Design and synthesis of La3+-, Sb3+-doped MOF-In2S3@FcDc-TAPT COFs hybrid materials with enhanced photocatalytic activity

  • Ren He
  • Kehui Xue
  • Jing Wang
  • Tianli Yang
  • Renrui Sun
  • Lin Wang
  • Xianglin Yu
  • Uche Omeoga
  • Wenlei WangEmail author
  • Ting Yang
  • Yunchu Hu
  • Shaofeng PiEmail author
Chemical routes to materials


Based on the synthesis of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT) and ferrocene-1,1′-dicarbaldehyde (FcDc), a variety of novel La3+-, Sb3+-doped MOF-In2S3@FcDc-TAPT COFs hybrid materials were designed and synthesized with NH2-MIL-68(In) as matrix. A dense cladding layer has formed on the surface of the MOF-In2S3 heterostructure through coating FcDc-TAPT COFs. The detection of C-N bonds confirmed that the hybrid materials were covalently bonded with the ferrocene-1,1′-dicarbaldehyde (FcDc)-modified covalent triazine-based frameworks (FcDc-TAPT). Then, the photocatalytic reduction of Cr(VI) in aqueous phase under visible light was implemented with the hybrid materials as photocatalysts. Doping La3+ or Sb3+ has obviously improved the photocatalytic degradation efficiency of Cr(VI). In particular, Sb3+-doped MOF-In2S3@FcDc-TAPT COFs had the best removal of Cr(VI) with removal rate of 99% within 20 min. By fitting the experimental data with the pseudo-first-order equation, the speed constants were obtained. The kinetics constant of Sb3+-doped MOF-In2S3@FcDc-TAPT COFs for Cr(VI) degradation was 0.4307 min−1, which was more than 19.87 times as much as that of the non-doped MOF-In2S3@FcDc-TAPT COFs hybrid materials. The DRS and PL results verified that the introduction of La3+ or Sb3+ into the hybrid materials could effectively inhibit the photogenic electron and promote the separation of electron–hole pairs. The cyclic and stability results displayed that the removal rate of Cr(VI) by Sb3+-doped MOF-In2S3@FcDc-TAPT COFs after five times of repeated use was still 95.39%; in particular, it was not significantly changed even after 150 d. It confirmed that the Sb3+-doped MOF-In2S3@FcDc-TAPT COFs was a very stable catalyst, due to the carbonyl and Cp ring conjugate of FcDc, which could produce delocalized electrons and stabilize the ions or free radicals.



The authors gratefully acknowledge the financial support of the National Natural Science Foundation of China (Grant No: 21607176), the Natural Science Foundation of Hunan Province, China (Grant No. 2017JJ3516), the Research Foundation of Education Bureau of Hunan Province, China (Grant No. 16B274), and The open fund for key discipline of Forestry of Central South University of Forestry and Technology (Grant No. 2016ZD11). The authors also thank the reviewers for their constructive comments and suggestions.

Compliance with ethical standards

Conflict of interest

The authors declare no competing financial interest.


  1. 1.
    Wang Y, Wang XC, Antonietti M (2012) Polymeric graphitic carbon nitride as a heterogeneous organocatalyst: from photochemistry to multipurpose catalysis to sustainable chemistry. Angew Chem Int Ed 51:68–89CrossRefGoogle Scholar
  2. 2.
    Chen W, Huang T, Hua YX, Liu TY, Liu XH, Chen SM (2016) Hierarchical CdIn2S4 microspheres wrapped by mesoporous g-C3N4 ultrathin nanosheets with enhanced visible light driven photocatalytic reduction activity. J Hazard Mater 320:529–538CrossRefGoogle Scholar
  3. 3.
    Farhat A, Keller J, Tait S, Radjenovic J (2015) Removal of persistent organic contaminants by electrochemically activated sulfate. Environ Sci Technol 49:14326–14333CrossRefGoogle Scholar
  4. 4.
    Ghanbari F, Moradi M (2017) Application of peroxymonosulfate and its activation methods for degradation of environmental organic pollutants: review. Chem Eng J 310:41–62CrossRefGoogle Scholar
  5. 5.
    Wen Y, Zhao Y, Guo MZ, Yu Y (2019) Synergetic effect of Fe2O3 and BiVO4 as photocatalyst nanocomposites for improved photo-Fenton catalytic activity. J Mater Sci 54:8236–8246. CrossRefGoogle Scholar
  6. 6.
    Yang Y, Wang GZ, Deng Q, Ng DH, Zhao HJ (2014) Microwave-assisted fabrication of nanoparticulate TiO2 microspheres for synergistic photocatalytic removal of Cr(VI) and methyl orange. ACS Appl Mater Interfaces 6:3008–3015CrossRefGoogle Scholar
  7. 7.
    Lin KY, Chang HA, Chen RC (2015) MOF-derived magnetic carbonaceous nanocomposite as a heterogeneous catalyst to activate oxone for decolorization of Rhodamine B in water. Chemosphere 130:66–72CrossRefGoogle Scholar
  8. 8.
    Mahadadalkar MA, Gosavi SW, Kale BB (2018) Interstitial charge transfer pathways in a TiO2/CdIn2S4 heterojunction photocatalyst for direct conversion of sunlight into fuel. J Mater Chem A 6:16064–16073CrossRefGoogle Scholar
  9. 9.
    Ray C, Pal T (2017) Recent advances of metal–metal oxide nanocomposites and their tailored nanostructures in numerous catalytic applications. J Mater Chem A 5:9465–9487CrossRefGoogle Scholar
  10. 10.
    Zeng T, Zhang XL, Wang SH, Niu HY, Cai YQ (2015) Spatial confinement of a Co3O4 catalyst in hollow Metal-Organic Frameworks as a nanoreactor for improved degradation of organic pollutants. Environ Sci Technol 49:2350–2357CrossRefGoogle Scholar
  11. 11.
    Ren L, Mao M, Li Y, Lan L, Zhang Z, Zhao X (2016) Novel photothermocatalytic synergetic effect leads to high catalytic activity and excellent durability of anatase TiO2 nanosheets with dominant 001 facets for benzene abatement. Appl Catal B Environ 198:303–310CrossRefGoogle Scholar
  12. 12.
    Yin Y, Jin Z, Hou F (2007) Enhanced solar water-splitting efficiency using core/sheath heterostructure CdS/TiO2 nanotube arrays. Nanotechnology 18:495608CrossRefGoogle Scholar
  13. 13.
    Sheikhiabadi PG, Salavati-Niasari M, Davar F (2012) Hydrothermal synthesis and optical properties of antimony sulfide micro and nano-size with different morphologies. Mater Lett 71:168–171CrossRefGoogle Scholar
  14. 14.
    Chen H, Peng YP, Chen TY, Chen KF, Chang KL, Dang Z, Lu GN, He H (2018) Enhanced photoelectrochemical degradation of Ibuprofen and generation of hydrogen via BiOI-deposited TiO2 nanotube arrays. Sci Total Environ 633:1198–1205CrossRefGoogle Scholar
  15. 15.
    Zheng Y, Wang W, Jiang D, Zhang L, Li X, Wang Z (2016) Ultrathin mesoporous Co3O4 nanosheets with excellent photo-/thermo-catalytic activity. J Mater Chem A 4:105–112CrossRefGoogle Scholar
  16. 16.
    Ma ZL, Dou S, Shen AL, Tao L, Dai LM, Wang SY (2015) Sulfur doped graphene derived from cycled lithium-sulfur batteries as metal-free electrocatalyst for oxygen reduction reaction. Angew Chem Int Ed 54:1888–1892CrossRefGoogle Scholar
  17. 17.
    Li XY, Pi YH, Wu LQ, Xia QB, Wu JL, Li Z, Xiao J (2017) Facilitation of the visible light-induced Fenton-like excitation of H2O2 via heterojunction of g-C3N4/NH2-iron terephthalate metal-organic framework for MB degradation. Appl Catal B Environ 202:653–663CrossRefGoogle Scholar
  18. 18.
    Llabres I, Xamena FX, Corma A, Garcia H (2007) Applications for metal-organic frameworks (MOFs) as quantum dot semiconductors. J Phys Chem C 111:80–85CrossRefGoogle Scholar
  19. 19.
    Pi YH, Li XY, Xia QB, Wu JL, Li Z, Li YW, Xiao J (2017) Formation of willow leaf-like structures composed of NH2-MIL68(In) on a multifunctional multiwalled carbon nanotube backbone for enhanced photocatalytic reduction of Cr(VI). Nano Res 10:3543–3556CrossRefGoogle Scholar
  20. 20.
    Dhakshinamoorthy A, Asiri AM, Garcia H (2016) Metal-organic framework (MOF) compounds: photocatalysts for redox reactions and solar fuel production. Angew Chem Int Ed 55:5414–5445CrossRefGoogle Scholar
  21. 21.
    Yang C, You X, Cheng JH, Zheng HD, Chen YC (2017) A novel visible-light-driven In-based MOF/graphene oxide composite photocatalyst with enhanced photocatalytic activity toward the degradation of amoxicillin. Appl Catal B Environ 200:673–680CrossRefGoogle Scholar
  22. 22.
    Abdelhameed RM, Simoes MM, Silva AM, Rocha J (2015) Enhanced photocatalytic activity of MIL-125 by post-synthetic modification with Cr(III) and Ag nanoparticles. Chemistry 21:11072–11081CrossRefGoogle Scholar
  23. 23.
    Wang H, Yuan X, Wu Y, Zeng G, Chen X, Leng L, Wu Z, Jiang L, Li H (2015) Facile synthesis of amino-functionalized titanium metal-organic frameworks and their superior visible-light photocatalytic activity for Cr(VI) reduction. J Hazard Mater 286:187–194CrossRefGoogle Scholar
  24. 24.
    Hong YZ, Li CS, Yin BX, Li D, Zhang ZY, Mao BD, Fan WQ, Gu W, Shi WD (2018) Promoting visible-light-induced photocatalytic degradation of tetracycline by an efficient and stable beta-Bi2O3@g-C3N4 core/shell nanocomposite. Chem Eng J 338:137–146CrossRefGoogle Scholar
  25. 25.
    Sang Y, Zhao Z, Zhao M, Hao P, Leng Y, Liu H (2015) From UV to near-infrared, WS2 nanosheet: a novel photocatalyst for full solar light spectrum photodegradation. Adv Mater 27:363–369CrossRefGoogle Scholar
  26. 26.
    Tang T, Lu G, Wang W, Wang R, Huang K, Qiu Z, Tao X, Dang Z (2018) Photocatalytic removal of organic phosphate esters by TiO2: effect of inorganic ions and humic acid. Chemosphere 206:26–32CrossRefGoogle Scholar
  27. 27.
    Gong Y, Zhao X, Zhang H, Yang B, Xiao K, Guo T, Zhang JJ, Shao HX, Wang YB, Yu G (2018) MOF-derived nitrogen doped carbon modified g-C3N4 heterostructure composite with enhanced photocatalytic activity for bisphenol a degradation with peroxymonosulfate under visible light irradiation. Appl Catal B Environ 233:35–45CrossRefGoogle Scholar
  28. 28.
    Zeng M, Chai ZG, Deng X, Li Q, Feng SQ, Wang J, Xu DS (2016) Core-shell CdS@ZIF-8 structures for improved selectivity in photocatalytic H2 generation from formic acid. Nano Res 9:2729–2734CrossRefGoogle Scholar
  29. 29.
    Zhang FM, Sheng JL, Yang ZD, Sun XJ, Tang HL, Lu M, Dong H, Shen FC, Liu J, Lan YQ (2018) Rational design of MOF/COF hybrid materials for photocatalytic H2 evolution in the presence of sacrificial electron donors. Angew Chem Int Ed 57:12106–12110CrossRefGoogle Scholar
  30. 30.
    Tao W, Chang J, Wu D, Gao Z, Duan X, Xu F, Jiang K (2013) Solvothermal synthesis of graphene-Sb2S3 composite and the degradation activity under visible light. Mater Res Bull 48:538–543CrossRefGoogle Scholar
  31. 31.
    Yang LQ, Huang JF, Shi L, Cao LY, Liu HM, Liu YY, Li YX, Song H, Jie YN, Ye JH (2018) Sb doped SnO2-decorated porous g-C3N4 nanosheet heterostructures with enhanced photocatalytic activities under visible light irradiation. Appl Catal B Environ 221:670–680CrossRefGoogle Scholar
  32. 32.
    Skiker R, Zouraibi M, Said M, Zia K (2018) Facile coprecipitation synthesis of novel Bi12TiO20/BiFeO3 heterostructure serie with enhanced photocatalytic activity for removal of methyl orange from water. J Phys Chem Solids 119:265–275CrossRefGoogle Scholar
  33. 33.
    Wang SB, Guan BY, Lu Y, Lou XW (2017) Formation of hierarchical In2S3-CdIn2S4 heterostructured nanotubes for efficient and stable visible light CO2 reduction. J Am Chem Soc 139:17305–17308CrossRefGoogle Scholar
  34. 34.
    Peng YW, Zhao MT, Chen B, Zhang ZC, Huang Y, Dai FN, Lai ZC, Cui XY, Tan CL, Zhang H (2018) Hybridization of MOFs and COFs: a new strategy for construction of MOF@COF core-shell hybrid materials. Adv Mater 30:1705454CrossRefGoogle Scholar
  35. 35.
    Wu WM, Lin R, Shen LJ, Liang RW, Yuan RS, Wu L (2013) Visible-light-induced photocatalytic hydrogenation of 4-nitroaniline over In2S3 photocatalyst in water. Catal Commun 40:1–4CrossRefGoogle Scholar
  36. 36.
    Berestok T, Guardia P, Portals JB, Estradé S, Llorca J, Peiró F, Cabot A, Brock SL (2018) Surface chemistry and nano-/microstructure engineering on photocatalytic In2S3 nanocrystals. Langmuir 34:6470–6479CrossRefGoogle Scholar
  37. 37.
    Wang Q, Tian S, Ning P (2014) Degradation mechanism of methylene blue in a heterogeneous Fenton-like reaction catalyzed by ferrocene. Ind Eng Chem Res 53:6334–6340CrossRefGoogle Scholar
  38. 38.
    Regmi C, Kshetri YK, Ray SK, Pandey RP, Lee SW (2017) Utilization of visible to NIR light energy by Yb3+, Er3+ and Tm3+ doped BiVO4 for the photocatalytic degradation of methylene blue. Appl Surf Sci 392:61–70CrossRefGoogle Scholar
  39. 39.
    Liang RW, Shen LJ, Jing FF, Wu WM, Qin N, Lin R, Wu L (2015) NH2-mediated indium metal–organic framework as a novel visible-light-driven photocatalyst for reduction of the aqueous Cr(VI). Appl Catal B Environ 162:245–251CrossRefGoogle Scholar
  40. 40.
    Chen J, Liu WX, Gao WW (2016) Tuning photocatalytic activity of In2S3 broadband spectrum photocatalyst based on morphology. Appl Surf Sci 368:288–297CrossRefGoogle Scholar
  41. 41.
    Choi IH, Jang SY, Kim HC, Huh S (2018) In6S7 nanoparticle-embedded and sulfur and nitrogen co-doped microporous carbons derived from In(tdc)2 metal-organic framework. Dalton Trans 47:1140–1150CrossRefGoogle Scholar
  42. 42.
    Wang ZM, Lu P, Chen SM, Gao Z, Shen FZ, Zhang WS, Xu YX, Kwok HS, Ma YG (2011) Phenanthro[9,10-d] imidazole as a new building block for blue light emitting materials. J Mater Chem 21:5451–5456CrossRefGoogle Scholar
  43. 43.
    Li X, Gao Q, Wang JF, Chen YF, Chen ZH, Xu HS, Tang W, Leng K, Ning GH, Wu JS, Xu QH, Quek SY, Lu YX, Loh KP (2018) Tuneable near white-emissive two-dimensional covalent organic frameworks. Nat Commun 9:2335CrossRefGoogle Scholar
  44. 44.
    Samuel MS, Subramaniyan V, Bhattacharya J, Parthiban C, Chand S, Singh NDP (2018) A GO-CS@MOF [Zn(BDC)(DMF)] material for the adsorption of chromium(VI) ions from aqueous solution. Compos Part B Eng 152:116–125CrossRefGoogle Scholar
  45. 45.
    Wu F, Huang HW, Xu TF, Lu WY, Li N, Chen WX (2017) Visible-light-assisted peroxymonosulfate activation and mechanism for the degradation of pharmaceuticals over pyridyl-functionalized graphitic carbon nitride coordinated with iron phthalocyanine. Appl Catal B Environ 218:230–239CrossRefGoogle Scholar
  46. 46.
    Zhang GG, Li GS, Lan ZA, Lin LH, Savateev A, Heil T, Zafeiratos S, Wang XC, Antonietti M (2017) Optimizing optical absorption, exciton dissociation, and charge transfer of a polymeric carbon nitride with ultrahigh solar hydrogen production activity. Angew Chem Int Ed 56:13445–13449CrossRefGoogle Scholar
  47. 47.
    Fan L, Guo R (2008) Fabrication of novel CdIn2S4 hollow spheres via a facile hydrothermal process. J Phys Chem C 112:10700–10706CrossRefGoogle Scholar
  48. 48.
    Gao E, Wang WZ, Shang M, Xu JH (2011) Synthesis and enhanced photocatalytic performance of graphene-Bi2WO6 composite. Phys Chem Chem Phys 13:2887–2893CrossRefGoogle Scholar
  49. 49.
    Jiang L, Yuan X, Zeng G, Chen X, Wu Z, Liang J, Zhang J, Wang H, Wang H (2017) Phosphorus- and sulfur-Codoped g-C3N4: facile preparation, mechanism insight, and application as efficient photocatalyst for tetracycline and methyl orange degradation under visible light irradiation. ACS Sustain Chem Eng 5:5831–5841CrossRefGoogle Scholar
  50. 50.
    Zhou L, Zhao C, Giri B, Allen P, Xu X, Joshi H, Fan Y, Titova LV, Rao PM (2016) High light absorption and charge separation efficiency at low applied voltage from Sb-doped SnO2/BiVO4 core/shell nanorod-array photoanodes. Nano Lett 16:3463–3474CrossRefGoogle Scholar
  51. 51.
    Xing CS, Wu ZD, Jiang DL, Chen M (2014) Hydrothermal synthesis of In2S3/g-C3N4 heterojunctions with enhanced photocatalytic activity. J Colloid Interf Sci 433:9–15CrossRefGoogle Scholar
  52. 52.
    Liu GD, Jiao XL, Qin ZH, Chen DR (2011) Solvothermal preparation and visible photocatalytic activity of polycrystalline β-In2S3 nanotube. Cryst Eng Commun 13:182–187CrossRefGoogle Scholar
  53. 53.
    Yin WJ, Bai LJ, Zhu YZ, Zhong SX, Zhao LH, Li ZQ, Bai S (2016) Embedding metal in the interface of a p-n heterojunction with a stack design for superior Z-scheme photocatalytic hydrogen evolution. ACS Appl Mater Interfaces 8:23133–23142CrossRefGoogle Scholar
  54. 54.
    Zhang LZ, Chen H, Zhao XF, Zhai Q, Yin DJ, Sun YF, Li JH (2016) The marriage of ferrocene and silicotungstate: an ingenious heterogeneous Fenton-like synergistic photocatalyst. Appl Catal B Environ 193:47–57CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.College of ScienceCentral South University of Forestry and TechnologyChangshaPeople’s Republic of China
  2. 2.School of Materials Science and EngineeringCentral South University of Forestry and TechnologyChangshaChina

Personalised recommendations