Skip to main content
Log in

One-step microwave hydrothermal preparation of Cd/Zr-bimetallic metal–organic frameworks for enhanced photochemical properties

  • Original Research
  • Published:
Advanced Composites and Hybrid Materials Aims and scope Submit manuscript

Abstract

A new bimetallic metal–organic framework (Cd/Zr-MOF) was successfully synthesized via microwave hydrothermal method using Zr4+ and Cd2+ as two metal ions and terephthalic acid (H2BDC) as organic ligand. The effects of Cd/Zr molar ratio and the reaction temperature on the Cd/Zr-MOF structure and its photocatalytic performance to degrade Rhodamine B (RhB) under simulated sunlight were explored in detail. The results show that the Cd/Zr-MOF with Cd/Zr molar ratio of 5:1 obtained at the reaction temperature of 160 °C exhibits the best photocatalytic performance, and the photocatalytic efficiency can reach 95.82% after 105 min irradiation, which is much higher than that of pure UiO-66 or pure Cd-MOF. The result of Mott–Schottky tests certified the formation of n–n heterojunction between Cd-MOF and UiO-66, which is conducive to the transfer and separation of photogenerated electrons and holes and is the main reason of the enhanced photocatalytic performance. In addition, the mechanism of photocatalytic degradation of Cd/Zr-MOF was studied by adding different eliminating agents. The photodegradation of RhB was mainly caused by superoxide ion (·O2) and electron hole (h+).

Graphical abstract

The Cd/Zr-MOF composites with excellent photocatalytic activity to Rhodamine B were synthesized via one-step microwave hydrothermal method.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11

Similar content being viewed by others

References

  1. Zhu W, Ge S, Shao Q (2016) Adsorption properties of ZrO2 hollow microboxes prepared using CaCO3 cubes as templates. RSC Adv 6(85):81736–81743

    Article  CAS  Google Scholar 

  2. Zhang M, Shang Q, Wan Y, Cheng Q, Liao G, Pan Z (2019) Self-template synthesis of double-shell TiO2@ZIF-8 hollow nanospheres via sonocrystallization with enhanced photocatalytic activities in hydrogen generation. Appl Catal B 241:149–158

    Article  CAS  Google Scholar 

  3. Ge S, Zhu W, Shao Q (2016) Fabrication and characterization of hollow zirconia microspheres using calcium carbonate as template. Z Phys Chem 230(11):1617–1628

    Article  CAS  Google Scholar 

  4. Zhao J, Ge S, Pan D, Pan Y (2019) Microwave hydrothermal synthesis of In2O3-ZnO nanocomposites and their enhanced photoelectrochemical properties. J Electrochem Soc 166(5):3074–3083

    Article  Google Scholar 

  5. Chen H, Liu T, Wang B, Liu Z, Li Y, Zhao Q, Wang N, He H, Liu H, Guo Z (2018) Highly efficient charge collection in dye-sensitized solar cells based on nanocomposite photoanode filled with indium-tin oxide interlayer. Adv Compos Hybrid Mater 1(2):356–363

    Article  CAS  Google Scholar 

  6. Jain R, Mathur M, Sikarwar S, Mittal A (2007) Removal of the hazardous dye rhodamine B through photocatalytic and adsorption treatments. J Environ Manage 85(4):956–964

    Article  CAS  Google Scholar 

  7. Hu L, Deng G, Lu W, Lu Y, Zhang Y (2017) Peroxymonosulfate activation by Mn3O4/metal-organic framework for degradation of refractory aqueous organic pollutant rhodamine B. Chin J Catal 38(8):1360–1372

    Article  CAS  Google Scholar 

  8. Zhao J, Ge S, Liu L, Shao Q, Mai X, Zhao CX, Hao L, Wu T, Yu Z, Guo Z (2017) Microwave solvothermal fabrication of zirconia hollow microspheres with different morphologies using pollen templates and their dye adsorption removal. Ind Eng Chem Res 57(1):231–241

    Article  Google Scholar 

  9. Liu Q, Zhou B, Xu M, Mao G (2017) Integration of nanosized ZIF-8 particles onto mesoporous TiO2 nanobeads for enhanced photocatalytic activity. RSC Adv 7(13):8004–8010

    Article  CAS  Google Scholar 

  10. Li R, Lin C, Wang N, Luo L, Chen Y, Li J, Guo Z (2018) Advanced composites of complex Ti-based oxides as anode materials for lithium-ion batteries. Adv Compos Hybrid Mater 1(3):440–459

    Article  CAS  Google Scholar 

  11. Lee JY, Jo WK (2016) Heterojunction-based two-dimensional N-doped TiO2/WO3 composite architectures for photocatalytic treatment of hazardous organic vapor. J Hazard Mater 314:22–31

    Article  CAS  Google Scholar 

  12. Liang Q, Cui S, Jin J, Liu C, Xu S, Yao C, Li Z (2018) Fabrication of BiOI@UiO-66(NH2)@g-C3N4 ternary Z-scheme heterojunction with enhanced visible-light photocatalytic activity. Appl Surf Sci 456:899–907

    Article  CAS  Google Scholar 

  13. Zhang J, Zhu Z, Feng X (2014) Construction of two-dimensional MoS2/CdS p-n nanohybrids for highly efficient photocatalytic hydrogen evolution. Chem Eur J 20(34):10632–10635

    Article  CAS  Google Scholar 

  14. Hao X, Cui Z, Zhou J, Wang Y, Hu Y, Wang Y, Zou Z (2018) Architecture of high efficient zinc vacancy mediated Z-scheme photocatalyst from metal-organic frameworks. Nano Energy 52:105–116

    Article  CAS  Google Scholar 

  15. Yuan Y-P, Yin L-S, Cao S-W, Xu G-S, Li C-H, Xue C (2015) Improving photocatalytic hydrogen production of metal–organic framework UiO-66 octahedrons by dye-sensitization. Appl Catal B 168–169:572–576

    Article  Google Scholar 

  16. Cheng C, Fang J, Lu S, Cen C, Chen Y, Ren L, Feng W, Fang Z (2016) Zirconium metal-organic framework supported highly-dispersed nanosized BiVO4 for enhanced visible-light photocatalytic applications. J Chem Technol Biotechnol 91(11):2785–2792

    Article  CAS  Google Scholar 

  17. Tu J, Zeng X, Xu F, Wu X, Tian Y, Hou X, Long Z (2017) Microwave-induced fast incorporation of titanium into UiO-66 metal-organic frameworks for enhanced photocatalytic properties. Chem Commun 53(23):3361–3364

    Article  CAS  Google Scholar 

  18. Mu X, Jiang J, Chao F, Lou Y, Chen J (2018) Ligand modification of UiO-66 with an unusual visible light photocatalytic behavior for RhB degradation. Dalton Trans 47(6):1895–1902

    Article  CAS  Google Scholar 

  19. Zhang X, Yang Y, Lv X, Wang Y, Liu N, Chen D, Cui L (2019) Adsorption/desorption kinetics and breakthrough of gaseous toluene for modified microporous-mesoporous UiO-66 metal organic framework. J Hazard Mater 366:140–150

    Article  CAS  Google Scholar 

  20. Xu G, Meng Z, Guo X, Zhu H, Deng K, Xiao C, Liu Y (2019) Molecular simulations on CO2 adsorption and adsorptive separation in fullerene impregnated MOF-177, MOF-180 and MOF-200. Comput Mater Sci 168:58–64

    Article  CAS  Google Scholar 

  21. Wang A, Zhou Y, Wang Z, Chen M, Sun L, Liu X (2016) Titanium incorporated with UiO-66(Zr)-type metal–organic framework (MOF) for photocatalytic application. RSC Adv 6(5):3671–3679

    Article  CAS  Google Scholar 

  22. Suresh K, Matzger AJ (2019) Enhanced drug delivery by dissolution of amorphous drug encapsulated in a water unstable metal–organic framework (MOF). Angew Chem Int Ed 58:16790–16794

    Article  CAS  Google Scholar 

  23. Sun D, Li Z (2017) Robust Ti- and Zr-based metal-organic frameworks for photocatalysis. Chin J Chem 35(2):135–147

    Article  CAS  Google Scholar 

  24. Hu B, Yuan JY, Tian JY, Wang M, Wang X, He L, Zhang Z, Wang ZW, Liu CS (2018) Co/Fe-bimetallic organic framework-derived carbon-incorporated cobalt-ferric mixed metal phosphide as a highly efficient photocatalyst under visible light. J Colloid Interface Sci 531:148–159

    Article  CAS  Google Scholar 

  25. Mu F, Zhou S, Wang Y, Wang J, Kong Y (2019) Bimetallic metal–organic frameworks-derived mesoporous CdxZn1−xS polyhedrons for enhanced photocatalytic hydrogen evolution. J Mater Res 34(10):1773–1784

    Article  CAS  Google Scholar 

  26. Zhong HX, Wang J, Zhang YW, Xu WL, Xing W, Xu D, Zhang YF, Zhang XB (2014) ZIF-8 derived graphene-based nitrogen-doped porous carbon sheets as highly efficient and durable oxygen reduction electrocatalysts. Angew Chem Int Ed 53(51):14235–14239

    Article  CAS  Google Scholar 

  27. Han Y, Liu M, Li K, Sun Q, Zhang W, Song C, Zhang G, Zhang ZC, Guo X (2017) In situ synthesis of titanium doped hybrid metal–organic framework UiO-66 with enhanced adsorption capacity for organic dyes. Inorg Chem Front 4(11):1870–1880

    Article  CAS  Google Scholar 

  28. Zhang Y, Shao Q, Jiang H, Liu L, Wu M, Lin J, Zhang J, Wu S, Dong M, Guo Z (2020) One-step co-precipitation synthesis of novel BiOCl/CeO2 composites with enhanced photodegradation of rhodamine B. Inorg Chem Front 7(6):1345–1361

    Article  CAS  Google Scholar 

  29. Surib NA, Sim LC, Leong KH, Kuila A, Saravanan P, Lo KM, Ibrahim S, Bahnemann D, Jang M (2017) Ag+, Fe3+ and Zn2+-intercalated cadmium(ii)-metal–organic frameworks for enhanced daylight photocatalysis. RSC Adv 7(81):51272–51280

    Article  CAS  Google Scholar 

  30. Han X, Tao K, Ma Q, Han L (2018) Microwave-assisted synthesis of pillared Ni-based metal–organic framework and its derived hierarchical NiO nanoparticles for supercapacitors. J Mater Sci - Mater Electron 29(17):14697–14704

    Article  CAS  Google Scholar 

  31. Albuquerque GH, Herman GS (2016) Chemically modulated microwave-assisted synthesis of MOF-74(Ni) and preparation of metal–organic framework-matrix based membranes for removal of metal ions from aqueous media. Cryst Growth Des 17(1):156–162

    Article  Google Scholar 

  32. Kudelin AK (2018) Effect of microwave radiation on the solvent-free synthesis of MOF-199. Russ J Phys Chem A 92(12):2359–2361

    Article  CAS  Google Scholar 

  33. Wang Y, Hu Y-J, Hao X, Peng P, Shi J-Y, Peng F, Sun R-C (2020) Hydrothermal synthesis and applications of advanced carbonaceous materials from biomass: a review. Adv Compos Hybrid Mater 3(3):267–284

    Article  CAS  Google Scholar 

  34. Li Y, Shang X, Li C, Huang X, Zheng J (2018) Novel p-n junction UiO-66/BiOI photocatalysts with efficient visible-light-induced photocatalytic activity. Water Sci & Technol 77:1441–1448

    Article  CAS  Google Scholar 

  35. Yang L-M, Ravindran P, Vajeeston P, Svelle S, Tilset M (2013) A quantum mechanically guided view of Cd-MOF-5 from formation energy, chemical bonding, electronic structure, and optical properties. Microporous Mesoporous Mater 175:50–58

    Article  CAS  Google Scholar 

  36. Díaz-García M, Sánchez-Sánchez M (2014) Synthesis and characterization of a new Cd-based metal-organic framework isostructural with MOF-74/CPO-27 materials. Microporous Mesoporous Mater 190:248–254

    Article  Google Scholar 

  37. Burgaz E, Erciyes A, Andac M, Andac O (2019) Synthesis and characterization of nano-sized metal organic framework-5 (MOF-5) by using consecutive combination of ultrasound and microwave irradiation methods. Inorg Chim Acta 485:118–124

    Article  CAS  Google Scholar 

  38. Sha Z, Sun J, Chan HSO, Jaenicke S, Wu J (2014) Bismuth tungstate incorporated zirconium metal–organic framework composite with enhanced visible-light photocatalytic performance. RSC Adv 4(110):64977–64984

    Article  CAS  Google Scholar 

  39. Ma X, Lou Y, Chen J (2018) New UiO-66/CuxS heterostructures: surface functionalization synthesis and their application in photocatalytic degradation of RhB. Bull Chem Soc Jpn 91(4):515–522

    Article  CAS  Google Scholar 

  40. Tong X, Yang Z, Feng J, Li Y, Zhang H (2018) BiOCl/UiO-66 composite with enhanced performance for photo-assisted degradation of dye from water. Appl Organomet Chem 32(2):e4049

    Article  Google Scholar 

  41. Zhang R, Du B, Li Q, Cao Z, Feng G, Wang X (2019) α-Fe2O3 nanoclusters confined into UiO-66 for efficient visible-light photodegradation performance. Appl Surf Sci 466:956–963

    Article  CAS  Google Scholar 

  42. Yang Z, Xu X, Liang X, Lei C, Gao L, Hao R, Lu D, Lei Z (2017) Fabrication of Ce doped UiO-66/graphene nanocomposites with enhanced visible light driven photoactivity for reduction of nitroaromatic compounds. Appl Surf Sci 420:276–285

    Article  CAS  Google Scholar 

  43. Xu X, Liu R, Cui Y, Liang X, Lei C, Meng S, Ma Y, Lei Z, Yang Z (2017) PANI/FeUiO-66 nanohybrids with enhanced visible-light promoted photocatalytic activity for the selectively aerobic oxidation of aromatic alcohols. Appl Catal B 210:484–494

    Article  CAS  Google Scholar 

  44. Liu X, Shao Q, Wang Y, Zheng Y, Song H, Wang J, Liu H, Guo Z (2020) One-pot in situ microwave hydrothermally grown zeoliticlImidazolate framework-8 on ZnIn-layered double oxides toward enhanced methylene blue photodegradation. Ind Eng Chem Res 59:16637–16648

    Article  CAS  Google Scholar 

  45. Qiu J, Feng Y, Zhang X, Jia M, Yao J (2017) Acid-promoted synthesis of UiO-66 for highly selective adsorption of anionic dyes: adsorption performance and mechanisms. J Colloid Interface Sci 499:151–158

    Article  CAS  Google Scholar 

  46. Sha Z, Sun J, Chan HSO, Jaenicke S, Wu J (2015) Enhanced photocatalytic activity of the AgI/UiO-66(Zr) composite for rhodamine B degradation under visible-light irradiation. ChemPlusChem 80(8):1321–1328

    Article  CAS  Google Scholar 

  47. Zhao X, Liu X, Zhang Z, Liu X, Zhang W (2016) Facile preparation of a novel SnO2@UiO-66/rGO hybrid with enhanced photocatalytic activity under visible light irradiation. RSC Adv 6(94):92011–92019

    Article  CAS  Google Scholar 

  48. Sha Z, Chan HS, Wu J (2015) Ag2CO3/UiO-66(Zr) composite with enhanced visible-light promoted photocatalytic activity for dye degradation. J Hazard Mater 299:132–140

    Article  CAS  Google Scholar 

  49. Zhang T, Zhu Z, Chen H, Bai Y, Xiao S, Zheng X, Xue Q, Yang S (2015) Iron-doping-enhanced photoelectrochemical water splitting performance of nanostructured WO3: a combined experimental and theoretical study. Nanoscale 7(7):2933–2940

    Article  CAS  Google Scholar 

  50. Li X, Yu J, Low J, Fang Y, Xiao J, Chen X (2015) Engineering heterogeneous semiconductors for solar water splitting. J Mater Chem A 3(6):2485–2534

    Article  CAS  Google Scholar 

  51. Zhang Y, Jin Z (2019) Effective electron-hole separation over a controllably constructed WP/UiO-66/CdS heterojunction to achieve efficiently improved visible-light-driven photocatalytic hydrogen evolution. Phys Chem Chem Phys 21(16):8326–8341

    Article  CAS  Google Scholar 

  52. Huang Q, Ma W, Yan X, Chen Y, Zhu S, Shen S (2013) Photocatalytic decomposition of gaseous HCHO by ZrxTi1−xO2 catalysts under UV–vis light irradiation with an energy-saving lamp. J Mol Catal A: Chem 366:261–265

    Article  CAS  Google Scholar 

  53. Kanjwal MA, Barakat NAM, Sheikh FA, Park SJ, Kim HY (2010) Photocatalytic activity of ZnO-TiO2 hierarchical nanostructure prepared by combined electrospinning and hydrothermal techniques. Macromol Res 18(3):233–240

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Qian Shao.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Publisher’s Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 109 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Cheng, W., Wang, Y., Ge, S. et al. One-step microwave hydrothermal preparation of Cd/Zr-bimetallic metal–organic frameworks for enhanced photochemical properties. Adv Compos Hybrid Mater 4, 150–161 (2021). https://doi.org/10.1007/s42114-020-00199-5

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s42114-020-00199-5

Keywords

Navigation