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  The barrier for CO2 functionalization to formate on hydrogenated Pt

Fingerhut, J., Borodin, D., Schwarzer, M., Skoulatakis, G., Auerbach, D. J., Wodtke, A. M., et al. (2021). The barrier for CO2 functionalization to formate on hydrogenated Pt. Journal of Physical Chemistry A, 125(34), 7396-7405. doi:10.1021/acs.jpca.1c04833.

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 Creators:
Fingerhut, J., Author
Borodin, D.1, Author           
Schwarzer, M., Author
Skoulatakis, G.1, Author           
Auerbach, D. J.2, Author           
Wodtke, A. M.2, Author           
Kitsopoulos, T. N.2, Author           
Affiliations:
1Department of Dynamics at Surfaces, MPI for Biophysical Chemistry, Max Planck Society, ou_persistent22              
2Department of Dynamics at Surfaces, MPI for biophysical chemistry, Max Planck Society, ou_578600              

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Free keywords: Oxygen, Energy, Activation energy, Organic reactions, Kinetics
 Abstract: Understanding heterogeneous catalysis is based on knowing the energetic stability of adsorbed reactants, intermediates, and products as well as the energetic barriers separating them. We report an experimental determination of the barrier to CO2 functionalization to form bidentate formate on a hydrogenated Pt surface and the corresponding reaction energy. This determination was possible using velocity resolved kinetics, which simultaneously provides information about both the dynamics and rates of surface chemical reactions. In these experiments, a pulse of isotopically labeled formic acid (DCOOH) doses the Pt surface rapidly forming bidentate formate (DCO*O*). We then record the (much slower) rate of decomposition of DCO*O* to form adsorbed D* and gas phase CO2. We establish the reaction mechanism by dosing with O2 to form adsorbed O*, which efficiently converts H* or D* to gas phase water. H2O is formed immediately reflecting rapid loss of the acidic proton associated with formation of formate, while D2O formation proceeds more slowly and on the same time scale as the CO2 production. The temperature dependence of the reaction rate yields an activation energy that reflects the energy of the transition state with respect to DCO*O*. The derived heat of formation for DCO*O* on Pt(111) agrees well with results of microcalorimetry. The maximum release of translational energy of the formed CO2 provides a measure of the energy of the transition state with respect to the products and the barrier to the reverse process, functionalization of CO2. The comparison between the results on Pt(111) and Pt(332) shows that the barrier for CO2 functionalization is reduced by the presence of steps. The approach taken here could provide a method to optimize catalysts for CO2 functionalization.

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Language(s): eng - English
 Dates: 2021-08-24
 Publication Status: Published online
 Pages: -
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.jpca.1c04833
 Degree: -

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Title: Journal of Physical Chemistry A
Source Genre: Journal
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Pages: - Volume / Issue: 125 (34) Sequence Number: - Start / End Page: 7396 - 7405 Identifier: -