Skip to main content
SpringerLink
Log in

Heat capacities and thermodynamic properties of Cr-MIL-101

  • Published:
Journal of Thermal Analysis and Calorimetry Aims and scope Submit manuscript

Abstract

The molar heat capacities of one-three-dimensional metal–organic frameworks (MOFs) Cr3F(H2O)2O(BDC)3 (Cr-MIL-101) were measured by temperature-modulated differential scanning calorimetry over the temperature range from 253 to 413 K for the first time. No phase transition or thermal anomaly was observed in the experimental temperature range. The fundamental thermodynamic parameters such as entropy and enthalpy relative to 298.15 K were calculated based on the experimentally determined molar heat capacities. The compound was characterized by atomic absorption spectrometer, elemental analysis, powder XRD and FTIR spectrum. Moreover, the thermal decomposition characteristics of Cr-MIL-101 were investigated by thermogravimetry–mass spectrometer (TG–MS). Three stages of mass loss were observed in the TG curve. TG–MS curve indicated that the oxidative degradation products of Cr-MIL-101 are mainly H2O and CO2.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Stock N, Biswas S. Synthesis of metal-organic frameworks (MOFs): routes to various MOF topologies, morphologies, and composites. Chem Rev. 2012;112(2):933–69. doi:10.1021/cr200304e.

    Article  CAS  Google Scholar 

  2. Hosny NM. Solvothermal synthesis, thermal and adsorption properties of metal-organic frameworks Zn and CoZn(DPB). J Thermal Anal Calorim. 2015;122(1):89–95. doi:10.1007/s10973-015-4721-y.

    Article  CAS  Google Scholar 

  3. Reinsch H. “Green” synthesis of metal-organic frameworks. Eur J Inorg Chem. 2016;2016(27):4290–9. doi:10.1002/ejic.201600286.

    Article  CAS  Google Scholar 

  4. Hosny NM, Al-Hussaini AS, Nowesser N, Zoromba MS. Effect of inclusion of some transition metal ions and use of the doped polymer in synthesizing α-Fe2O3 nanoparticles via thermal decomposition rout. J Therm Anal Calorim. 2016;124(1):287–93. doi:10.1007/s10973-015-5121-z.

    Article  CAS  Google Scholar 

  5. He Y, Zhou W, Qian G, Chen B. Methane storage in metal-organic frameworks. Chem Soc Rev. 2014;43(16):5657–78. doi:10.1039/C4CS00032C.

    Article  CAS  Google Scholar 

  6. Seoane B, Coronas J, Gascon I, Benavides ME, Karvan O, Caro J, et al. Metal-organic framework based mixed matrix membranes: a solution for highly efficient CO2 capture? Chem Soc Rev. 2015;44(8):2421–54. doi:10.1039/C4CS00437J.

    Article  CAS  Google Scholar 

  7. Andirova D, Cogswell CF, Lei Y, Choi S. Effect of the structural constituents of metal organic frameworks on carbon dioxide capture. Microporous Mesoporous Mater. 2016;219:276–305. doi:10.1016/j.micromeso.2015.07.029.

    Article  CAS  Google Scholar 

  8. Liu J, Chen L, Cui H, Zhang J, Zhang L, Su C-Y. Applications of metal-organic frameworks in heterogeneous supramolecular catalysis. Chem Soc Rev. 2014;43(16):6011–61. doi:10.1039/C4CS00094C.

    Article  CAS  Google Scholar 

  9. Chughtai AH, Ahmad N, Younus HA, Laypkov A, Verpoort F. Metal-organic frameworks: versatile heterogeneous catalysts for efficient catalytic organic transformations. Chem Soc Rev. 2015;44(19):6804–49. doi:10.1039/C4CS00395K.

    Article  CAS  Google Scholar 

  10. Hu Z, Deibert BJ, Li J. Luminescent metal-organic frameworks for chemical sensing and explosive detection. Chem Soc Rev. 2014;43(16):5815–40. doi:10.1039/C4CS00010B.

    Article  CAS  Google Scholar 

  11. Qiu S, Xue M, Zhu G. Metal-organic framework membranes: from synthesis to separation application. Chem Soc Rev. 2014;43(16):6116–40. doi:10.1039/C4CS00159A.

    Article  CAS  Google Scholar 

  12. Banerjee D, Cairns AJ, Liu J, Motkuri RK, Nune SK, Fernandez CA, et al. Potential of metal-organic frameworks for separation of xenon and krypton. Acc Chem Res. 2015;48(2):211–9. doi:10.1021/ar5003126.

    Article  CAS  Google Scholar 

  13. He C, Liu D, Lin W. Nanomedicine applications of hybrid nanomaterials built from metal-ligand coordination bonds: nanoscale metal-organic frameworks and nanoscale coordination polymers. Chem Rev. 2015;115(19):11079–108. doi:10.1021/acs.chemrev.5b00125.

    Article  CAS  Google Scholar 

  14. Wunderlich B. The tribulations and successes on the road from DSC to TMDSC in the 20th century the prospects for the 21st century. J Therm Anal Calorim. 2004;78(1):7–31. doi:10.1023/b:jtan.0000042150.03836.27.

    Article  CAS  Google Scholar 

  15. Song LF, Jiao CL, Jiang CH, Zhang JA, Sun LX, Xu F, et al. Heat capacities and thermodynamic properties of MgNDC. J Therm Anal Calorim. 2011;103(1):365–72. doi:10.1007/s10973-010-0777-x.

    Article  CAS  Google Scholar 

  16. Androsch R. Heat capacity measurements using temperature-modulated heat flux DSC with close control of the heater temperature. J Therm Anal Calorim. 2000;61(1):75–89. doi:10.1023/a:1010104406353.

    Article  CAS  Google Scholar 

  17. Wunderlich B, Jin YM, Boller A. Mathematical description of differential scanning calorimetry based on periodic temperature modulation. Thermochim Acta. 1994;238:277–93. doi:10.1016/s0040-6031(94)85214-6.

    Article  CAS  Google Scholar 

  18. Danley RL. New modulated DSC measurement technique. Thermochim Acta. 2003;402(1–2):91–8.

    Article  CAS  Google Scholar 

  19. Wunderlich B. The contributions of MDSC to the understanding of the thermodynamics of polymers. J Therm Anal Calorim. 2006;85(1):179–87. doi:10.1007/s10973-005-7347-7.

    Article  CAS  Google Scholar 

  20. Ferey G, Mellot-Draznieks C, Serre C, Millange F, Dutour J, Surble S, et al. A chromium terephthalate-based solid with unusually large pore volumes and surface area. Science. 2005;309(5743):2040–2. doi:10.1126/science.1116275.

    Article  CAS  Google Scholar 

  21. Latroche M, Surble S, Serre C, Mellot-Draznieks C, Llewellyn PL, Lee JH, et al. Hydrogen storage in the giant-pore metal-organic frameworks MIL-100 and MIL-101. Angew Chem Int Ed. 2006;45(48):8227–31. doi:10.1002/anie.200600105.

    Article  CAS  Google Scholar 

  22. Llewellyn PL, Bourrelly S, Serre C, Vimont A, Daturi M, Hamon L, et al. High uptakes of CO2 and CH4 in mesoporous metal-organic frameworks MIL-100 and MIL-101. Langmuir. 2008;24(14):7245–50. doi:10.1021/la800227x.

    Article  CAS  Google Scholar 

  23. Hong DY, Hwang YK, Serre C, Ferey G, Chang JS. Porous chromium terephthalate MIL-101 with coordinatively unsaturated sites: surface functionalization, encapsulation, sorption and catalysis. Adv Funct Mater. 2009;19(10):1537–52. doi:10.1002/adfm.200801130.

    Article  CAS  Google Scholar 

  24. Archer DG. Thermodynamic properties of synthetic sapphire (α-Al2O3), standard reference material 720 and the effect of temperature-scale differences on thermodynamic properties. J Phys Chem Ref Data. 1993;22(6):1441–53.

    Article  CAS  Google Scholar 

  25. Ginnings DC, Furukawa GT. Heat capacity standards for the range 14 to 1200°K. J Am Chem Soc. 1953;75(3):522–7. doi:10.1021/ja01099a004.

    Article  CAS  Google Scholar 

  26. Jiang C-H, Song L-F, Jiao C-L, Zhang J, Sun L-X, Xu F, et al. Determination of heat capacities and thermodynamic properties of two structurally unrelated but isotypic calcium and manganese(II) 2,6-naphthalene dicarboxylate-based MOFs. J Therm Anal Calorim. 2011;103(3):1095–103. doi:10.1007/s10973-010-1197-7.

    Article  CAS  Google Scholar 

  27. Loiseau T, Serre C, Huguenard C, Fink G, Taulelle F, Henry M, et al. A rationale for the large breathing of the porous aluminum terephthalate (MIL-53) upon hydration. Chem A Eur J. 2004;10(6):1373–82. doi:10.1002/chem.200305413.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 21503129, 21572126), Foundation of Henan Educational Committee (No. 15A150073).

Author information

Authors and Affiliations

  1. Henan Engineering Laboratory of Green Synthesis for Pharmaceuticals, School of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu, 476000, People’s Republic of China

    Shuang Liu, Lan-Tao Liu, Yan-Li Zhou & Wen-xian Zhao

  2. School of Chemistry and Chemical Engineering, Shangqiu Normal University, Shangqiu, 476000, People’s Republic of China

    Shuang Liu, Lan-Tao Liu & Wen-xian Zhao

  3. School of Chemistry and Chemical Engineering, Guilin University of Electronic Technology, Guilin, 541000, People’s Republic of China

    Fen Xu

  4. College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, 450052, People’s Republic of China

    Wen-xian Zhao

Authors
  1. Shuang Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Fen Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Lan-Tao Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yan-Li Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Wen-xian Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Lan-Tao Liu.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Liu, S., Xu, F., Liu, LT. et al. Heat capacities and thermodynamic properties of Cr-MIL-101. J Therm Anal Calorim 129, 509–514 (2017). https://doi.org/10.1007/s10973-017-6168-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10973-017-6168-9

Keywords

Search

Navigation