Skip to main content

Advertisement

SpringerLink
Log in

Electron and Energy Transfer Mechanisms: The Double Nature of TiO2 Heterogeneous Photocatalysis

  • Review
  • Published:
Topics in Current Chemistry Aims and scope Submit manuscript

Abstract

Photocatalytic chemical transformations in the presence of irradiated TiO2 are generally considered in terms of interfacial electron transfer. However, more elusive energy-transfer-driven reactions have been also hypothesized to occur, mainly on the basis of the indirect evidence of detected reaction products whose existence could not be justified simply by electron transfer. Unlike in homogeneous and colloidal systems, where energy transfer mechanisms have been investigated deeply for several organic syntheses, understanding of similar processes in heterogeneous systems is at only a nascent level. However, this gap of knowledge can be filled by considering the important achievements of synthetic heterogeneous photocatalysis, which bring the field closer to industrial exploitation. The present manuscript summarizes the main findings of previous literature reports and, also on the basis of some novel experimental evidences, tentatively proposes that the energy transfer in TiO2 photocatalysis could possess a Förster-like nature.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Kisch H (2015) Semiconductor photocatalysis: principles and applications. Wiley-VCH, Weinheim

    Google Scholar 

  2. Jańczyk A, Krakowska E, Stochel G, Macyk W (2006) Singlet oxygen photogeneration at surface modified titanium dioxide. J Am Chem Soc 128:15574–15575. https://doi.org/10.1021/ja065970m

  3. Buchalska M, Łabuz P, Bujak Ł, Szewczyk G, Sarna T, Maćkowski S, Macyk W (2013) New insight into singlet oxygen generation at surface modified nanocrystalline TiO2—the effect of near-infrared irradiation. Dalton Trans 42:9468–9475. https://doi.org/10.1039/C3DT50399B

  4. Strieth-Kalthoff F, James MJ, Teders M, Pitzer L, Glorius F (2018) Energy transfer catalysis mediated by visible light: principles, applications, directions. Chem Soc Rev 47:7190–7202. https://doi.org/10.1039/C8CS00054A

  5. Ravelli D, Protti S, Neri P, Fagnoni M, Albini A (2011) Photochemical technologies assessed: the case of rose oxide. Green Chem 13:1876–1884. https://doi.org/10.1039/C0GC00507J

  6. Ciriminna R, Parrino F, De Pasquale C, Palmisano L, Pagliaro M (2018) Photocatalytic partial oxidation of limonene to 1,2 limonene oxide. Chem Commun 54:1008–1011. https://doi.org/10.1039/C7CC09788C

  7. Parrino F, De Pasquale C, Palmisano L (2019) Influence of surface-related phenomena on mechanism, selectivity, and conversion of TiO2-induced photocatalytic reactions. Chemsuschem 12(3). https://doi.org/10.1002/cssc.201801898

  8. Huang Y, Qiu F, Chen R, Yan D, Zhu X (2020) Fluorescence resonance energy transfer-based drug delivery systems for enhanced photodynamic therapy. J Mater Chem B 8:3772–3788. https://doi.org/10.1039/D0TB00262C

  9. Medintz IL, Mattoussi H (2009) Quantum dot-based resonance energy transfer and its growing application in biology. Phys Chem Chem Phys 11:17–45. https://doi.org/10.1039/B813919A

  10. Scholes GD, Mirkovic T, Turner DB, Fassioli F, Buchleitner A (2012) Solar light harvesting by energy transfer: from ecology to coherence. Energy Environ Sci 5:9374–9393. https://doi.org/10.1039/C2EE23013E

  11. Claussen JC, Algar WR, Hildebrandt N, Susumu K, Ancona MG, Medintz IL (2013) Biophotonic logic devices based on quantum dots and temporally-staggered Förster energy transfer relays. Nanoscale 5:12156–12170. https://doi.org/10.1039/C3NR03655C

  12. Bellardita M, Ceccato R, Dirè S, Loddo V, Palmisano L, Parrino F (2019) Energy transfer in heterogeneous photocatalysis. Substantia 3(2) Suppl. 6:49–57. https://doi.org/10.13128/Substantia-765

  13. Turro NJ (1977) Energy transfer processes. Pure Appl Chem 49:405–429. https://doi.org/10.1351/pac197749040405

  14. Förster T (1948) Zwischenmolekulare Energiewanderung und Fluoreszenz. Ann Phys 6:54–75. https://doi.org/10.1002/andp.19484370105

  15. Dexter DL (1953) A theory of sensitized luminescence in solids. J Chem Phys 21:836–850. https://doi.org/10.1063/1.1699044

  16. Wang CY, Pagel R, Dohrmann JK, Bahnemann DW (2006) Antenna mechanism and deaggregation concept: novel mechanistic principles for photocatalysis. C R Chimie 9:761–773. https://doi.org/10.1016/j.crci.2005.02.053

  17. Anpo M, Che M (1999) Applications of photoluminescence techniques to the characterization of solid surfaces in relation to adsorption, catalysis, and photocatalysis. Adv Catal 44:119–257. https://doi.org/10.1016/S0360-0564(08)60513-1

  18. Strome DH, Klier K (1980) Effects of carbon monoxide absorption on the luminescence of reduced copper-exchanged Y zeolite. J Phys Chem 9:981–984. https://doi.org/10.1021/j100446a010

  19. Tian Y, Tatsuma T (2004) Plasmon induced photoelectrochemistry at metal nanoparticles supported on nanoporous TiO2. Chem Commun 2004:1810–1811. https://doi.org/10.1039/B405061D

  20. Liu Z, Hou W, Pavaskar P, Aykol M, Cronin SB (2011) Plasmon resonant enhancement of photocatalytic water splitting under visible illumination. Nano Lett 11(3):1111–1116. https://doi.org/10.1021/nl104005n

  21. Kochuveedu ST, Jang YH, Kim DH (2013) A study on the mechanism for the interaction of light with noble metal-metal oxide semiconductor nanostructures for various photophysical applications. Chem Soc Rev 42:8467–8493. https://doi.org/10.1039/c3cs60043b

  22. Christopher P, Xin H, Linic S (2011) Visible-light-enhanced catalytic oxidation reactions on plasmonic silver nanostructures. Nat Chem 3:467–472. https://doi.org/10.1038/nchem.1032

  23. Li J, Cushing SK, Meng F, Senty TR, Bristow AD, Wu N (2015) Plasmon-induced resonance energy transfer for solar energy conversion. Nat Photon 9:601–607. https://doi.org/10.1038/nphoton.2015.142

  24. Nosaka Y, Daimon T, Nosaka AY, Murakami Y (2004) Singlet oxygen formation in photocatalytic TiO2 aqueous suspension. Phys Chem Chem Phys 6:2917–2918. https://doi.org/10.1039/B405084C

  25. Muuronen M, Parker SM, Berardo E, Le A, Zwijnenburg MA, Furche F (2017) Mechanism of photocatalytic water oxidation on small TiO2 nanoparticles. Chem Sci 8:2179–2183. https://doi.org/10.1039/C6SC04378J

  26. Parrino F, Livraghi S, Giamello E, Ceccato R, Palmisano L (2020) Role of hydroxyl, superoxide, and nitrate radicals on the fate of bromide ions in photocatalytic TiO2 suspensions. ACS Catal 10:7922–7931. https://doi.org/10.1021/acscatal.0c02010

  27. Daimon T, Nosaka Y (2007) Formation and behavior of singlet molecular oxygen in TiO2 photocatalysis studied by detection of near-infrared phosphorescence. J Phys Chem C 111:4420–4424. https://doi.org/10.1021/jp070028y

  28. Kiselev VM, Kislyakov IM, Burchinov AN (2016) Generation of singlet oxygen on the surface of metal oxides. Opt Spectrosc 86:66–76. https://doi.org/10.1134/S0030400X16040123

  29. Demyanenko AV, Bogomolov AS, Dozmorov NV, Svyatova AI, Pyryaeva AP, Goldort VG, Kochubei SA, Baklanov AV (2019) Singlet oxygen 1O2 in photocatalysis on TiO2 Where does it come from? J Phys Chem C 123:2175–2181. https://doi.org/10.1021/acs.jpcc.8b09381

    Article  CAS  Google Scholar 

  30. Nosaka Y, Nosaka AY (2019) Comment on “Singlet oxygen 1O2 in photocatalysis on TiO2 Where does it come from?” J Phys Chem C 123:27993–27995. https://doi.org/10.1021/acs.jpcc.9b08464

    Article  CAS  Google Scholar 

  31. Demyanenko AV, Bogomolov AS, Dozmorov NV, Svyatova AI, Pyryaeva AP, Goldort VG, Kochubei SA, Baklanov AV (2019) Reply to “Comment on ‘Singlet oxygen 1O2 in photocatalysis on TiO2 Where does it come from?” J Phys Chem C 123:28515–28518. https://doi.org/10.1021/acs.jpcc.9b09500

  32. Gottuso A, Köckritz A, Saladino ML, Armetta F, De Pasquale C, Nasillo G, Parrino F (2020) Catalytic and photocatalytic epoxidation of limonene: using mesoporous silica nanoparticles as functional support for a Janus-like approach. J Catal 391:202–211. https://doi.org/10.1016/j.jcat.2020.08.025

  33. Parrino F, D’Arienzo M, Callone E, Conta R, Di Credico B, Mascotto S, Meyer A, Scotti R, Dirè S (2021) TiO2 containing hybrid nanocomposites with active–passive oxygen scavenging capability. Chem Eng J 417:129135. https://doi.org/10.1016/j.cej.2021.129135

  34. Anpo M, Yamada Y, Kubokawa Y, Coluccia S, Zecchina A, Che M (1988) Photoluminescence properties of MgO powders with coordinatively unsaturated surface ions. J Chem Soc Faraday Trans I 84:751–764. https://doi.org/10.1039/F19888400751

  35. Anpo M, Yabuta M, Kodama S, Kubokawa Y (1986) Photocatalytic isomerization of butenes over TiO2. Photo-formed active species and characteristics of reaction. Bull Chem Soc Jpn 59:259–264. https://doi.org/10.1246/bcsj.59.259

  36. Oh YC, Li X, Cubbage J, Jenks W (2004) Mechanisms of catalyst action in the TiO2-mediated photocatalytic degradation and cis–trans isomerization of maleic and fumaric acid. Appl Catal B: Environ 54:105–114. https://doi.org/10.1016/j.apcatb.2004.05.024

  37. Parrino F, Di Paola A, Loddo V, Pibiri I, Bellardita M, Palmisano L (2016) Photochemical and photocatalytic isomerization of trans-caffeic acid and cyclization of cis-caffeic acid to esculetin. Appl Catal B: Environ 182:347–355. https://doi.org/10.1016/j.apcatb.2015.09.045

  38. Hurum DC, Gray KA, Rajh T, Thurnauer MC (2005) Recombination pathways in the Degussa P25 formulation of TiO2: surface versus lattice mechanisms. J Phys Chem B 109:977–980. https://doi.org/10.1021/jp045395d

  39. Hurum DC, Agrios AG, Crist SE, Gray KA, Rajh T, Thurnauer MC (2006) Probing reaction mechanisms in mixed phase TiO2 by EPR. J Electron Spectrosc 150:155–163. https://doi.org/10.1016/j.elspec.2005.01.294

  40. Anpo M, Shima T, Fujii T, Suzuki S, Che M (1987) ESR studies of active surface titanium ions on anchored Ti-oxide catalysts. Chem Lett 16:1997–2000. https://doi.org/10.1246/cl.1987.1997

  41. Ke SC, Wang TC, Wong MS, Gopal NO (2006) Low temperature kinetics and energetics of the electron and hole traps in irradiated TiO2 nanoparticles as revealed by EPR spectroscopy. J Phys Chem B 110:11628–11634. https://doi.org/10.1021/jp0612578

  42. Howe RF, Gratzel M (1987) EPR study of hydrated anatase under UV irradiation. J Phys Chem 91:3906–3909. https://doi.org/10.1021/j100298a035

  43. Attwood AL, Murphy DM, Edwards JL, Egerton TA, Harrison RW (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

  44. Carter E, Carley AF, Murphy DM (2007) Evidence for O2– radical stabilization at surface oxygen vacancies on polycrystalline TiO2. J Phys Chem C 111:10630–10638. https://doi.org/10.1021/jp0729516

  45. D’Arienzo M, Carbajo J, Bahamonde A, Crippa M, Polizzi S, Scotti R, Wahba L, Morazzoni F (2011) Photogenerated defects in shape-controlled TiO2 anatase nanocrystals: a probe to evaluate the role of crystal facets in photocatalytic processes. J Am Chem Soc 133:17652–17661. https://doi.org/10.1021/ja204838s

  46. D’Arienzo M, Dozzi MV, Redaelli M, Di Credico B, Morazzoni F, Scotti R, Polizzi S (2015) Crystal surfaces and fate of photogenerated defects in shape-controlled anatase nanocrystals: drawing useful relations to improve the H2 yield in methanol photosteam reforming. J Phys Chem C 119:12385–12393. https://doi.org/10.1021/acs.jpcc.5b01814

Download references

Funding

No funding was received for conducting this study.

Author information

Authors and Affiliations

  1. Department of Industrial Engineering (DII), University of Trento, Via Sommarive 9, 38123, Trento, Italy

    Francesco Parrino, Sandra Dirè & Riccardo Ceccato

  2. Department of Materials Science (INSTM), University of Milano-Bicocca, Via R. Cozzi 55, 20125, Milano, Italy

    Massimiliano D’Arienzo & Silvia Mostoni

  3. Department of Engineering, University of Palermo, Viale delle Scienze ed. 6, 90128, Palermo, Italy

    Marianna Bellardita & Leonardo Palmisano

Authors
  1. Francesco Parrino
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Massimiliano D’Arienzo
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Silvia Mostoni
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Sandra Dirè
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Riccardo Ceccato
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Marianna Bellardita
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Leonardo Palmisano
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Francesco Parrino.

Ethics declarations

Conflict of Interest

The authors have no conflicts of interest or competing interests to declare.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

This article is part of the Topical Collection “Solar-driven catalysis”; edited by Nicolas Keller, Fernando Fresno, Agnieszka Ruppert and Patricia Garcia-Munoz.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 26 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Parrino, F., D’Arienzo, M., Mostoni, S. et al. Electron and Energy Transfer Mechanisms: The Double Nature of TiO2 Heterogeneous Photocatalysis. Top Curr Chem (Z) 380, 2 (2022). https://doi.org/10.1007/s41061-021-00358-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s41061-021-00358-2

Keywords

Search

Navigation