Metallofullerenes as fuel cell electrocatalysts: A theoretical investigation of adsorbates on C59Pt

Gabriel, Margaret A.; Genovese, Luigi; Krosnicki, Guillaume; Lemaire, Olivier; Deutsch, Thierry; Franco, Alejandro A.

doi:10.1039/b927111b

Cited by 25 publications

(21 citation statements)

References 42 publications

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“…For all the heterofullerenes, H 2 O was observed to be directed towards the hexagonal void with both O−H bonds pointing parallel to the heterofullerene surface (Figure a–d). These adsorption geometries were similar to those reported for Pt‐doped heterofullerenes . The O−H atomic bonds were 0.97 Å for both the C 59 M heterofullerenes.…”

Section: Resultssupporting

confidence: 84%

Computational Design of New Heterofullerene‐Based Biomimetic α‐Carbonic Anhydrase Analogues

Verma

Deshpande

2016

ChemPhysChem

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The biomimetic CO hydration activity of Ru/Rh-doped fullerenes was revealed by using density functional theory calculations. The mechanism of CO hydration on the proposed heterofullerenes followed the mechanistic action of α-carbonic anhydrases, and consisted of the adsorption and deprotonation of H O, CO interaction with hydroxyl groups, CO bending, and proton transfer to give the HCO-3 product. Free-energy landscapes for the reaction showed the catalysts to be active for the reaction. H O adsorption over the catalysts was exergonic whereas CO adsorption over the catalyst-OH complex was observed to be an endergonic process. Intramolecular proton transfer resulting in the final product, HCO-3 , was found to be the rate-limiting step for the reaction on C N M (M=Ru/Rh), whereas H O dissociation was found to be the rate-limiting step for the reaction on C M (M=Ru/Rh). C N M catalysts were found to be superior to C M catalysts for biomimetic CO hydration, as indicated by the free-energy landscapes and energy requirements.

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Section: Resultssupporting

confidence: 84%

Computational Design of New Heterofullerene‐Based Biomimetic α‐Carbonic Anhydrase Analogues

Verma

Deshpande

2016

ChemPhysChem

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“…As a first test case, we apply our activated scheme to a molecular system for which BigDFT has proven to be efficient for a large variety of systems, e.g., C 59 Pt, 33 Si 30 C 30 (Ref. 34), and B 80 .…”

Section: A Defects In C 20 Clustersmentioning

confidence: 99%

Optimized energy landscape exploration using the ab initio based activation-relaxation technique

Machado-Charry

Béland

Caliste

et al. 2011

The Journal of Chemical Physics

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Unbiased open-ended methods for finding transition states are powerful tools to understand diffusion and relaxation mechanisms associated with defect diffusion, growth processes, and catalysis. They have been little used, however, in conjunction with ab initio packages as these algorithms demanded large computational effort to generate even a single event. Here, we revisit the activation-relaxation technique (ART nouveau) and introduce a two-step convergence to the saddle point, combining the previously used Lanczós algorithm with the direct inversion in interactive subspace scheme. This combination makes it possible to generate events (from an initial minimum through a saddle point up to a final minimum) in a systematic fashion with a net 300-700 force evaluations per successful event. ART nouveau is coupled with BigDFT, a Kohn-Sham density functional theory (DFT) electronic structure code using a wavelet basis set with excellent efficiency on parallel computation, and applied to study the potential energy surface of C(20) clusters, vacancy diffusion in bulk silicon, and reconstruction of the 4H-SiC surface.

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“…Some of these were on the C 60 -like backside of the metallofullerene, but most Figure 2. The last one is also shown in (32). All four sites are strongly bound to the metallofullerene and binding energies for all of the OH adsorbates, even those not shown, ranged from 0.04 to 3.43 eV.…”

Section: Calculating G Valuesmentioning

confidence: 94%

“…Many ORR adsorbates were investigated on C 59 Pt (32), including the H atom and the OH, OOH, O 2 , and H 2 O molecules. In order to find the adsorption sites, the atom or molecule was placed at different places on the surface of the metallofullerene and the structure was allowed to relax.…”

Section: Calculating G Valuesmentioning

confidence: 99%

Fullerene-Based Materials as Catalysts for Fuel Cells

Gabriel¹,

Deutsch²,

Franco³

2010

ECS Trans.

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Nano-structured catalyst degradation in state-of-the-art polymer electrolyte membrane fuel cells (PEMFCs) is one of the main shortcomings that limit the large-scale development and commercialization of this technology. During normal operating conditions of the fuel cell, the PEMFC lifetime tends to be limited by coarsening of the cathode's Pt-based catalyst and by corrosion of the cathode's carbon black support. Because of their chemical properties, metallofullerenes, such as C 59 Pt or PtC 60 , may be more electrochemically stable than the Pt/C mixture. In this paper we investigate, by theoretical methods, the stability of oxygen reduction reaction (ORR) adsorbates on these metallofullerenes.

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Metallofullerenes as fuel cell electrocatalysts: A theoretical investigation of adsorbates on C59Pt

Cited by 25 publications

References 42 publications

Computational Design of New Heterofullerene‐Based Biomimetic α‐Carbonic Anhydrase Analogues

Computational Design of New Heterofullerene‐Based Biomimetic α‐Carbonic Anhydrase Analogues

Optimized energy landscape exploration using the ab initio based activation-relaxation technique

Fullerene-Based Materials as Catalysts for Fuel Cells

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