Supported metal particle catalysts for sulfuric acid decomposition reaction: How activity depends on nanoparticle structure, size, and composition

Sergey Rashkeev, Daniel M. Ginosar, Lucia M. Petkovic, Helen H. Farrell

Research output: Chapter in Book/Report/Conference proceedingConference contribution

Abstract

Production of hydrogen by splitting water in thermochemical water-splitting cycles, such as the sulfur-based group that employs the catalytic decomposition of sulfuric acid into SO2 and O2 is of considerable interest. Most of these processes occur at high temperatures (T > 1,000 K) and exposes catalysts to the extreme conditions such as steam, oxygen, and acid vapor that severely damage these catalysts within a short time. To develop an understanding of the factors that cause catalyst deactivation, we performed density-functional-theory (DFT)-based first-principles calculations and computer simulations for transition metal (TM) particles positioned on the two types of substrate (gamma-alumina and TiO2-rutile). We found that the catalytic activity of the considered systems is defined by several factors, namely: (i) The efficiency of detaching oxygen atoms from the sulfur-containing species; (ii) The ability of the cluster to eliminate oxygen from its surface, in order to regain the catalytically active sites and to continue the process; (iii) The ability of the cluster to keep its size to avoid sintering (that reduces the number of low-coordinated catalytically active sites at the surface of the cluster). We found that the clusters of Pd and Pt are more efficient (at T > 1,000 K) in eliminating oxygen from the surface than the clusters of other TM's considered (Rh, Ir, Ru, and Os). However, the sintering of Rh, Ir, Ru, and Os clusters is significantly suppressed in comparison with the sintering of Pd and Pt clusters of the same size. At the present, we are searching (experimentally and theoretically) for the most optimal combination of the structure, size, and composition of TM nanoparticles, for which the catalytic activity of sulfuric acid decomposition will be the highest.

Original languageEnglish
Title of host publicationACS National Meeting Book of Abstracts
Publication statusPublished - 31 Dec 2007
Externally publishedYes
Event234th ACS National Meeting - Boston, MA, United States
Duration: 19 Aug 200723 Aug 2007

Other

Other234th ACS National Meeting
CountryUnited States
CityBoston, MA
Period19/8/0723/8/07

Fingerprint

Metals
Oxygen
Nanoparticles
Decomposition
Catalysts
Sintering
Chemical analysis
Sulfur
Transition metals
Catalyst activity
Regain
Catalyst deactivation
Water
Aluminum Oxide
Metal nanoparticles
Steam
Density functional theory
Hydrogen
Vapors
Atoms

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Supported metal particle catalysts for sulfuric acid decomposition reaction : How activity depends on nanoparticle structure, size, and composition. / Rashkeev, Sergey; Ginosar, Daniel M.; Petkovic, Lucia M.; Farrell, Helen H.

ACS National Meeting Book of Abstracts. 2007.

Research output: Chapter in Book/Report/Conference proceedingConference contribution

Rashkeev, S, Ginosar, DM, Petkovic, LM & Farrell, HH 2007, Supported metal particle catalysts for sulfuric acid decomposition reaction: How activity depends on nanoparticle structure, size, and composition. in ACS National Meeting Book of Abstracts. 234th ACS National Meeting, Boston, MA, United States, 19/8/07.
Rashkeev, Sergey ; Ginosar, Daniel M. ; Petkovic, Lucia M. ; Farrell, Helen H. / Supported metal particle catalysts for sulfuric acid decomposition reaction : How activity depends on nanoparticle structure, size, and composition. ACS National Meeting Book of Abstracts. 2007.
@inproceedings{24eb8b91b1c64c6bb1abcd2eeab2e2b2,
title = "Supported metal particle catalysts for sulfuric acid decomposition reaction: How activity depends on nanoparticle structure, size, and composition",
abstract = "Production of hydrogen by splitting water in thermochemical water-splitting cycles, such as the sulfur-based group that employs the catalytic decomposition of sulfuric acid into SO2 and O2 is of considerable interest. Most of these processes occur at high temperatures (T > 1,000 K) and exposes catalysts to the extreme conditions such as steam, oxygen, and acid vapor that severely damage these catalysts within a short time. To develop an understanding of the factors that cause catalyst deactivation, we performed density-functional-theory (DFT)-based first-principles calculations and computer simulations for transition metal (TM) particles positioned on the two types of substrate (gamma-alumina and TiO2-rutile). We found that the catalytic activity of the considered systems is defined by several factors, namely: (i) The efficiency of detaching oxygen atoms from the sulfur-containing species; (ii) The ability of the cluster to eliminate oxygen from its surface, in order to regain the catalytically active sites and to continue the process; (iii) The ability of the cluster to keep its size to avoid sintering (that reduces the number of low-coordinated catalytically active sites at the surface of the cluster). We found that the clusters of Pd and Pt are more efficient (at T > 1,000 K) in eliminating oxygen from the surface than the clusters of other TM's considered (Rh, Ir, Ru, and Os). However, the sintering of Rh, Ir, Ru, and Os clusters is significantly suppressed in comparison with the sintering of Pd and Pt clusters of the same size. At the present, we are searching (experimentally and theoretically) for the most optimal combination of the structure, size, and composition of TM nanoparticles, for which the catalytic activity of sulfuric acid decomposition will be the highest.",
author = "Sergey Rashkeev and Ginosar, {Daniel M.} and Petkovic, {Lucia M.} and Farrell, {Helen H.}",
year = "2007",
month = "12",
day = "31",
language = "English",
isbn = "0841269556",
booktitle = "ACS National Meeting Book of Abstracts",

}

TY - GEN

T1 - Supported metal particle catalysts for sulfuric acid decomposition reaction

T2 - How activity depends on nanoparticle structure, size, and composition

AU - Rashkeev, Sergey

AU - Ginosar, Daniel M.

AU - Petkovic, Lucia M.

AU - Farrell, Helen H.

PY - 2007/12/31

Y1 - 2007/12/31

N2 - Production of hydrogen by splitting water in thermochemical water-splitting cycles, such as the sulfur-based group that employs the catalytic decomposition of sulfuric acid into SO2 and O2 is of considerable interest. Most of these processes occur at high temperatures (T > 1,000 K) and exposes catalysts to the extreme conditions such as steam, oxygen, and acid vapor that severely damage these catalysts within a short time. To develop an understanding of the factors that cause catalyst deactivation, we performed density-functional-theory (DFT)-based first-principles calculations and computer simulations for transition metal (TM) particles positioned on the two types of substrate (gamma-alumina and TiO2-rutile). We found that the catalytic activity of the considered systems is defined by several factors, namely: (i) The efficiency of detaching oxygen atoms from the sulfur-containing species; (ii) The ability of the cluster to eliminate oxygen from its surface, in order to regain the catalytically active sites and to continue the process; (iii) The ability of the cluster to keep its size to avoid sintering (that reduces the number of low-coordinated catalytically active sites at the surface of the cluster). We found that the clusters of Pd and Pt are more efficient (at T > 1,000 K) in eliminating oxygen from the surface than the clusters of other TM's considered (Rh, Ir, Ru, and Os). However, the sintering of Rh, Ir, Ru, and Os clusters is significantly suppressed in comparison with the sintering of Pd and Pt clusters of the same size. At the present, we are searching (experimentally and theoretically) for the most optimal combination of the structure, size, and composition of TM nanoparticles, for which the catalytic activity of sulfuric acid decomposition will be the highest.

AB - Production of hydrogen by splitting water in thermochemical water-splitting cycles, such as the sulfur-based group that employs the catalytic decomposition of sulfuric acid into SO2 and O2 is of considerable interest. Most of these processes occur at high temperatures (T > 1,000 K) and exposes catalysts to the extreme conditions such as steam, oxygen, and acid vapor that severely damage these catalysts within a short time. To develop an understanding of the factors that cause catalyst deactivation, we performed density-functional-theory (DFT)-based first-principles calculations and computer simulations for transition metal (TM) particles positioned on the two types of substrate (gamma-alumina and TiO2-rutile). We found that the catalytic activity of the considered systems is defined by several factors, namely: (i) The efficiency of detaching oxygen atoms from the sulfur-containing species; (ii) The ability of the cluster to eliminate oxygen from its surface, in order to regain the catalytically active sites and to continue the process; (iii) The ability of the cluster to keep its size to avoid sintering (that reduces the number of low-coordinated catalytically active sites at the surface of the cluster). We found that the clusters of Pd and Pt are more efficient (at T > 1,000 K) in eliminating oxygen from the surface than the clusters of other TM's considered (Rh, Ir, Ru, and Os). However, the sintering of Rh, Ir, Ru, and Os clusters is significantly suppressed in comparison with the sintering of Pd and Pt clusters of the same size. At the present, we are searching (experimentally and theoretically) for the most optimal combination of the structure, size, and composition of TM nanoparticles, for which the catalytic activity of sulfuric acid decomposition will be the highest.

UR - http://www.scopus.com/inward/record.url?scp=37349087182&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=37349087182&partnerID=8YFLogxK

M3 - Conference contribution

AN - SCOPUS:37349087182

SN - 0841269556

SN - 9780841269552

BT - ACS National Meeting Book of Abstracts

ER -