kuzmin GN, Serpone N (2008) Wavelength-dependent photostimulated adsorption of molecular O2 and H2 on second generation titania photocatalysts: the case of the visible-light-active N-doped TiO2 system. Chem Phys Lett 454:279–283. https://doi.org/10.1016/j.cplett.2008.02.010
Thuy NM, Van DQ, Thi L, Hai H (2012) The visible light activity of the TiO 2 and TiO 2: V4 + photocatalyst. Nanomater Nanotechnol 2:14
Ola O, Maroto-Valer MM (2015) Transition metal oxide based TiO2 nanoparticles for visible light induced CO2 photoreduction. Appl Catal A Gen 502:114–121. https://doi.org/10.1016/j.apcata.2015.06.007
Cavalheiro AA, Bruno JC, Saeki MJ et al (2008) Effect of scandium on the structural and photocatalytic properties of titanium dioxide thin films. J Mater Sci 43:602–608. https://doi.org/10.1007/s10853-007-1743-2
Berglund SP, Hoang S, Minter RL et al (2013) Investigation of 35 elements as single metal oxides, mixed metal oxides, or dopants for titanium dioxide for dye-sensitized solar cells. J Phys Chem C 117:25248–25258. https://doi.org/10.1021/jp4073747
Zhang DR, Liu HL, Han SY, Piao WX (2013) Synthesis of Sc and V-doped TiO2 nanoparticles and photodegradation of rhodamine-B. J Ind Eng Chem 19:1838–1844. https://doi.org/10.1016/j.jiec.2013.02.029
Patterson AL (1939) The scherrer formula for x-ray particle size determination. Phys Rev 56:978–982. https://doi.org/10.1103/PhysRev.56.978
Bowman JC, Krumhansl JA, Stock JR (1955) Interpretation of the strain broadening components in x-ray diffraction patterns. J Appl Phys 26:1057. https://doi.org/10.1063/1.1722137
Sadewasser SGT (2012) Experimental technique and working modes. In: Sadewasser S, Glatzel T (eds) Kelvin probe force microscopy. Springer, Cham, pp 7–24
Tian B, Li C, Gu F et al (2009) Flame sprayed V-doped TiO2 nanoparticles with enhanced photocatalytic activity under visible light irradiation. Chem Eng J 151:220–227. https://doi.org/10.1016/j.cej.2009.02.030
Khan M, Song Y, Chen N, Cao W (2013) Effect of v doping concentration on the electronic structure, optical and photocatalytic properties of nano-sized V-doped anatase TiO2. Mater Chem Phys 142:148–153. https://doi.org/10.1016/j.matchemphys.2013.06.050
Davidson A, Che M (1992) Temperature-induced diffusion of probe vanadium(IV) ions into the matrix of titanium dioxide as investigated by ESR techniques. J Phys Chem 96:9909–9915. https://doi.org/10.1021/j100203a061
Kokorin AI, Arakelyan VM, Arutyunian VM (2003) Spectroscopic study of polycrystalline TiO2 doped with vanadium. Russ Chem Bull 52:93–97. https://doi.org/10.1023/A:1022488013375
Gillis E, Boesman E (1966) E. P. R.-Studies of V2O5 single crystals. I. Defect centres in pure, non‐stoichiometric vanadium pentoxide. Phys Status Solidi 14:337–347. https://doi.org/10.1002/pssb.19660140211
Kubec F, Šroubek Z (1972) Paramagnetic resonance of interstitial V4 + in TiO2. J Chem Phys 57:1660–1663. https://doi.org/10.1063/1.1678451
Maira AJ, Augugliaro V, Coronado JM et al (2002) EPR study of the surface characteristics of nanostructured TiO 2 under UV irradiation. Langmuir 17:5368–5374. https://doi.org/10.1021/la010153f
Kumar CP, Gopal NO, Wang TC et al (2006) EPR investigation of TiO2 nanoparticles with temperature-dependent properties. J Phys Chem B 110:5223–5229. https://doi.org/10.1021/jp057053t
MacDonald IR, Rhydderch S, E Holt et al (2012) EPR studies of electron and hole trapping in titania photocatalysts. Catal Today 182:39–45
Yang S, Halliburton LE, Manivannan A et al (2009) Photoinduced electron paramagnetic resonance study of electron traps in TiO2 crystals: oxygen vacancies and Ti3 + ions. Appl Phys Lett 94:2–5. https://doi.org/10.1063/1.3124656
Howe RF, Grätzel M (1985) EPR observation of trapped electrons in colloidal TiO2. J Phys Chem 89:4495–4499. https://doi.org/10.1021/j100267a018
Le Mercier T, Mariot JM, Parent P et al (1995) Formation of Ti3 + ions at the surface of laser-irradiated rutile. Appl Surf Sci 86:382–386. https://doi.org/10.1016/0169-4332(94)00421-8
Attwood AL, Murphy DM, Edwards JL et al (2003) An EPR study of thermally and photochemically generated oxygen radicals on hydrated and dehydrated titania surfaces. Res Chem Intermed 29:449–465. https://doi.org/10.1163/156856703322148991
Böer KW, Pohl UW (2017) Carrier recombination and noise. Semiconduct Phys. Springer, Cham, pp 1–55
We are grateful to the Resource Center (RC) “Nanophotonics”, RC “Centre for Innovative Technologies of Composite Nanomaterials”, RC “X-ray Diffraction Studies”, RC “Centre for Diagnostics of Functional Materials for Medicine, Pharmacology and Nanoelectronics” and RC “Geomodel” of the Research Park at the Saint-Petersburg State University for helpful assistance in the characterization of the samples.
This research was supported by Russian Foundation for Basic Research (RFBR) via a research grant N18–29–23035_mk and by Saint-Petersburg State University via a research project (Pure ID 51124539).
Conflict of interest
The authors declared that they have no conflict of interest.
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Electronic supplementary material 1 (DOC 1035 kb)
About this article
Cite this article
Murzin, P.D., Murashkina, A.A., Emeline, A.V. et al. Effect of Sc3+/V5+ Co-Doping on Photocatalytic Activity of TiO2. Top Catal (2020). https://doi.org/10.1007/s11244-020-01292-1
- Phenol photodegradation
- Work function
- Shallow traps
- Intrinsic defects