Journal of Materials Science

, Volume 53, Issue 17, pp 12065–12078 | Cite as

Visible-light responsive Cr(VI) reduction by carbonyl modification Nb3O7(OH) nanoaggregates

  • Tianning Wang
  • Jinshu Wang
  • Junshu Wu
  • Yucheng Du
  • Yongli Li
  • Hongyi Li
  • Yilong Yang
  • Xinjian Jia
Chemical routes to materials


Nanostructured photocatalysts have become a subject of much interest, with most research focusing on the visible-light sensitization in order to effectively utilize incoming solar energy for environmental remediation. Herein, we design an acetic acid-assisted solvothermal strategy, enabling Nb3O7(OH) nanoaggregates with C=C and C=O functional groups on the surface and extending the absorption edge located at 550 nm approximately. The success extension of harvesting light from intrinsic UV region below 380 nm to visible region relies on effective surface modification by carbonyl groups originated from citric acid in acetic acid solution. Specifically, the unique C=O-rich surface state and advantageous structural features render them particularly attractive for Cr(VI) photoreduction applications with the assistance of hole scavenger tartaric acid. No phase or morphology transition occurs during Cr(VI) reduction. The reaction rate slows down and the photoresponse area turns back into intrinsic UV region of Nb3O7(OH) with the prolonging reaction time, originating from the exhaustion of surface C=O functional groups. This work is expected to help to elucidate the rational design and efficient synthesis of visible-light absorption catalyst materials for actual applications in the near future.



This study was funded by National Key R&D Program of China (2017YFB0310804), National Natural Science Foundation (51402008, 51534009, 51621003, 52621003, 51225402), Beijing Natural Science Foundation (2151001), Beijing Municipal Commission of Education Foundation (KZ201610005002), and Beijing municipal high-level innovative team building program (IDHT 20170502).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

10853_2018_2496_MOESM1_ESM.doc (18.4 mb)
Supplementary material 1 (DOC 18808 kb)


  1. 1.
    Blowes D (2002) Tracking hexavalent Cr in groundwater. Science 295:2024–2025CrossRefGoogle Scholar
  2. 2.
    Deng YC, Tang L, Zeng GM, Zhu ZJ, Yan M, Zhou YY, Wang JJ, Liu YN, Wang JJ (2017) Insight into highly efficient simultaneous photocatalytic removal of Cr(VI) and 2, 4-dichlorophenol under visible light irradiation by phosphorus doped porous ultrathin g-C3N4 nanosheets from aqueous media: performance and reaction mechanism. Appl Catal B 203:343–354CrossRefGoogle Scholar
  3. 3.
    Liu H, Deng L, Zhang ZF, Guan J, Yang Y, Zhu ZF (2015) One-step in situ hydrothermal synthesis of SnS2/reduced graphene oxide nanocomposites with high performance in visible light-driven photocatalytic reduction of aqueous Cr(VI). J Mater Sci 50:3207–3211. CrossRefGoogle Scholar
  4. 4.
    Marinho BA, Djellabi R, Cristóvão RO, Loureiro JM, Boaventura RAR, Dias MM, Lopes JCB, Vilara VJP (2017) Intensification of heterogeneous TiO2 photocatalysis using an innovative micro–meso-structured-reactor for Cr(VI) reduction under simulated solar light. Chem Eng J 318:76–88CrossRefGoogle Scholar
  5. 5.
    Abdullah H, Gultom NS, Kuo DH (2017) Indium oxysulfide nanosheet photocatalyst for the hexavalent chromium detoxification and hydrogen evolution reaction. J Mater Sci 52:1–16. CrossRefGoogle Scholar
  6. 6.
    Abdullah H, Kuo DH, Chen YH (2016) High-efficient n-type TiO2/p-type Cu2O nanodiode photocatalyst to detoxify hexavalent chromium under visible light irradiation. J Mater Sci 51:8209–8223. CrossRefGoogle Scholar
  7. 7.
    Li N, Tian Y, Zhao JH, Zhang J, Zhang J, Zuo W, Ding Y (2017) Efficient removal of chromium from water by Mn3O4@ ZnO/Mn3O4 composite under simulated sunlight irradiation: synergy of photocatalytic reduction and adsorption. Appl Catal B 214:126–136CrossRefGoogle Scholar
  8. 8.
    Peng ZL, Xiong CM, Wang W, Tan FT, Xv Y, Wang XY, Qiao XL (2017) Facile modification of nanoscale zero-valent iron with high stability for Cr(VI) remediation. Sci Total Environ 596:266–273CrossRefGoogle Scholar
  9. 9.
    Bai Y, Ye L, Chen T, Wong PK (2017) Synthesis of hierarchical bismuth-rich Bi4O5BrxI2−x solid solutions for enhanced photocatalytic activities of CO2 conversion and Cr(VI) reduction under visible light. Appl Catal B 203:633–640CrossRefGoogle Scholar
  10. 10.
    Mondal C, Ganguly M, Pal J, Roy A, Jana J, Tal T (2014) Morphology controlled synthesis of SnS2 nanomaterial for promoting photocatalytic reduction of aqueous Cr(VI) under visible light. Langmuir 30:4157–4164CrossRefGoogle Scholar
  11. 11.
    Liu F, Xue DF (2009) Controlled fabrication of Nb2O5 hollow nanospheres and nanotubes. Mod Phys Lett B 23:3769–3775CrossRefGoogle Scholar
  12. 12.
    Liu J, Xue DF, Li KY (2011) Single-crystalline nanoporous Nb2O5 nanotubes. Nanoscale Res Lett 6:1–8Google Scholar
  13. 13.
    Liu MN, Xue DF (2008) Amine-assisted route to fabricate LiNbO3 particles with a tunable shape. J Phys Chem C 112:6346–6351CrossRefGoogle Scholar
  14. 14.
    Agarwal G, Reddy GB (2005) Study of surface morphology and optical properties of Nb2O5 thin films with annealing. J Mater Sci Mater Electron 16:21–24CrossRefGoogle Scholar
  15. 15.
    Zhao WL, Zhao W, Zhu GL, Lin TQ, Xu FF, Huang FQ (2016) Black Nb2O5 nanorods with improved solar absorption and enhanced photocatalytic activity. Dalton Trans 45:3888–3894CrossRefGoogle Scholar
  16. 16.
    Khan W, Betzler SB, Sipr O, Ciston J, Blaha P, Scheu C, Minar J (2016) Theoretical and Experimental Study on the Optoelectronic, Properties of Nb3O7(OH) and Nb2O5 Photoelectrodes. J Phys Chem C 120:23329–23338CrossRefGoogle Scholar
  17. 17.
    Wu JS, Wang JS, Li HY, Xue DF (2013) Solution-phase tailored growth of NB3O7(OH) thin films. Thin Solid Films 544:545–550CrossRefGoogle Scholar
  18. 18.
    Zhang HM, Wang Y, Liu PR, Chou SL, Wang JZ, Liu HW, Wang GZ, Zhou HJ (2016) Highly ordered single crystalline nanowire array assembled three-dimensional Nb3O7(OH) and Nb2O5 superstructures for energy storage and conversion applications. ACS Nano 10:507–514CrossRefGoogle Scholar
  19. 19.
    Zhang HM, Wang Y, Yang DJ, Li YB, Liu HW, Liu PR, Wood BJ, Zhao HJ (2012) Directly hydrothermal growth of single crystal Nb3O7(OH) nanorod film for high performance dye-sensitized solar cells. Adv Mater 24:1598–1603CrossRefGoogle Scholar
  20. 20.
    Le S, Reddy DA, Kim TK (2016) Well-wrapped reduced graphene oxide nanosheets on Nb3O7(OH) nanostructures as good electron collectors and transporters for efficient photocatalytic degradation of rhodamine B and phenol. Rsc Adv 6:37180–37188CrossRefGoogle Scholar
  21. 21.
    Hmadeh M, Hoepfner V, Larios E, Liao K, Jia J, Jose-Yacaman M, Ozin GA (2014) New hydrogen-evolution heteronanostructured photocatalysts: Pt-Nb3O7(OH) and Cu-Nb3O7(OH). Chemsuschem 7:2104–2109CrossRefGoogle Scholar
  22. 22.
    Park YS, Kim WY, Park HW, Tachikawa T, Majima T (2009) Carbon-doped TiO2, photocatalyst synthesized without using an external carbon precursor and the visible light activity. Appl Catal B 91:355–361CrossRefGoogle Scholar
  23. 23.
    Ge SX, Jia HM, Zhao HX, Zheng Z, Zhang LZ (2010) Niobium pentoxide hollow nanospheres with enhanced visible light photocatalytic activity. J Mater Chem 20:3052–3058CrossRefGoogle Scholar
  24. 24.
    Hu SL, Tian RX, Wu LL, Zhao Q, Yang JL, Liu J, Cao SR (2013) Chemical regulation of carbon quantum dots from synthesis to photocatalytic activity. Chem Asian J 8:1035–1041CrossRefGoogle Scholar
  25. 25.
    Wang YX, Ao ZM, Sun HQ, Duan XG, Wang SB (2016) Activation of peroxymonosulfate by carbonaceous oxygen groups: experimental and density functional theory calculations. Appl Catal B 198:295–302CrossRefGoogle Scholar
  26. 26.
    Huang YP, Ma H, Wang SG, Shen MW, Guo R, Cao XY, Zhu MF, Shi XY (2012) Efficient catalytic reduction of hexavalent chromium using palladium nanoparticle-immobilized electrospun polymer nanofibers. ACS Appl Mater Interfaces 4:3054–3061CrossRefGoogle Scholar
  27. 27.
    Dandapat A, Jana D, De G (2011) Pd nanoparticles supported mesoporous γ-Al2O3 film as a reusable catalyst for reduction of toxic CrVI to CrIII in aqueous solution. Appl Catal A 396:34–39CrossRefGoogle Scholar
  28. 28.
    Wu JS, Wang JS, Li HY, Li YL, Du YC, Yang YL, Jia XJ (2017) Surface activation of MnNb2O6 nanosheets by oxalic acid for enhanced photocatalysis. Appl Surf Sci 403:314–325CrossRefGoogle Scholar
  29. 29.
    Betzler SB, Wisnet A, Breitbach B, Mitterbauer C, Weickert J, Schmidt-Mended L, Scheu C (2014) Template-free synthesis of novel, highly-ordered 3D hierarchical Nb3O7(OH) superstructures with semiconductive and photoactive properties. J Mater Chem A 2:12005–12013CrossRefGoogle Scholar
  30. 30.
    Yue ZK, Chu DM, Huang H, Huang J, Yang P, Du YK, Zhu MS, Lu C (2015) A novel heterogeneous hybrid by incorporation of Nb2O5 microspheres and reduced graphene oxide for photocatalytic H2 evolution under visible light irradiation. RSC Adv 5:47117–47124CrossRefGoogle Scholar
  31. 31.
    Furukawa S, Ohno Y, Shishido T, Teramura K, Tanaka T (2011) Reaction mechanism and the role of copper in the photooxidation of alcohol over Cu/Nb2O5. ChemPhysChem 12:2823–2830CrossRefGoogle Scholar
  32. 32.
    Ge SX, Jia HM, Zhao HX, Zheng Z, Zhang LZ (2010) First observation of visible light photocatalytic activity of carbon modified Nb2O5 nanostructures. J Mater Chem 20:3052–3058CrossRefGoogle Scholar
  33. 33.
    Prado AGS, Bolzon LB, Pedroso CP, Moura AO, Costa LL (2008) Nb2O5 as efficient and recyclable photocatalyst for indigo carmine degradation. Appl Catal B 82:219–224CrossRefGoogle Scholar
  34. 34.
    Wei XN, Wang HL, Wang XK, Jiang WF (2017) Facile synthesis of tunable carbon modified mesoporous TiO2 for visible light photocatalytic application. Appl Surf Sci 412:357–365CrossRefGoogle Scholar
  35. 35.
    ZhaoY Li Y, Cheng HH, Hu Y, Shi GQ, Dai LM, Qu LT (2011) Nitrogen-doped graphene quantum dots with oxygen-rich functional groups. J Am Chem Soc 134:15–18CrossRefGoogle Scholar
  36. 36.
    Hu SL, Guo Y, Liu W, Bai PK, Sun JS, Cao SR (2011) Controllable synthesis and Photoluminescence (PL) of amorphous and crystalline carbon nanoparticles. J Phys Chem Solids 72:749–754CrossRefGoogle Scholar
  37. 37.
    Li Y, Hu Y, Zhao Y, Shi GQ, Deng LE, Hou YB, Liangti QuLT (2011) An electrochemical avenue to green-luminescent graphene quantum dots as potential electron-acceptors for photovoltaics. Adv Mater 23:776–780CrossRefGoogle Scholar
  38. 38.
    Djellabi R, Ghorab MF, Nouacer S, Smara A, Khireddine O (2016) Cr(VI) photocatalytic reduction under sunlight followed by Cr(III) extraction from TiO2 surface. Mater Lett 176:106–109CrossRefGoogle Scholar
  39. 39.
    Djellabi R, Ghorab MF (2014) Photoreduction of toxic chromium using TiO2-immobilized under natural sunlight: effects of some hole scavengers and process parameters. Desalin Water Treat 55:1900–1907CrossRefGoogle Scholar
  40. 40.
    Wang N, Zhu LH, Deng KJ, She YB, Yu YM, Tang HQ (2010) Visible light photocatalytic reduction of Cr(VI) on TiO2 in situ modified with small molecular weight organic acids. Appl Catal B 95:400–407CrossRefGoogle Scholar
  41. 41.
    Yang JK, Lee SM (2006) Removal of Cr(VI) and humic acid by using TiO2 photocatalysis. Chemosphere 63:1677–1684CrossRefGoogle Scholar
  42. 42.
    Hashemzadeh F, Gaffarinejad A, Rahimi R (2015) Porous p-NiO/n-Nb2O5 nanocomposites prepared by an EISA route with enhanced photocatalytic activity in simultaneous Cr(VI) reduction and methyl orange decolorization under visible light irradiation. J Hazard Mater 286:64–74CrossRefGoogle Scholar
  43. 43.
    Hackbarth FV, Maass D, Souza AAUD, Vilar VJP, Souza SMAGUD (2016) Removal of hexavalent chromium from electroplating wastewaters using marine macroalga Pelvetia canaliculata as natural electron donor. Chem Eng J 290:477–489CrossRefGoogle Scholar
  44. 44.
    Litter MI (1999) Heterogeneous photocatalysis: transition metal ions in photocatalytic systems. Appl Catal B 23:89–114CrossRefGoogle Scholar
  45. 45.
    Betzler SB, Harzer T, Ciston J, Dahmen U, Dehm G, Scheu C (2016) Heat-induced phase transformation of three-dimensional Nb3O7(OH) superstructures: effect of atmosphere and electron beam. Cryst Growth Des 16:4309–4317CrossRefGoogle Scholar
  46. 46.
    Xiao ZD, Li M, Xu MH, Lu ZH (1998) The influence of new binding state of dye-molecules to TiO2, electrode surface on IPCE performance. J Phys Chem Solids 59:911–914CrossRefGoogle Scholar
  47. 47.
    Bellot-Gurlet L, Pages-Camagna S, Coupry C (2006) Raman spectroscopy in art and archaeology. J Raman Spectrosc 379:962–965CrossRefGoogle Scholar
  48. 48.
    Bronzato M, Calvini P, Federici C, Bogialli S, Favaro G, Meneghetti M, Mba M, Brustolon M, Zoleo A (2013) Degradation products from naturally aged paper leaves of a 16th-century-printed book: a spectrochemical study. Chem A Eur J 19:9569–9577CrossRefGoogle Scholar
  49. 49.
    Mitoraj D, Kisch H (2010) On the mechanism of urea-induced titania modification. Chemistry 16:261–269CrossRefGoogle Scholar
  50. 50.
    Pitzer L, Sandfort F, Striethkalthoff F, Glorius F (2017) Intermolecular radical addition to carbonyls enabled by visible light photoredox initiated hole catalysis. J Am Chem Soc 139:13652–13655CrossRefGoogle Scholar
  51. 51.
    Samsudin EM, Hamid SBA, Juan JC, Basirun WJ, Kandjani AE, Bhargava SK (2016) Effective role of trifluoroacetic acid (TFA) to enhance the photocatalytic activity of F-doped TiO2, prepared by modified sol–gel method. Appl Surf Sci 365:57–68CrossRefGoogle Scholar
  52. 52.
    Tong H, Ouyang SX, Bi YP, Umezawa N, Oshikiri M, Ye JH (2012) Nano-photocatalytic materials: possibilities and challenges. Adv Mater 24:229–251CrossRefGoogle Scholar
  53. 53.
    Ravelli D, Protti S, Fagnoni M (2016) Carbon-carbon bond forming reactions via photogenerated intermediates. Chem Rev 116:9850–9913CrossRefGoogle Scholar

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Authors and Affiliations

  1. 1.School of Materials Science and EngineeringBeijing University of TechnologyChaoyang District, BeijingChina

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