Protolytic Reactions at Electrified TiO2 P25 Interface: Quantitative and Thermodynamic Characterization
Protolytic reactions on the surface of a titania photocatalyst (TiO2 P25 containing chlorine impurities) were studied using potentiometric and calorimetric acid-base titration. The impurity was removed by either washing or heat treatment. The efficiency of purification was tested by chlorine (TOX) a...
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| Published in | Molecules (Basel, Switzerland) Vol. 30; no. 3; p. 696 |
|---|---|
| Main Authors | , , , , , |
| Format | Journal Article |
| Language | English |
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Basel
MDPI AG
05.02.2025
MDPI |
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| Online Access | Get full text |
| ISSN | 1420-3049 1420-3049 |
| DOI | 10.3390/molecules30030696 |
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| Abstract | Protolytic reactions on the surface of a titania photocatalyst (TiO2 P25 containing chlorine impurities) were studied using potentiometric and calorimetric acid-base titration. The impurity was removed by either washing or heat treatment. The efficiency of purification was tested by chlorine (TOX) analysis and acid-base titration. Common intersection points of −0.023 and −0.021 mmol/g were obtained for the original and 400 °C heat-treated samples, which are in good agreement with the measured TOX value of 28 mmol/kg. The point of zero charge of the purified sample was determined to be 6.50. Titration data were fitted to simulate protolytic reactions during isothermal calorimetric titrations of purified titania. The evolved heat was measured, and data points were corrected with the heat of mixing and neutralization. The quantity of charged surface species formed in each step of titration was calculated using the parameters from the constant capacitance model fit. The partial molar enthalpy values of the exothermic and endothermic processes of surface protonation (ΔHpr, −17.47 to −16.10 kJ/mol) and deprotonation (ΔHdepr, 32.53 to 27.08 kJ/mol) depend slightly on the ionic strength of suspensions. The average standard enthalpy of one proton transfer reaction is −23.54 ± 1.75 kJ/mol, which is consistent with the literature. |
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| AbstractList | Protolytic reactions on the surface of a titania photocatalyst (TiO2 P25 containing chlorine impurities) were studied using potentiometric and calorimetric acid-base titration. The impurity was removed by either washing or heat treatment. The efficiency of purification was tested by chlorine (TOX) analysis and acid-base titration. Common intersection points of −0.023 and −0.021 mmol/g were obtained for the original and 400 °C heat-treated samples, which are in good agreement with the measured TOX value of 28 mmol/kg. The point of zero charge of the purified sample was determined to be 6.50. Titration data were fitted to simulate protolytic reactions during isothermal calorimetric titrations of purified titania. The evolved heat was measured, and data points were corrected with the heat of mixing and neutralization. The quantity of charged surface species formed in each step of titration was calculated using the parameters from the constant capacitance model fit. The partial molar enthalpy values of the exothermic and endothermic processes of surface protonation (ΔHpr, −17.47 to −16.10 kJ/mol) and deprotonation (ΔHdepr, 32.53 to 27.08 kJ/mol) depend slightly on the ionic strength of suspensions. The average standard enthalpy of one proton transfer reaction is −23.54 ± 1.75 kJ/mol, which is consistent with the literature. Protolytic reactions on the surface of a titania photocatalyst (TiO2 P25 containing chlorine impurities) were studied using potentiometric and calorimetric acid-base titration. The impurity was removed by either washing or heat treatment. The efficiency of purification was tested by chlorine (TOX) analysis and acid-base titration. Common intersection points of -0.023 and -0.021 mmol/g were obtained for the original and 400 °C heat-treated samples, which are in good agreement with the measured TOX value of 28 mmol/kg. The point of zero charge of the purified sample was determined to be 6.50. Titration data were fitted to simulate protolytic reactions during isothermal calorimetric titrations of purified titania. The evolved heat was measured, and data points were corrected with the heat of mixing and neutralization. The quantity of charged surface species formed in each step of titration was calculated using the parameters from the constant capacitance model fit. The partial molar enthalpy values of the exothermic and endothermic processes of surface protonation (ΔHpr, -17.47 to -16.10 kJ/mol) and deprotonation (ΔHdepr, 32.53 to 27.08 kJ/mol) depend slightly on the ionic strength of suspensions. The average standard enthalpy of one proton transfer reaction is -23.54 ± 1.75 kJ/mol, which is consistent with the literature.Protolytic reactions on the surface of a titania photocatalyst (TiO2 P25 containing chlorine impurities) were studied using potentiometric and calorimetric acid-base titration. The impurity was removed by either washing or heat treatment. The efficiency of purification was tested by chlorine (TOX) analysis and acid-base titration. Common intersection points of -0.023 and -0.021 mmol/g were obtained for the original and 400 °C heat-treated samples, which are in good agreement with the measured TOX value of 28 mmol/kg. The point of zero charge of the purified sample was determined to be 6.50. Titration data were fitted to simulate protolytic reactions during isothermal calorimetric titrations of purified titania. The evolved heat was measured, and data points were corrected with the heat of mixing and neutralization. The quantity of charged surface species formed in each step of titration was calculated using the parameters from the constant capacitance model fit. The partial molar enthalpy values of the exothermic and endothermic processes of surface protonation (ΔHpr, -17.47 to -16.10 kJ/mol) and deprotonation (ΔHdepr, 32.53 to 27.08 kJ/mol) depend slightly on the ionic strength of suspensions. The average standard enthalpy of one proton transfer reaction is -23.54 ± 1.75 kJ/mol, which is consistent with the literature. Protolytic reactions on the surface of a titania photocatalyst (TiO 2 P25 containing chlorine impurities) were studied using potentiometric and calorimetric acid-base titration. The impurity was removed by either washing or heat treatment. The efficiency of purification was tested by chlorine (TOX) analysis and acid-base titration. Common intersection points of −0.023 and −0.021 mmol/g were obtained for the original and 400 °C heat-treated samples, which are in good agreement with the measured TOX value of 28 mmol/kg. The point of zero charge of the purified sample was determined to be 6.50. Titration data were fitted to simulate protolytic reactions during isothermal calorimetric titrations of purified titania. The evolved heat was measured, and data points were corrected with the heat of mixing and neutralization. The quantity of charged surface species formed in each step of titration was calculated using the parameters from the constant capacitance model fit. The partial molar enthalpy values of the exothermic and endothermic processes of surface protonation (ΔH pr , −17.47 to −16.10 kJ/mol) and deprotonation (ΔH depr , 32.53 to 27.08 kJ/mol) depend slightly on the ionic strength of suspensions. The average standard enthalpy of one proton transfer reaction is −23.54 ± 1.75 kJ/mol, which is consistent with the literature. |
| Author | Szekeres, Márta Klumpp, Erwin Nesztor, Dániel Gerencsér-Berta, Renáta Tombácz, Etelka Lewandowski, Hans |
| AuthorAffiliation | 3 Institute of Bio- and Geosciences, Agrosphere (IBG-3), Forschungszentrum Jülich GmbH, Wilhelm-Johnen-Straße, 52425 Jülich, Germany e.klumpp@fz-juelich.de (E.K.) 2 Department of Physical Chemistry and Materials Science, University of Szeged, Rerrich Béla tér 1, H-6720 Szeged, Hungary 1 Soós Ernő Research and Development Center, University of Pannonia, Zrínyi u. 18., H-8800 Nagykanizsa, Hungary |
| AuthorAffiliation_xml | – name: 2 Department of Physical Chemistry and Materials Science, University of Szeged, Rerrich Béla tér 1, H-6720 Szeged, Hungary – name: 3 Institute of Bio- and Geosciences, Agrosphere (IBG-3), Forschungszentrum Jülich GmbH, Wilhelm-Johnen-Straße, 52425 Jülich, Germany e.klumpp@fz-juelich.de (E.K.) – name: 1 Soós Ernő Research and Development Center, University of Pannonia, Zrínyi u. 18., H-8800 Nagykanizsa, Hungary |
| Author_xml | – sequence: 1 givenname: Etelka orcidid: 0000-0002-2068-0459 surname: Tombácz fullname: Tombácz, Etelka – sequence: 2 givenname: Dániel surname: Nesztor fullname: Nesztor, Dániel – sequence: 3 givenname: Márta surname: Szekeres fullname: Szekeres, Márta – sequence: 4 givenname: Hans surname: Lewandowski fullname: Lewandowski, Hans – sequence: 5 givenname: Erwin surname: Klumpp fullname: Klumpp, Erwin – sequence: 6 givenname: Renáta orcidid: 0000-0003-0370-8277 surname: Gerencsér-Berta fullname: Gerencsér-Berta, Renáta |
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| Snippet | Protolytic reactions on the surface of a titania photocatalyst (TiO2 P25 containing chlorine impurities) were studied using potentiometric and calorimetric... Protolytic reactions on the surface of a titania photocatalyst (TiO 2 P25 containing chlorine impurities) were studied using potentiometric and calorimetric... |
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| SubjectTerms | Acids Adsorption calorimetry Electrolytes Energy Heat Nanoparticles Photocatalysis Pollutants potentiometry Protons surface charging surface complexation model (SCM) TiO2 P25 titania |
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| Title | Protolytic Reactions at Electrified TiO2 P25 Interface: Quantitative and Thermodynamic Characterization |
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