Journal of Thermal Analysis and Calorimetry

, Volume 110, Issue 2, pp 949–954 | Cite as

Heat capacities and thermodynamic properties of M(HBTC)(4,4′-bipy)·3DMF (M = Ni and Co)



Two metal–organic frameworks (MOFs) of M(HBTC)(4,4′-bipy)·3DMF [M = Ni (for 1) and Co (for 2); H3BTC = 1,3,5-benzenetricarboxylic acid (1,3,5-BTC); 4,4′-bipy = 4,4′-bipyridine; DMF = N,N′-dimethylformamide] were synthesized by a one-pot solution reaction and a solvothermal method, respectively, and characterized by powder X-ray diffraction and FT-IR spectra. The low-temperature molar heat capacities of M(HBTC)(4,4′-bipy)·3DMF were measured by temperature-modulated differential scanning calorimetry (TMDSC) for the first time. The thermodynamic parameters such as entropy and enthalpy relative to reference temperature 298.15 K were derived based on the above molar heat capacity data. Moreover, the thermal stability and the decomposition mechanism of M(HBTC)(4,4′-bipy)·3DMF were investigated by thermogravimetry analysis (TGA). The experimental results through TGA measurement demonstrate that both of the two compounds have a three-stage mass loss in air flow.


Metal–organic framework Molar heat capacity TGA TMDSC 



The authors wish to acknowledge the financial support from the National Basic Research Program (973 program) of China (2010CB631303), the National Natural Science Foundation of China (No. 20833009, 20873148, 20903095, 50901070, 51071146, 51071081, and U0734005), National Natural Science Foundation of Liaoning (No. 20102224), Liaoning BaiQianWan Talents Program (Project No. 2010921050), IUPAC (Project No. 2008-006-3-100), The Joint Project of Guangdong Province and Chinese Academy of Sciences (2010A090100034), Dalian Scientific Project (2009A11GX052) and the State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology (Grant No. KFJJ10-1Z).


  1. 1.
    Deng HX, Doonan CJ, Furukawa H, Ferreira RB, Towne J, Knobler CB, Wang B, Yaghi OM. Multiple functional groups of varying ratios in metal-organic frameworks. Science. 2010;327:846–50.CrossRefGoogle Scholar
  2. 2.
    Millward AR, Yaghi OM. Metal-organic frameworks with exceptionally high capacity for storage of carbon dioxide at room temperature. J Am Chem Soc. 2005;127:17998–9.CrossRefGoogle Scholar
  3. 3.
    Snurr RQ, Bae YS, Spokoyny AM, Farha OK, Hupp JT, Mirkin CA. Separation of gas mixtures using Co(II) carborane-based porous coordination polymers. Chem Commun. 2010;46:3478–80.CrossRefGoogle Scholar
  4. 4.
    Kreno LE, Hupp JT, Van Duyne RP. Metal-organic framework thin film for enhanced localized surface plasmon resonance gas sensing. Anal Chem. 2010;82:8042–6.CrossRefGoogle Scholar
  5. 5.
    Lee J, Farha OK, Roberts J, Scheidt KA, Nguyen ST, Hupp JT. Metal-organic framework materials as catalysts. Chem Soc Rev. 2009;38:1450–9.CrossRefGoogle Scholar
  6. 6.
    Song LF, Jiang CH, Jiao CL, Zhang J, Sun LX, Xu F, Jiao QZ, Xing YH, Du Y, Cao Z, Huang FL. Heat capacities and thermodynamic properties of one manganese-based MOFs. J Therm Anal Calorim. 2010;102:1161–6.CrossRefGoogle Scholar
  7. 7.
    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;78:7–31.CrossRefGoogle Scholar
  8. 8.
    Androsch R. Heat capacity measurements using temperature-modulated heat flux DSC with close control of the heater temperature. J Therm Anal Calorim. 2000;61:75–89.CrossRefGoogle Scholar
  9. 9.
    Wunderlich B. The contributions of MDSC to the understanding of the thermodynamics of polymers. J Therm Anal Calorim. 2006;85:179–87.CrossRefGoogle Scholar
  10. 10.
    Divi S, Chellappa R, Chandra D. Heat capacity measurement of organic thermal energy materials. J Chem Thermodyn. 2006;38:1312–26.CrossRefGoogle Scholar
  11. 11.
    Danley RL. New modulated DSC measurement technique. Thermochim Acta. 2003;402:91–8.CrossRefGoogle Scholar
  12. 12.
    Qiu SJ, Chu HL, Zhang J, Qi YN, Sun LX, Xu F. Heat capacities and thermodynamic properties of CoPc and CoTMPP. J Therm Anal Calorim. 2008;91:841–8.CrossRefGoogle Scholar
  13. 13.
    Zhang J, Liu YY, Zeng JL, Xu F, Sun LX, You WS, et al. Thermodynamic properties and thermal stability of the synthetic zinc formate dihydrate. J Therm Anal Calorim. 2008;91:861–6.CrossRefGoogle Scholar
  14. 14.
    Jiao CL, Song LF, Jiang CH, Zhang J, Si XL, Qiu SJ, Wang S, Sun LX, Xu F, Li F, Zhao JL. Low-temperature heat capacities and thermodynamic properties of Mn3(HEDTA)2·H2O. J Therm Anal Calorim. 2010;102:1155–60.CrossRefGoogle Scholar
  15. 15.
    Gao CY, Liu SX, Xie LH, Ren YH, Cao JF, Sun CY. Design and construction of a microporous metal-organic framework based on the pillared-layer motif. Cryst Eng Commun. 2007;9:545–7.Google Scholar
  16. 16.
    Li YQ, Xie L, Liu Y, Yang R, Li XG. Favorable hydrogen storage properties of M(HBTC)(4,4′-bipy)·3DMF (M = Ni and Co). Inorg Chem. 2008;47:10372–7.CrossRefGoogle Scholar
  17. 17.
    Archer DG. Thermodynamic properties of synthetic sapphire (alpha-Al2O3), standard reference material 720 and the effect of temperature-scale differences on thermodynamic properties. J Phys Chem Ref Data. 1993;22:1441–53.CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2011

Authors and Affiliations

  • Yi-Xi Zhou
    • 1
    • 2
  • Li-Xian Sun
    • 2
  • Zhong Cao
    • 1
  • Jian Zhang
    • 2
  • Fen Xu
    • 3
  • Li-Fang Song
    • 2
  • Zi-Ming Zhao
    • 2
  • Yong-Jin Zou
    • 2
  1. 1.School of Chemistry and Biological EngineeringChangsha University of Science and TechnologyChangshaPeople’s Republic of China
  2. 2.Materials and Thermochemistry Laboratory, Dalian Institute of Chemical PhysicsChinese Academy of SciencesDalianPeople’s Republic of China
  3. 3.Faculty of Chemistry and Chemical EngineeringLiaoning Normal UniversityDalianPeople’s Republic of China

Personalised recommendations