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Department of Physical Chemistry, University of Pardubice
Calorimetry and thermal analysis in adsorbents and catalysts characterization Roman Bulánek Department of Physical Chemistry, University of Pardubice Kalsem, Velké Bílovice,
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History of TA in catalysis
VIIth Czechoslovak Conference on Thermal Analysis – „Thermanal 76“
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History of TA in catalysis
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Presence of TA in catalysis
Annual school and workshop since 2007
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Presence of TA in catalysis
Annual school and workshop, since 2007
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Outline Adsorption calorimetry Temperature programmed techniques
Non-specific interaction forces – methane in pure silica zeolites Temperature effect on specific interaction – H-bonding of CO Investigation of cationic sites in zeolites Temperature programmed techniques Nature and sitting of Cu+ sites in high-silica zeolites
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Heat of adsorption adsorption
Adsorption site heat vibration adsorption Adsorbate 1 – Tuesday 5/28/2019 afternoon 16:20 E. Koudelková, R. Bulánek: Kalorimetrie a adsorpční děje
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Heat of adsorption Adsorption site heat vibration adsorption Adsorbate The adsorbate-adsorbent energy of interaction (derived from the heat measurements1) is a basic data for any modelling and understanding of adsorption phenomena. 1 – Tuesday 5/28/2019 afternoon 16:20 E. Koudelková, R. Bulánek: Kalorimetrie a adsorpční děje
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Heat of adsorption Adsorption site heat vibration adsorption Adsorbate The adsorbate-adsorbent energy of interaction (derived from the heat measurements1) is a basic data for any modelling and understanding of adsorption phenomena. Calorimetry provides basic data for adsorption theory and modelling – bridging the gap between theory and experiment 1 – Tuesday 5/28/2019 afternoon 16:20 E. Koudelková, R. Bulánek: Kalorimetrie a adsorpční děje
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Adsorption calorimetry
Volumetric line + calorimeter Qi pd1 pr1 pd2 pr2 vacuum SETARAM BT 2.15
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Case 1 – dispersion interaction
Specific interaction 10 – 200 kJ/mol Non-specific interaction 5 – 50 kJ/mol
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Case 1 – dispersion interaction
Specific interaction 10 – 200 kJ/mol Non-specific interaction 5 – 50 kJ/mol
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Case 1 – dispersion interaction
Specific interaction 10 – 200 kJ/mol Non-specific interaction 5 – 50 kJ/mol Quantum chemical calculations DFT: dispersion forces not included several dispersion-corrected DFT exist DFT/CC Experimental CH4/PSZ system Precise measurement of HOA by calorimetry
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Case 1 – dispersion interaction
Zeolites 300K UTL 0.95 x 0.71 nm 0.85 x 0.55 nm OKO 0.66 x 0.62 nm 0.54 x 0.53 nm UTL OKO MFI PCR + PCR 0.58 x 0.38 nm 0.45 x 0.36 nm CH4 0.38 nm MFI 0.56 x 0.53 nm 0.55 x 0.51 nm Phys. Chem. Chem. Phys., 2017, 19,
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Case 1 – dispersion interaction
Zeolites 300K UTL 0.95 x 0.71 nm 0.85 x 0.55 nm Qa-exp (kJ/mol) Qa-theor (kJ/mol) OKO 0.66 x 0.62 nm 0.54 x 0.53 nm UTL OKO MFI PCR 15.8 17.9 20.2 22.1 + 18.9 19.2 20.8 21.7 PCR 0.58 x 0.38 nm 0.45 x 0.36 nm CH4 0.38 nm MFI 0.56 x 0.53 nm 0.55 x 0.51 nm Phys. Chem. Chem. Phys., 2017, 19,
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Case 1 – dispersion interaction
Zeolites UTL 0.95 x 0.71 nm 0.85 x 0.55 nm Effect of temperature? Qa-exp (kJ/mol) Qa-theor (kJ/mol) OKO 0.66 x 0.62 nm 0.54 x 0.53 nm UTL OKO MFI PCR 15.8 17.9 20.2 22.1 + 18.9 19.2 20.8 21.7 PCR 0.58 x 0.38 nm 0.45 x 0.36 nm CH4 0.38 nm MFI 0.56 x 0.53 nm 0.55 x 0.51 nm Phys. Chem. Chem. Phys., 2017, 19,
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Case 1 – dispersion interaction
Phys. Chem. Chem. Phys., 2017, 19,
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Case 1 – dispersion interaction
AI-FF MD 20 ns production run with 2 fs step Temperature effect – thermal moving Phys. Chem. Chem. Phys., 2017, 19,
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Case 1 – dispersion interaction
AI-FF MD 20 ns production run with 2 fs step 150K Phys. Chem. Chem. Phys., 2017, 19,
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Case 1 – dispersion interaction
AI-FF MD 20 ns production run with 2 fs step 150K 200K Phys. Chem. Chem. Phys., 2017, 19,
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Case 1 – dispersion interaction
AI-FF MD 20 ns production run with 2 fs step 200K 250K 150K Phys. Chem. Chem. Phys., 2017, 19,
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Case 1 – dispersion interaction
AI-FF MD 20 ns production run with 2 fs step DFT/CC correction scheme fulfil high accuracy requirement 300K 150K 200K 250K Phys. Chem. Chem. Phys., 2017, 19,
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Case 1 – dispersion interaction
experimental theoretical Phys. Chem. Chem. Phys., 2017, 19,
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Case 2 – H-bonded CO complexes
Brønsted acid site One of the most important industrial catalysts - FCC Al Si How acidic is?
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Case 2 – H-bonded CO complexes
Brønsted acid site Interaction of weak basis – scaling the acid strength One of the most important industrial catalysts - FCC Big effort to measure adsorption heat of CO Published data very scattered CO 7.5 kJ/mol !!! Al Si 200 K 300 K How acidic is? J. Phys. Chem. C 122 (2018)
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Case 2 – H-bonded CO complexes
Brønsted acid site Interaction of weak basis – scaling the acid strength One of the most important industrial catalysts - FCC Big effort to measure adsorption heat of CO Published data very scattered DFT/CC 33.0 – 27.5 kJ/mol 26.0 – 21.9 kJ/mol CO 7.5 kJ/mol !!! Al Si 200 K 300 K How acidic is? J. Phys. Chem. C 122 (2018)
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Case 2 – H-bonded CO complexes
J. Phys. Chem. C 122 (2018)
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Case 2 – H-bonded CO complexes
Brønsted acid site Interaction of weak basis – scaling the acid strength Big effort to measure adsorption heat of CO Published data very scattered CO/Li-FER Al Si CO/H-FER How acidic is? 200 K 300 K J. Phys. Chem. C 122 (2018)
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Case 3 – Hydrocarbons adsorption
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Case 3 – Hydrocarbons adsorption
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Case 3 – Hydrocarbons adsorption
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Case 3 – Hydrocarbons adsorption
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Case 3 – Hydrocarbons adsorption
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Case 3 – Hydrocarbons adsorption
C3H6/Na-FER Micropor. Mesopor. Mater. 280 (2019)
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Case 3 – bridged complexes
Micropor. Mesopor. Mater. 279 (2019)
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Conclusions The use of thermal analysis and calorimetry techniques is quite an old and known field of applications for catalytic investigations. … … Especially, adsorption calorimetry is very fruitfully employed in describing the processes occurring at the gas-solid interface…. …Recognizing the increasing importance of material science and surface chemistry, it is certain that calorimetry and thermal analysis these methods will still be indispensable, and perhaps even more important, tools than before … Aline Auroux, 2013 Preface of the book Calorimetry and Thermal Methods in Catalysis
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Department of Physical Chemistry, University of Pardubice
Pavel Čičmanec, Eva Koudelková, Yosra Ghrib, Alicia Martinéz de Yuso, Jan Vaculík, Jakub Halamek, Francisca Solanea de Oliveira Ramos Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Prague Ota Bludský, Miroslav Rubeš, Michal Trachta Czech Science Foundation: projects No. S S 106/12/G015 Centre of Excellence
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Děkuji za pozornost
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