Hydrogen Evolution Reaction on the Single-Shell Carbon-Encapsulated Iron Nanoparticle: A Density Functional Theory Insight

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Hydrogen Evolution Reaction on the Single-Shell Carbon-Encapsulated Iron Nanoparticle : A Density Functional Theory Insight. / Cilpa-Karhu, Geraldine; Pakkanen, Olli J.; Laasonen, Kari.

julkaisussa: Journal of Physical Chemistry C, Vuosikerta 123, Nro 22, 06.06.2019, s. 13569-13577.

Tutkimustuotos: Lehtiartikkelivertaisarvioitu

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Bibtex - Lataa

@article{5b44a075d4cb457aadddf0e61c5f3cdc,
title = "Hydrogen Evolution Reaction on the Single-Shell Carbon-Encapsulated Iron Nanoparticle: A Density Functional Theory Insight",
abstract = "Platinum (Pt)-free catalysts for the hydrogen evolution reaction (HER) is currently a blooming research topic in view of the high cost and scarcity of Pt. Experiments on single-shell carbon-encapsulated iron nanoparticles (SCEINs) have proven comparable HER catalytic efficiency with the best Pt catalyst. However, an understanding of the structure-to-efficiency is missing. We performed ab initio density functional theory calculations on a realistic model of SCEINs, namely Fe55@C240, to shed light on the catalytic properties of SCEINs and studied C60 and C240 fullerenes for comparison. Both the thermodynamic free energy approach (ΔGH) and kinetic (Volmer-Heyrovsk{\'y}/Tafel reaction barrier Ea) calculations were realized on these systems. Our calculations proved that Fe55 has a key role in enhancing the hydrogen binding on C240. Volmer-Heyrovsk{\'y} is the preferred mechanism, Heyrovsk{\'y} being the limiting reaction with Ea > 1 eV. Non-zero coverage of the carbon surface enhances ΔGH without significantly affecting Ea. Because the ΔGH-to-Ea relationship is nonlinear, we proposed a computationally efficient strategy based on the DDEC6 bond order (BO) method to preselect potential HER sites before any calculations. Ea proved to be highly site- and (C-Fe) BO-dependent, leading to the highly heterogeneous catalytic ability of Fe55@C240. ΔGH/Ea best pairs can then be optimized by playing with the surface coverage.",
author = "Geraldine Cilpa-Karhu and Pakkanen, {Olli J.} and Kari Laasonen",
year = "2019",
month = "6",
day = "6",
doi = "10.1021/acs.jpcc.9b01041",
language = "English",
volume = "123",
pages = "13569--13577",
journal = "Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "AMERICAN CHEMICAL SOCIETY",
number = "22",

}

RIS - Lataa

TY - JOUR

T1 - Hydrogen Evolution Reaction on the Single-Shell Carbon-Encapsulated Iron Nanoparticle

T2 - A Density Functional Theory Insight

AU - Cilpa-Karhu, Geraldine

AU - Pakkanen, Olli J.

AU - Laasonen, Kari

PY - 2019/6/6

Y1 - 2019/6/6

N2 - Platinum (Pt)-free catalysts for the hydrogen evolution reaction (HER) is currently a blooming research topic in view of the high cost and scarcity of Pt. Experiments on single-shell carbon-encapsulated iron nanoparticles (SCEINs) have proven comparable HER catalytic efficiency with the best Pt catalyst. However, an understanding of the structure-to-efficiency is missing. We performed ab initio density functional theory calculations on a realistic model of SCEINs, namely Fe55@C240, to shed light on the catalytic properties of SCEINs and studied C60 and C240 fullerenes for comparison. Both the thermodynamic free energy approach (ΔGH) and kinetic (Volmer-Heyrovský/Tafel reaction barrier Ea) calculations were realized on these systems. Our calculations proved that Fe55 has a key role in enhancing the hydrogen binding on C240. Volmer-Heyrovský is the preferred mechanism, Heyrovský being the limiting reaction with Ea > 1 eV. Non-zero coverage of the carbon surface enhances ΔGH without significantly affecting Ea. Because the ΔGH-to-Ea relationship is nonlinear, we proposed a computationally efficient strategy based on the DDEC6 bond order (BO) method to preselect potential HER sites before any calculations. Ea proved to be highly site- and (C-Fe) BO-dependent, leading to the highly heterogeneous catalytic ability of Fe55@C240. ΔGH/Ea best pairs can then be optimized by playing with the surface coverage.

AB - Platinum (Pt)-free catalysts for the hydrogen evolution reaction (HER) is currently a blooming research topic in view of the high cost and scarcity of Pt. Experiments on single-shell carbon-encapsulated iron nanoparticles (SCEINs) have proven comparable HER catalytic efficiency with the best Pt catalyst. However, an understanding of the structure-to-efficiency is missing. We performed ab initio density functional theory calculations on a realistic model of SCEINs, namely Fe55@C240, to shed light on the catalytic properties of SCEINs and studied C60 and C240 fullerenes for comparison. Both the thermodynamic free energy approach (ΔGH) and kinetic (Volmer-Heyrovský/Tafel reaction barrier Ea) calculations were realized on these systems. Our calculations proved that Fe55 has a key role in enhancing the hydrogen binding on C240. Volmer-Heyrovský is the preferred mechanism, Heyrovský being the limiting reaction with Ea > 1 eV. Non-zero coverage of the carbon surface enhances ΔGH without significantly affecting Ea. Because the ΔGH-to-Ea relationship is nonlinear, we proposed a computationally efficient strategy based on the DDEC6 bond order (BO) method to preselect potential HER sites before any calculations. Ea proved to be highly site- and (C-Fe) BO-dependent, leading to the highly heterogeneous catalytic ability of Fe55@C240. ΔGH/Ea best pairs can then be optimized by playing with the surface coverage.

UR - http://www.scopus.com/inward/record.url?scp=85066414074&partnerID=8YFLogxK

U2 - 10.1021/acs.jpcc.9b01041

DO - 10.1021/acs.jpcc.9b01041

M3 - Article

VL - 123

SP - 13569

EP - 13577

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 22

ER -

ID: 34665667