Insight into Proton Transfer in Phosphotungstic Acid Functionalized Mesoporous Silica-Based Proton Exchange Membrane Fuel Cells.

We have developed for fuel cells a novel proton exchange membrane (PEM) using inorganic phosphotungstic acid (HPW) as proton carrier and mesoporous silica as matrix (HPW-meso-silica) . The proton conductivity measured by electrochemical impedance spectroscopy is 0.11 S cm at 90 °C and 100% relative...

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Publicado en:Journal of the American Chemical Society Vol. 136; no. 13; pp. 4954 - 4965
Autores principales: Yuhua Zhou, Jing Yang, Haibin Su, Jie Zeng, San Ping Jiang, Goddard, William A.
Formato: Artículo
Publicado: American Chemical Society 4/2/2014
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Acceso en línea:Ver este registro en EBSCOhost
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      dt: 4/2/2014
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      pub: American Chemical Society
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        10.1021/ja411268q
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        atl: Insight into Proton Transfer in Phosphotungstic Acid Functionalized Mesoporous Silica-Based Proton Exchange Membrane Fuel Cells.
      aug:
        au:
          Yuhua Zhou
          Jing Yang
          Haibin Su
          Jie Zeng
          San Ping Jiang
          Goddard, William A.
        affil:
          School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798 Singapore
          Institute of High Performance Computing, 1 Fusionopolis Way, Connexis 138632, Singapore
          Fuels and Energy Technology Institute & Department of Chemical Engineering, Curtin University, Perth, Western Australia 6102, Australia
          Materials and Process Simulation Center, California Institute of Technology, Pasadena, California 91125, United States
      su:
        Proton transfer reactions
        Phosphotungstic acids
        Proton exchange membrane fuel cells
        Silica
        Humidity
      sug:
        subj:
          Proton transfer reactions
          Phosphotungstic acids
          Proton exchange membrane fuel cells
          Silica
          Humidity
      ab: We have developed for fuel cells a novel proton exchange membrane (PEM) using inorganic phosphotungstic acid (HPW) as proton carrier and mesoporous silica as matrix (HPW-meso-silica) . The proton conductivity measured by electrochemical impedance spectroscopy is 0.11 S cm at 90 °C and 100% relative humidity (RH) with a low activation energy of ∼14 kJ mol. In order to determine the energetics associated with proton migration within the HPW-meso-silica PEM and to determine the mechanism of proton hopping, we report density functional theory (DFT) calculations using the generalized gradient approximation (GGA). These DFT calculations revealed that the proton transfer process involves both intramolecular and intermolecular proton transfer pathways. When the adjacent HPWs are close (less than 17.0 Å apart), the calculated activation energy for intramolecular proton transfer within a HPW molecule is higher (29.1-18.8 kJ/mol) than the barrier for intermolecular proton transfer along the hydrogen bond. We find that the overall barrier for proton movement within the HPW-meso-silica membranes is determined by the intramolecular proton transfer pathway, which explains why the proton conductivity remains unchanged when the weight percentage of HPW on meso-silica is above 67 wt %. In contrast, the activation energy of proton transfer on a clean SiO (111) surface is computed to be as high as ∼40 kJ mol, confirming the very low proton conductivity on clean silica surfaces observed experimentally.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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