Journal of Materials Science

, Volume 54, Issue 3, pp 1967–1976 | Cite as

Cubic-like BaZrO3 nanocrystals with exposed {001}/{011} facets and tuned electronic band structure for enhanced photocatalytic hydrogen production

  • Jie Meng
  • Zhenyun Lan
  • Qingyun Lin
  • Tao Chen
  • Xing Chen
  • Xiao WeiEmail author
  • Yunhao LuEmail author
  • Jixue Li
  • Ze ZhangEmail author


Facet engineering to expose specific surfaces has received rapid growth attention to promote the photocatalytic performance. In this work, we reported that BaZrO3 nanocrystals with {001}/{011} facets and corresponding higher reducing capacity could effectively improve the photocatalytic hydrogen evolution in pure water. The tuned electronic band structure arising from exposed specific {001}/{011} facets and the higher surface area are the main reasons to promote photocatalytic activity. The conduction band bottom for BaZrO3 nanocrystals with {001}/{011} facets synthesized by solvothermal method (denoted as BZO-HT) is about 0.31 eV higher than that of sample prepared by hydrothermal reaction (denoted as BZO-H). During the evaluation of photocatalytic activity in pure water, the H2 production rate for BZO-HT (27.80 μmol/g/h) is 9.4 times and six times higher than BZO-H and commercial BaZrO3 (denoted as BZO-C), respectively. This work provides a reference for other facets-related photocatalysts’ design for pure water reduction or splitting.



This work was supported by National Natural Science Foundation of China (Grant Nos. 11234011, 11327901, 51102208) and the Fundamental Research Funds for the Central Universities (2014QNA4008, 2017QNA4011).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

10853_2018_2995_MOESM1_ESM.docx (947 kb)
Supplementary material 1 (DOCX 947 kb)


  1. 1.
    Balzani V, Credi A, Venturi M (2008) Photochemical conversion of solar energy. Chemsuschem 1:26–58CrossRefGoogle Scholar
  2. 2.
    Maeda K, Domen K (2010) Photocatalytic water splitting: recent progress and future challenges. J Phys Chem Lett 1:2655–2661CrossRefGoogle Scholar
  3. 3.
    Huang H, Xiao K, He Y et al (2016) In situ assembly of BiOI@Bi12O17Cl2 pn junction: charge induced unique front-lateral surfaces coupling heterostructure with high exposure of BiOI 001 active facets for robust and nonselective photocatalysis. Appl Catal B 199:75–86CrossRefGoogle Scholar
  4. 4.
    Miseki Y, Fujiyoshi S, Gunji T, Sayama K (2017) Photocatalytic Z-scheme water splitting for independent H2/O2 production via a stepwise operation employing a vanadate redox mediator under visible light. J Phys Chem C 121:9691–9697CrossRefGoogle Scholar
  5. 5.
    Yuan Y, Zhao Z, Zheng J et al (2010) Polymerizable complex synthesis of BaZr1−xSnxO3 photocatalysts: role of Sn4+ in the band structure and their photocatalytic water splitting activities. J Mater Chem 20:6772–6779CrossRefGoogle Scholar
  6. 6.
    Kudo A, Kato H, Nakagawa S (2000) Water splitting into H2 and O2 on new Sr2M2O7 (M = Nb and Ta) photocatalysts with layered perovskite structures: factors affecting the photocatalytic activity. J Phys Chem B 104:571–575CrossRefGoogle Scholar
  7. 7.
    Sato J, Kobayashi H, Ikarashi K, Saito N, Nishiyama H, Inoue Y (2004) Photocatalytic activity for water decomposition of RuO2-dispersed Zn2GeO4 with d10 configuration. J Phys Chem B 108:4369–4375CrossRefGoogle Scholar
  8. 8.
    Yuan Y, Zhang X, Liu L et al (2008) Synthesis and photocatalytic characterization of a new photocatalyst BaZrO3. Int J Hydrogen Energy 33:5941–5946CrossRefGoogle Scholar
  9. 9.
    Meng J, Fu X, Du K et al (2018) BaZrO3 hollow nanostructure with Fe(III) doping for photocatalytic hydrogen evolution under visible light. Int J Hydrogen Energy 43:9224–9232CrossRefGoogle Scholar
  10. 10.
    Khan Z, Qureshi M (2012) Tantalum doped BaZrO3 for efficient photocatalytic hydrogen generation by water splitting. Catal Commun 28:82–85CrossRefGoogle Scholar
  11. 11.
    Maeda K, Domen K (2012) Water oxidation using a particulate BaZrO3–BaTaO2N solid-solution photocatalyst that operates under a wide range of visible light. Angew Chem 51:9865–9869CrossRefGoogle Scholar
  12. 12.
    Maeda K, Domen K (2014) Preparation of BaZrO3–BaTaO2N solid solutions and the photocatalytic activities for water reduction and oxidation under visible light. J Catal 310:67–74CrossRefGoogle Scholar
  13. 13.
    Ye TN, Xu M, Fu W et al (2014) The crystallinity effect of mesocrystalline BaZrO3 hollow nanospheres on charge separation for photocatalysis. Chem Commun 50:3021–3023CrossRefGoogle Scholar
  14. 14.
    Bai S, Wang L, Li Z, Xiong Y (2017) Facet-engineered surface and interface design of photocatalytic materials. Adv Sci 4:1600216CrossRefGoogle Scholar
  15. 15.
    Wang W, Li G, Xia D, An T, Zhao H, Wong PK (2017) Photocatalytic nanomaterials for solar-driven bacterial inactivation: recent progress and challenges. Environ Sci Nano 4:782–799CrossRefGoogle Scholar
  16. 16.
    Huang H, Tu S, Zeng C, Zhang T, Reshak AH, Zhang Y (2017) Macroscopic polarization enhancement promoting photo- and piezoelectric-induced charge separation and molecular oxygen activation. Angew Chem Int Ed 56:11860–11864CrossRefGoogle Scholar
  17. 17.
    Huang H, Wang J, Dong F et al (2015) Highly efficient Bi2O2CO3 single-crystal lamellas with dominantly exposed 001 facets. Cryst Growth Des 15:534–537CrossRefGoogle Scholar
  18. 18.
    Xie YP, Liu G, Yin L, Cheng HM (2012) Crystal facet-dependent photocatalytic oxidation and reduction reactivity of monoclinic WO3 for solar energy conversion. J Mater Chem 22:6746–6751CrossRefGoogle Scholar
  19. 19.
    Huang H, He Y, Li X et al (2015) Bi2O2(OH)(NO3) as a desirable [Bi2O2]2+ layered photocatalyst: strong intrinsic polarity, rational band structure and 001 active facets co-beneficial for robust photooxidation capability. J Mater Chem A 3:24547–24556CrossRefGoogle Scholar
  20. 20.
    Xu H, Ouyang S, Li P, Kako T, Ye J (2013) High-active anatase TiO2 nanosheets exposed with 95%{100} facets toward efficient H2 evolution and CO2 photoreduction. ACS Appl Mater Interfaces 5:1348–1354CrossRefGoogle Scholar
  21. 21.
    Wang J, Bian Z, Zhu J, Li H (2013) Ordered mesoporous TiO2 with exposed (001) facets and enhanced activity in photocatalytic selective oxidation of alcohols. J Mater Chem A 1:1296–1302CrossRefGoogle Scholar
  22. 22.
    Liu S, Yu J, Jaroniec M (2010) Tunable photocatalytic selectivity of hollow TiO2 microspheres composed of anatase polyhedra with exposed 001 facets. J Am Chem Soc 132:11914–11916CrossRefGoogle Scholar
  23. 23.
    Li R, Zhang F, Wang D et al (2013) Spatial separation of photogenerated electrons and holes among 010 and 110 crystal facets of BiVO4. Nat Commun 4:1432CrossRefGoogle Scholar
  24. 24.
    Gong H, Ma R, Mao F, Liu K, Cao H, Yan H (2016) Light-induced spatial separation of charges toward different crystal facets of square-like WO3. Chem Commun 52:11979–11982CrossRefGoogle Scholar
  25. 25.
    Perdew JP, Burke K, Ernzerhof M (1996) D of physics, NOL 70118J. quantum theory group Tulane University. Phys Rev Lett 77:3865CrossRefGoogle Scholar
  26. 26.
    Kresse G, Furthmüller J (1996) Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B 54:11169CrossRefGoogle Scholar
  27. 27.
    Kanie K, Seino Y, Matsubara M, Nakaya M, Muramatsu A (2014) Hydrothermal synthesis of BaZrO3 fine particles controlled in size and shape and fluorescence behavior by europium doping. New J Chem 38:3548–3555CrossRefGoogle Scholar
  28. 28.
    Kanie K, Sugimoto T (2004) Shape control of anatase TiO2 nanoparticles by amino acids in a gel–sol system. Chem Commun 21(14):1584–1585CrossRefGoogle Scholar
  29. 29.
    Eglitis R (2007) First-principles calculations of BaZrO3 (001) and (011) surfaces. J Phys Condens Matter 19:356004CrossRefGoogle Scholar
  30. 30.
    Eglitis R (2013) Ab initio calculations of the atomic and electronic structure of BaZrO3 (111) surfaces. Solid State Ion 230:43–47CrossRefGoogle Scholar
  31. 31.
    Eglitis R (2014) Ab initio calculations of SrTiO3, BaTiO3, PbTiO3, CaTiO3, SrZrO3, PbZrO3 and BaZrO3 (001), (011) and (111) surfaces as well as F centers, polarons, KTN solid solutions and Nb impurities therein. Int J Mod Phys B 28:1430009CrossRefGoogle Scholar
  32. 32.
    Lu Z, Tang Y, Chen L, Li Y (2004) Shape-controlled synthesis and characterization of BaZrO3 microcrystals. J Cryst Growth 266:539–544CrossRefGoogle Scholar
  33. 33.
    Andrés J, Gracia L, Gouveia AF, Ferrer MM, Longo E (2015) Effects of surface stability on the morphological transformation of metals and metal oxides as investigated by first-principles calculations. Nanotechnology 26:405703CrossRefGoogle Scholar
  34. 34.
    Fuenzalida V, Pilleux M (1995) Hydrothermally grown BaZrO3 films on zirconium metal: microstructure, X-ray photoelectron spectroscopy, and Auger electron spectroscopy depth profiling. J Mater Res 10:2749–2754CrossRefGoogle Scholar
  35. 35.
    Du P, Schneider J, Jarosz P, Eisenberg R (2006) Photocatalytic generation of hydrogen from water using a platinum(II) terpyridyl acetylide chromophore. J Am Chem Soc 128:7726–7727CrossRefGoogle Scholar
  36. 36.
    Tan H, Zhao Z, Zhu W-b et al (2014) Oxygen vacancy enhanced photocatalytic activity of pervoskite SrTiO3. ACS Appl Mater Interfaces 6:19184–19190CrossRefGoogle Scholar
  37. 37.
    Kim DS, Han SJ, Kwak SY (2007) Synthesis and photocatalytic activity of mesoporous TiO2 with the surface area, crystallite size, and pore size. J Colloid Interface Sci 316:85–91CrossRefGoogle Scholar
  38. 38.
    Li R, Weng Y, Zhou X et al (2015) Achieving overall water splitting using titanium dioxide-based photocatalysts of different phases. Energy Environ Sci 8:2377–2382CrossRefGoogle Scholar
  39. 39.
    Si Y, Cao S, Wu Z et al (2017) The effect of directed photogenerated carrier separation on photocatalytic hydrogen production. Nano Energy 41:488–493CrossRefGoogle Scholar
  40. 40.
    Zhang N, Chen C, Mei Z et al (2016) Monoclinic tungsten oxide with 100 facet orientation and tuned electronic band structure for enhanced photocatalytic oxidations. ACS Appl Mater Interfaces 8:10367–10374CrossRefGoogle Scholar
  41. 41.
    Yu J, Low J, Xiao W, Zhou P, Jaroniec M (2014) Enhanced photocatalytic CO2-reduction activity of anatase TiO2 by coexposed 001 and 101 facets. J Am Chem Soc 136:8839–8842CrossRefGoogle Scholar
  42. 42.
    Zhu M, Kim S, Mao L et al (2017) Metal-free photocatalyst for H2 evolution in visible to near-infrared region: black phosphorus/graphitic carbon nitride. J Am Chem Soc 139:13234–13242CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Center of Electron Microscopy, State Key Laboratory of Silicon Materials, and School of Materials Science and EngineeringZhejiang UniversityHangzhouPeople’s Republic of China
  2. 2.State Key Laboratory of Silicon Materials, School of Materials Science and EngineeringZhejiang UniversityHangzhouPeople’s Republic of China

Personalised recommendations