Catalytic activity of Pt<sub>38</sub> in the oxygen reduction reaction from first-principles simulations

Sementa, Luca; Andreussi, Oliviero; Goddard, William A.; Fortunelli, Alessandro

doi:10.1039/c6cy00750c

Cited by 26 publications

(25 citation statements)

References 47 publications

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“…Applications of condensed-matter continuum approaches in electro-chemistry and electro-catalysis in wet environments are among the main purposes that have driven these recent developments. [29,34,105,[107][108][109][110][113][114][115][116][117][118][119][120][121][122] There are different simulation strategies of increasing complexity that can be attempted and that could take substantial advantage from the use of continuum embedding techniques.…”

Section: Modeling Electro-chemistrymentioning

confidence: 99%

“…As an example, Fortunelli et al showed that tuning the dielectric screening of the wet environment can increase by more than one order of magnitude the catalytic reactivity of Pt for the oxygen reduction reaction. [105,106,118] Similarly, the use of the computational hydrogen electrode technique may also take advantage of simulations in continuum environments.…”

Section: Modeling Electro-chemistrymentioning

confidence: 99%

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Continuum embeddings in condensed‐matter simulations

Andreussi

Fisicaro

2018

Int J of Quantum Chemistry

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Continuum models have a long tradition in computational chemistry, where they have provided a compact and efficient way to characterize environment effects in quantum-mechanical simulations of solvated systems. Fattebert and Gygi pioneered the development of continuum dielectric embedding schemes for periodic systems and their seamless extension toward molecular dynamics simulations. Following their work, continuum embedding approaches in condensedmatter simulations have thrived. The possibility to model wet and electrified interfaces, with a reduced computational overhead with respect to isolated systems, is opening new perspectives in the characterization of materials and devices. Important applications of these new techniques are in the field of catalysis, electro-chemistry, electro-catalysis, etc. Here we will address the main physical and computational aspects of continuum embedding schemes recently developed for condensed-matter simulations, underlying their peculiarities and their differences with respect to the quantum-chemistry state-of-the-art.condensed matter, continuum models, electro-chemistry, materials, solvation 1 | INTRODUCTION An embedding liquid environment can substantially affect the electronic properties, geometries and spectroscopic responses of the embedded system. Dealing with this kind of effects is a difficult computational task, due to the multiscale nature of the system. A brute force approach to handle these effects would require including all of the solvent atomistic details in the quantum-mechanical (QM) calculation of the solvated system. The total number of degrees of freedom, in particular the number of electrons that need to be described in a first-principles calculation, can thus increase by orders of magnitude. As a result, a calculation that would be feasible in vacuum can easily become untreatable in solution. Moreover, statistical sampling and averaging of the results over different configurations of the liquid would be required, thus further increasing the computational cost of such an approach. These limitations have motivated the development of incredibly powerful simulation programs, [1][2][3] able to take advantage of the rapid evolution of scientific computing hardware and software, for example, by fully exploiting parallel and hybrid architectures. Regardless of its computational feasibility, the explicit description of liquid environments may also suffer from some well-known limitations of current state-of-the-art ab initio methods, in particular regarding their structural [4][5][6][7] and dielectric [8][9][10] properties.On the other hand, when looking at the properties of a solvated system, it is often the case that the detailed effects caused by solute-solvent interactions are less important than the intrinsic properties of the solute. If this is the case, one can exploit a hierarchical approach, where solvent degrees of freedom are treated with a computationally less expensive technique, but are coupled with an highly accurate description of the solvated system...

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Section: Modeling Electro-chemistrymentioning

confidence: 99%

Section: Modeling Electro-chemistrymentioning

confidence: 99%

Continuum embeddings in condensed‐matter simulations

Andreussi

Fisicaro

2018

Int J of Quantum Chemistry

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“…The ORR activity of truncated octahedral Pt 38 clusters as a catalyst was investigated via first-principles simulations by Fortunelli's group. For Pt 38 clusters, the rate-determining step is the H 2 O formation, while for an extended surface such as the Pt (111) crystal plane, the O hydration is actually the overall reaction barrier [79]. Recently, Nigam et al carried out density function theory (DFT) calculations to examine the viability of alumina-supported Pt clusters (Pt n @Al 2 O 3 , n = 1-7, 10) as ORR electrocatalysts [80].…”

Section: Pt Clusters For Orrmentioning

confidence: 99%

Oxygen Reduction Reaction Catalyzed by Noble Metal Clusters

Tang

Wang

2018

Catalysts

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Highly-efficient catalysts for the oxygen reduction reaction (ORR) have been extensively investigated for the development of proton exchange membrane fuel cells (PEMFCs). The state-ofthe-art Pt/C catalysts suffer from high price, limited accessibility of Pt, sluggish reaction kinetics, as well as undesirable long-term durability. Engineering ultra-small noble metal clusters with high surface-to-volume ratios and robust stabilities for ORR represents a new avenue. After a simple introduction regarding the significance of ORR and the recent development of noble metal clusters, the general ORR mechanism in both acidic and basic media is firstly discussed. Subsequently, we will summarize the recent efforts employing Pt, Au, Ag, Pd and Ru clusters, as well as the alloyed bi-metallic clusters for acquiring highly efficient catalysts to enhance both the activity and stability of ORR. Molecular noble metal clusters with definitive composition to reveal the relevant ORR mechanism will be particularly highlighted. Finally, the current challenges, the future outlook, as well as the perspectives in this booming field will be proposed, featuring the great opportunities and potentials to engineering noble metal clusters as highly-efficient and durable cathodic catalysts for fuel cell applications.

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“…To this end, we exploit and further develop the self-consistent continuum solvation (SCCS) approach proposed by Andreussi et al 27 to simulate semiconductor electrodes under applied voltage in electrolytic media. While this method has been successful in modeling metal electrodes, [28][29][30][31][32] no previous study has focused on describing band bending at semiconductor electrodes using a self-consistent continuum solvation approach. To illustrate band bending, the electrostatic profile of a semiconductor-electrolyte interface is shown in Fig.…”

Section: Introductionmentioning

confidence: 99%

Quantum-continuum calculation of the surface states and electrical response of silicon in solution

Campbell

Dabo

2017

Phys. Rev. B

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A wide range of electrochemical reactions of practical importance occur at the interface between a semiconductor and an electrolyte. We present an embedded density-functional theory method using the recently released self-consistent continuum solvation (SCCS) approach to study these interfaces. In this model, a quantum description of the surface is incorporated into a continuum representation of the bending of the bands within the electrode. The model is applied to understand the electrical response of ten relevant surface terminations for silicon electrodes in solution, providing microscopic insights into the low-voltage region, where surface states determine the electrification of the semiconductor electrode. arXiv:1701.01758v5 [cond-mat.mtrl-sci]

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Catalytic activity of Pt₃₈ in the oxygen reduction reaction from first-principles simulations

Cited by 26 publications

References 47 publications

Continuum embeddings in condensed‐matter simulations

Continuum embeddings in condensed‐matter simulations

Oxygen Reduction Reaction Catalyzed by Noble Metal Clusters

Quantum-continuum calculation of the surface states and electrical response of silicon in solution

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Catalytic activity of Pt38 in the oxygen reduction reaction from first-principles simulations

Cited by 26 publications

References 47 publications

Continuum embeddings in condensed‐matter simulations

Continuum embeddings in condensed‐matter simulations

Oxygen Reduction Reaction Catalyzed by Noble Metal Clusters

Quantum-continuum calculation of the surface states and electrical response of silicon in solution

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Catalytic activity of Pt₃₈ in the oxygen reduction reaction from first-principles simulations