Environmental Science and Pollution Research

, Volume 19, Issue 9, pp 3666–3675 | Cite as

On the way to the creation of next generation photoactive materials

  • A. V. Emeline
  • V. N. Kuznetsov
  • V. K. Ryabchuk
  • N. Serpone
Photocatalysis: fundamentals and applications in JEP 2011, Bordeaux



Transition from first- to second-generation photocatalysts has followed the notion that greater absorption of light in the visible region would yield greater spectral sensitivity and greater photoactivity. Though a promising strategy, in practice, it did not meet expectation because of various side issues, which in many cases has led to loss of photoactivity and chemical reactivity. This article examines some earlier notions that arose from applications of different metal oxides (e.g., TiO2, ZnO, MgO among others) that made these oxides good photocatalysts in many processes.


Phenomena that proved relevant in developing next generation photoactive materials are considered: the dependence of the activity of photocatalysts on the band gap energy, the spectral variations of the activity of photoactive materials, and the spectral variations of selectivity of photoactive materials. The tendency to decrease the energy of actinic photons through doping in forming second-generation photocatalysts is completely opposite the fundamental observation in first-generation photocatalysts whereby the activity increased with increasing band gap energy. Extension of spectral sensitivity of second-generation photoactive materials also caused a decrease of their photoactivity; hence, some notions are reconsidered to produce next(third) generation photoactive materials.


The article proposes the following concepts to develop next generation photocatalysts: (1) multi(two)-photon excitation of photoactive materials with lower energy photons to achieve the same excited state as with higher energy photons, (2) utilization of heterojunctions to drive electronic processes in the desired direction, and (3) selective photoexcitation of localized electronic states to gain better selectivity.


Heterogeneous photocatalysis Metal oxides Photoactivity Selectivity Spectral sensitivity Heterostructures 



This work was partially supported by a Grant from the Russian Foundation for Basic Research (No. 10-03-00638-a). One of us (NS) thanks Prof. Albini of the Universita di Pavia for his continued kind hospitality in his laboratory. We are particularly grateful to Prof. Basov for providing us with the original data for Fig. 1.


  1. Anpo M, Takeuchi M (2003) The design and development of highly reactive titanium oxide photocatalysts operating under visible light irradiation. J Catal 216:505–516CrossRefGoogle Scholar
  2. Asahi R, Morikawa T, Ohwaki T, Aoki K, Taga Y (2001) Visible-light photocatalysis in nitrogen-doped titanium oxides. Science 293:269–271CrossRefGoogle Scholar
  3. Baru V, Wolkenstein TH (1978) Effect of irradiation on surface properties of semiconductors. Nauka, MoscowGoogle Scholar
  4. Basov LL Solonitsyn YuP (1973) Measurement of the absolute quantum yield of heterogenic photochemical reactions. USSR application no. 1971–1630307, patent no. SU 387730 (A1) 1973–06–22Google Scholar
  5. Basov LL, Solonitsyn YUP, Terenin AN (1965) Influence of illumination on the adsorptivity of some oxides. Dokl Akad Nauk SSSR 164:122–124Google Scholar
  6. Basov LL, Kuzmin GN, Prudnikov IM, Solonitsyn YUP (1976) Photoadsorption processes on metal oxides. In: Vilesov THI (ed) Uspehi fotoniki (advances in photonics). LGU, Leningrad, pp 82–120, Iss. 6Google Scholar
  7. Chen X, Burda C (2008) The electronic origin of the visible-light absorption properties of C-, N- and S-doped TiO2 nanomaterials. J Am Chem Soc 130:5018–5019CrossRefGoogle Scholar
  8. Chen X, Glans P-A, Qiu X, Dayal S, Jennings WD, Smith KE, Burda C, Guoc J (2008) X-ray spectroscopic study of the electronic structure of visible-light responsive N-, C- and S-doped TiO2. J Electron Spectrosc Relat Phenom 162:67–73CrossRefGoogle Scholar
  9. Choi C, Park H, Hoffmann MR (2010) Effects of single metal-ion doping on the visible-light photoreactivity of TiO2. J Phys Chem C 114:783–792CrossRefGoogle Scholar
  10. Emeline AV, Serpone N (2002) Spectral selectivity of photocatalyzed reactions on the surface of titanium dioxide nanoparticles. J Phys Chem B 106:12221–12226CrossRefGoogle Scholar
  11. Emeline AV, Kuzmin GN, Purevdorj D, Shenderovich IG (1997) Spectral and temperature dependencies of the quantum yield of gases photoadsorption on powdered titania. Kinet Kataliz 38:446–450Google Scholar
  12. Emeline AV, Ryabchuk VK, Serpone N (1999) Spectral dependencies of the quantum yield of photochemical processes on the surface of nano-/micro-particulates of wide band gap metal oxides: I. Theoretical approach. J Phys Chem B 103:1316–1325CrossRefGoogle Scholar
  13. Emeline AV, Kuzmin GN, Purevdorj D, Ryabchuk VK, Serpone N (2000a) Spectral dependencies of the quantum yield of photochemical processes on the surface of wide band-gap solids: III. Gas/solid systems. J Phys Chem B 104:2989–2998CrossRefGoogle Scholar
  14. Emeline AV, Salinaro A, Serpone N (2000b) Spectral dependence and wavelength selectivity in heterogeneous photocatalysis. I. Experimental evidence from the photocatalyzed transformation of phenols. J Phys Chem B104:11202–11210Google Scholar
  15. Emeline AV, Frolov AV, Ryabchuk VK, Serpone N (2003) Spectral dependencies of the quantum yield of photochemical processes on the surface of nano-/micro-particulates of wide bandgap metal oxides. IV. Theoretical modeling of the activity and selectivity of semiconductor photocatalysts with inclusion of sub-surface electric fields in the space charge region. J Phys Chem B 107:7109–7119CrossRefGoogle Scholar
  16. Emeline AV, Kuzmin GN, Basov LL, Serpone N (2005) Photoactivity and photoselectivity of dielectric metal-oxide photocatalyst (ZrO2) probed by photoinduced reduction of oxygen and oxidation of hydrogen. J Photochem Photobiol Chem 174:214–221CrossRefGoogle Scholar
  17. Emeline AV, Zhang X, Jin M, Murakami T, Fujishima A (2006) Application of the “black body like” reactor for the measurements of the quantum yield of photochemical reactions in heterogeneous systems. J Phys Chem B 110:7409–7413CrossRefGoogle Scholar
  18. Emeline AV, Sheremetyeva NV, Khomchenko NV, Ryabchuk VK, Serpone N (2007) Photoinduced formation of defects and nitrogen-stabilization of color centers in N-doped titanium dioxide. J Phys Chem C 111:11456–11462CrossRefGoogle Scholar
  19. Emeline AV, Kuzmin GN, Serpone N (2008) Quantum yields and their wavelength-dependence in the photoreduction of O2 and photooxidation of H2 on a visible-light-active N-doped TiO2 system. Chem Phys Lett 454:279–283CrossRefGoogle Scholar
  20. Emeline AV, Zhang X, Jin M, Murokami T, Fujishima A (2009a) Spectral dependences of the activity and selectivity of N-doped TiO2 in photodegradation of phenols. J Photochem Photobiol Chem 207:13–19CrossRefGoogle Scholar
  21. Emeline AV, Sheremetyeva NV, Khomchenko NV, Kuzmin GN, Ryabchuk VK, Teoh WY, Amal R (2009b) Spectroscopic studies of pristine and fluorinated nano-ZrO2 in photostimulated heterogeneous processes. J Phys Chem C 113:4566–4583CrossRefGoogle Scholar
  22. Frank SN, Bard AJ (1977) Heterogeneous photocatalytic oxidation of cyanide and sulfite in aqueous solutions at semiconductor powders. J Phys Chem 81:1484–1488CrossRefGoogle Scholar
  23. Fujishima A, Honda K (1972) Electrochemical photolysis of water at a semiconductor electrode. Nature 238:37–38CrossRefGoogle Scholar
  24. Fujishima A, Zhang X, Tryk DA (2008) TiO2 photocatalysis and related surface phenomena. Surf Sci Rep 63:515–582CrossRefGoogle Scholar
  25. Gerischer H (1981) The principles of photoelectrochemical energy conversions. In: Cardon F, Gomes WP, Dekeyser W (eds) Photovoltaic and photoelectrochemical solar energy conversion. Plenum Press, New York, pp 199–262CrossRefGoogle Scholar
  26. Haerudin H, Bertel S, Kramer R (1998) Surface stoichiometry of “titanium suboxide”. Part I volumetric and FTIR study. J Chem Soc Faraday Trans 94:1481–1487CrossRefGoogle Scholar
  27. Henderson MA (2011) A surface science perspective on TiO2 photocatalysis. Surf Sci Rep 66:185–297CrossRefGoogle Scholar
  28. Henderson B, Werts JE (1977) Defects in the alkaline earth oxide and applications to radiation damage and catalysis. Taylor and Francis, LondonGoogle Scholar
  29. Kasparov KYA, Terenin AN (1941) Optical investigations of activated adsorption. I. Photodecomposition of NH3 adsorbed on catalysts. Acta Physicochim USSR 15:343–365Google Scholar
  30. Kelly KL, Coronado E, Zhao LL, Schatz GC (2003) The optical properties of metal nanoparticles: the influence of size, shape, and dielectric environment. J Phys Chem B 107:668–677CrossRefGoogle Scholar
  31. Kiselev VTH, Krilov VO (1979) Electronic phenomena in adsorption and catalysis on semiconductors and dielectrics. Nauka, MoscowGoogle Scholar
  32. Kotomin EA, Popov AI (1998) Radiation induced point defects in simple oxides. Nucl Instrum Meth Phys Res B 141:1–15CrossRefGoogle Scholar
  33. Kuznetsov VN, Serpone N (2006) Visible light absorption by various titanium dioxide specimens. J Phys Chem B 110:25203–25209CrossRefGoogle Scholar
  34. Kuznetsov VN, Serpone N (2009) On the origin of the spectral bands in the visible absorption spectra of visible light active TiO speciments: analysis and assignments. J Phys Chem C 113:15110–15123CrossRefGoogle Scholar
  35. Noguez C (2007) Surface plasmons on metal nanoparticles: the influence of shape and physical environment. J Phys Chem C 111:3806–3819CrossRefGoogle Scholar
  36. Rekoske JE, Barteau MA (1997) Isothermal reduction kinetics of titanium dioxide-based materials. J Phys Chem B 101:1113–1124CrossRefGoogle Scholar
  37. Ryabchuk VK, Basov LL, Solonitsyn YUP (1989) Dependencies of photoadsorption and photocatalytic behavior of alkali halide crystals on spectral range of photoexcitation. Chem Phys (Russ) 8:1475–1482Google Scholar
  38. Sekiya T, Yagisawa T, Kamiya N, Mulmi D, Kurita S, Murakami Y, Kodaira T (2004) Defects in anatase TiO2 single crystal controlled by heat treatments. J Phys Soc Jpn 73:703–710CrossRefGoogle Scholar
  39. Serpone N (2006) Is the band gap of pristine TiO2 narrowed by anion- and cation-doping of titanium dioxide in second-generation photocatalysts? J Phys Chem B 110:24287–24293CrossRefGoogle Scholar
  40. Serpone N, Emeline AV (2005) Modeling heterogeneous photocatalysis by metal-oxide nanostructured semiconductor and insulator materials: factors that affects the activity and selectivity of photocatalysts. Res Chem Intermed 31:391–432CrossRefGoogle Scholar
  41. Serpone N, Lawless D, Disdier J, Herrmann J-M (1994) Spectroscopic, photoconductivity, and photocatalytic studies of TiO2 colloids: naked and with the lattice doped with Cr3+, Fe3+, and V5+ cations. Langmuir 10:643–652CrossRefGoogle Scholar
  42. Serpone N, Emeline AV, Kuznetsov VN, Ryabchuk VK (2008) Visible-light-active titania photocatalysts. The case of N-doped TiO2s—properties and some fundamental issues. Int J Photoenergy 1:1–19Google Scholar
  43. Solonitsyn YUP, Kuzmin GN, Shurigyn AL, Yurkin VM (1976) Quantum yield of photoadsorption, photo- and X-ray induced adsorption capacity of TiO2 with respect to hydrogen and methane. Kinet Kataliz 7:1267–1372Google Scholar
  44. Stoneham AM (1975) Theory of defects in solids. Clarendon, OxfordGoogle Scholar
  45. Zhang H, Chen H, Bahnemann DF (2009) Photoelectrocatalytic materials for environmental applications. J Mater Chem 19:5089–5121CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2012

Authors and Affiliations

  1. 1.Department of Photonics, V.A. Fock Institute of PhysicsSaint Petersburg State UniversitySaint PetersburgRussia
  2. 2.Dipartimento di ChimicaUniversita di PaviaPaviaItaly

Personalised recommendations