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Title: Exploring the Effect of Gold Support on the Oxygen Reduction Reaction Activity of Metal Porphycenes

It has been a long-standing goal to find alternative, cost effective catalysts for oxygen reduction reaction (ORR) in fuel cells. Molecular complexes capable of efficiently catalyzing ORR, when supported on a conducting solid surface could provide interesting hybrid materials combining the best of homogeneous and heterogeneous catalysis. Here, we utilize density functional theory to study the ORR activity of molecular (unsupported) and gold supported 3d metal (II)-porphycenes (MPc). All the 3d metal-porphycenes adsorb strongly on the Au(111) support with negative free energy of formation ranging from 1.0–3.0 eV while solvation lowers the energy of molecular MPc by only 0.5 eV compared to the gas phase. These indicate that the 3d MPc are stable and anchored firmly to the gold surface under ORR conditions. Based on our analysis, the gold support enhances the ORR activity in some of the examined MPc systems. We find that the molecular MnPc and FePc are the best ORR electrocatalysts with theoretical overpotentials of 0.44 V and 0.36 V. Thus, this work highlights the important role of the support in preserving/increasing the activity of molecular catalyst.
Authors:
ORCiD logo [1] ;  [2] ;  [3]
  1. Stanford Univ., Stanford, CA (United States); Technical Univ. of Denmark, Lyngby (Denmark)
  2. Stanford Univ., Stanford, CA (United States)
  3. Stanford Univ., Stanford, CA (United States); Technical Univ. of Denmark, Lyngby (Denmark); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Grant/Contract Number:
AC02-76SF00515
Type:
Accepted Manuscript
Journal Name:
ChemCatChem
Additional Journal Information:
Journal Volume: 10; Journal Issue: 23; Journal ID: ISSN 1867-3880
Publisher:
ChemPubSoc Europe
Research Org:
SLAC National Accelerator Lab. (SLAC), Menlo Park, CA (United States); Toyota Research Inst.
Sponsoring Org:
USDOE Office of Science (SC)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; heterogeneous catalysis; homogeneous catalysis; metal-porphycenes; oxygen reduction reaction; electrocatalysis
OSTI Identifier:
1503581

Anand, Megha, Siahrostami, Samira, and Nørskov, Jens K. Exploring the Effect of Gold Support on the Oxygen Reduction Reaction Activity of Metal Porphycenes. United States: N. p., Web. doi:10.1002/cctc.201801408.
Anand, Megha, Siahrostami, Samira, & Nørskov, Jens K. Exploring the Effect of Gold Support on the Oxygen Reduction Reaction Activity of Metal Porphycenes. United States. doi:10.1002/cctc.201801408.
Anand, Megha, Siahrostami, Samira, and Nørskov, Jens K. 2018. "Exploring the Effect of Gold Support on the Oxygen Reduction Reaction Activity of Metal Porphycenes". United States. doi:10.1002/cctc.201801408.
@article{osti_1503581,
title = {Exploring the Effect of Gold Support on the Oxygen Reduction Reaction Activity of Metal Porphycenes},
author = {Anand, Megha and Siahrostami, Samira and Nørskov, Jens K.},
abstractNote = {It has been a long-standing goal to find alternative, cost effective catalysts for oxygen reduction reaction (ORR) in fuel cells. Molecular complexes capable of efficiently catalyzing ORR, when supported on a conducting solid surface could provide interesting hybrid materials combining the best of homogeneous and heterogeneous catalysis. Here, we utilize density functional theory to study the ORR activity of molecular (unsupported) and gold supported 3d metal (II)-porphycenes (MPc). All the 3d metal-porphycenes adsorb strongly on the Au(111) support with negative free energy of formation ranging from 1.0–3.0 eV while solvation lowers the energy of molecular MPc by only 0.5 eV compared to the gas phase. These indicate that the 3d MPc are stable and anchored firmly to the gold surface under ORR conditions. Based on our analysis, the gold support enhances the ORR activity in some of the examined MPc systems. We find that the molecular MnPc and FePc are the best ORR electrocatalysts with theoretical overpotentials of 0.44 V and 0.36 V. Thus, this work highlights the important role of the support in preserving/increasing the activity of molecular catalyst.},
doi = {10.1002/cctc.201801408},
journal = {ChemCatChem},
number = 23,
volume = 10,
place = {United States},
year = {2018},
month = {11}
}

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