Effect of La as Promoter in the Photoreduction of CO2 Over TiO2 Catalysts


In this work, TiO2 has been modified by treating it thermally together with different proportions (0.5–15 wt%) of La2O3. The resulting materials have been extensively characterized by XRD, TEM, N2 adsorption isotherms, temperature-programmed CO2 desorption, Raman, UV–Vis photoluminescence and X-ray photoelectron spectroscopies. The activity tests of these materials for the gas-phase photocatalytic reduction of carbon dioxide show that the main products of the reaction are in all cases CO and CH4, together with H2 from the parallel reduction of water. After the preparation procedure, La phases are best described as oxycarbonates, and lead to improved activity with respect to TiO2 with La contents up to 5 wt%. Higher loadings do not, however, lead to further enhanced activity. Retarded electron–hole recombination and enhanced CO2 adsorption are invoked as the key factors contributing to this activity improvement, which is optimized in the case of 0.5 wt% La leading to higher productions of CO and CH4 and increased quantum efficiency with respect to titania.

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  1. 1.

    Framework Convention on Climate Change (2014) United Nations. http://unfccc.int/paris_agreement/items/9485.php

  2. 2.

    de la Peña O’Shea VA, Serrano DP, Coronado JM (2015) In: Rozhkova E, Ariga K (eds) From molecules to materials. Pathways to artificial photosynthesis, Springer, London

    Google Scholar 

  3. 3.

    Li K, An X, Park KH, Khraisheh M, Tang J (2014) Catal Today 224:3–12

    CAS  Article  Google Scholar 

  4. 4.

    Yuan L, Xu YJ (2015) Appl Surf Sci 342:154–167

    CAS  Article  Google Scholar 

  5. 5.

    Ola O, Maroto-Valer MM (2015) J Photochem Photobiol C 24:16–42

    CAS  Article  Google Scholar 

  6. 6.

    Protti S, Albini A, Serpone N (2014) Phys Chem Chem Phys 16:19790–19827

    CAS  Article  Google Scholar 

  7. 7.

    Fresno F, Portela R, Suárez S, Coronado JM (2014) J Mater Chem A 2:2863

    CAS  Article  Google Scholar 

  8. 8.

    Tu W, Zhou Y, Zou Z (2014) Adv Mater 16:4607–4626

    Article  Google Scholar 

  9. 9.

    Chen D, Zhang X, Lee AF (2015) J Mater Chem A 3:14487–14516

    CAS  Article  Google Scholar 

  10. 10.

    Xie S, Zhang Q, Liu G, Wang Y (2016) Chem Commun 52:35–59

    CAS  Article  Google Scholar 

  11. 11.

    Lee AF (2015) J Mater Chem A 3:14487–14516

    Article  Google Scholar 

  12. 12.

    Bai S, Yin W, Wang L, Li Z, Xiong Y (2016) RCS Adv 6:57446–57463

    CAS  Google Scholar 

  13. 13.

    Liu L, Zhao C, Pitts D, Li Y (2014) Catal Sci Technol 4:1539–1546

    CAS  Article  Google Scholar 

  14. 14.

    Xie S, Wang Y, Zhang Q, Fan W, Deng W, Wang Y (2013) Chem Commun 49:2451–2453

    CAS  Article  Google Scholar 

  15. 15.

    Kay A, Graetzel M (2002) Chem Mater 14:2930

    CAS  Article  Google Scholar 

  16. 16.

    Orera A, Larraz G, Sanjuán ML (2013) J Eur Ceram Soc 33:2103

    CAS  Article  Google Scholar 

  17. 17.

    Taylor RP, Schrader GL (1991) Ind Eng Chem Res 30:1016–1023

    CAS  Article  Google Scholar 

  18. 18.

    Zhang ZL, Verykios XE (1996) Appl Catal A 138:109–133

    CAS  Article  Google Scholar 

  19. 19.

    Yu H, Xue B, Liu P, Qiu J, Wen W, Zhang S, Zhao H (2012) ACS Appl Mater Interfaces 4:1289–1294

    CAS  Article  Google Scholar 

  20. 20.

    Liu QY, Fang ZB, Ji T, Liu SY, Tan YS, Chen JJ, Zhu YY (2014) Chin Phys Lett 31:027702

    Article  Google Scholar 

  21. 21.

    Collado L, Jana P, Sierra B, Coronado JM, Pizarro P, Serrano DP, de la Peña O’Shea VA (2013) Chem Eng J 224:128–135

    CAS  Article  Google Scholar 

  22. 22.

    Zhang J, Li M, Feng Z, Chen J, Li C (2006) J Phys Chem B 110:927–935

    CAS  Article  Google Scholar 

  23. 23.

    Grätzel M (1989) Heterogeneous photochemical electron transfer. XRC Press Inc, Boca Raton

    Google Scholar 

  24. 24.

    Liu B, Wen L, Zhao X (2007) Mater Chem Phys 106:350–353

    CAS  Article  Google Scholar 

  25. 25.

    Pan DC, Zhao NN, Wang Q, Jiang S, Ji X, An L (2005) Adv Mater 17:1991–1995

    CAS  Article  Google Scholar 

  26. 26.

    Liqiang J, Yichun Q, Baiqi W, Shudan L, Baojiang J, Libin Y, Wei F, Honggang F, Jiazhong S (2006) Sol Energy Mater Sol Cells 90:1773–1787

    Article  Google Scholar 

  27. 27.

    Sunding MF, Hadidi K, Diplas S, Løvvika OM, Norby TE, Gunnæs AE (2011) J Electron Spectrosc Relat Phenom 184:399–409

    CAS  Article  Google Scholar 

  28. 28.

    Mullica DF, Lok CKC, Perkins HO, Young V (1985) Phys Rev B 31:4039–4042

    CAS  Article  Google Scholar 

  29. 29.

    Collado L (2015) PhD Thesis, Universidad Rey Juan Carlos

  30. 30.

    Collado L, Reynal A, Coronado JM, Serrano DP, Durrant JR, de la Peña O’Shea VA (2015) Appl Catal B 178:177–185

    CAS  Article  Google Scholar 

  31. 31.

    Villa K, Murcia-López S, Morante JR, Andreu T (2016) Appl Catal B 187:30–35

    CAS  Article  Google Scholar 

  32. 32.

    León M, Diaz E, Bennici S, Vega A, Ordóñez S, Auroux A (2010) Ind Eng Chem Res 49:3663–3671

    Article  Google Scholar 

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This work has received financial support from the Spanish Ministry of Economy and Competitiveness through the project SolarFuel (ENE2014-55071-JIN). Funding of the FOTOFUEL Network (ENE2016-82025-REDT) by this Ministry is gratefully acknowledged. F.F. thanks financial support from the Amarout-II PEOPLE-COFUND Marie Skłodowska-Curie Action.

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Correspondence to F. Fresno or V. A. de la Peña O’Shea.

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Reñones, P., Fresno, F., Fierro, J.L.G. et al. Effect of La as Promoter in the Photoreduction of CO2 Over TiO2 Catalysts. Top Catal 60, 1119–1128 (2017). https://doi.org/10.1007/s11244-017-0797-x

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  • CO2 photoreduction
  • Artificial photosynthesis
  • TiO2
  • Lanthanum
  • Promoter