Segregation of K and its effects on the growth, decoration, and adsorption properties of Rh nanoparticles on TiO 2(110)

A. Berkó, Nándor Balázs, György Kassab, L. Óvári

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

In order to understand the promoting mechanism of alkali additives, we have studied potassium overlayers on TiO 2(1 1 0). The surface was prepared by thermal segregation of K from the bulk to the surface above 750-800 K. The bulk diffusion of the Ti/O ions is required for the migration of large K ions inside the lattice. STM and LEIS revealed that segregated potassium forms small clusters of 1-2 nm on the surface, containing also oxygen. These clusters are located preferentially on the one-dimensional defect sites (Ti 2O 3 strings) of the (1 × 1) rutile surface and on the Ti 2O 3 rows of the (1 × n) reconstructed surfaces. According to XPS, the potassium on the surface after segregation at 1000 K is only partially ionized and the Ti 2p region is dominated by the Ti 4+ component. XPS and LEIS provided evidence of a very clear preference for the Rh clusters to grow near 300 K not on the potassium structures but on the potassium-free parts of titania surface. This finding may imply the absence of a direct contact between Rh and K at low Rh coverages. Nevertheless, evaporation of Rh on K/TiO 2(1 1 0) results in more cationic K sites, due to an electron transfer from K to Rh through titania. The decoration and encapsulation of Rh nanoparticles by TiO x proceed also in the presence of potassium. The capping layer does not contain potassium. At large Rh cluster sizes, the wheel-like structure of the cover layer could be identified with a structure found on top of Rh crystallites formed on the K-free titania surface. The presence of potassium stabilized CO on Rh nanoparticles, which is attributed to the indirect charge transfer from potassium structures to rhodium (long range effect).

Original languageEnglish
Pages (from-to)179-189
Number of pages11
JournalJournal of Catalysis
Volume289
DOIs
Publication statusPublished - May 2012

Fingerprint

Potassium
potassium
Nanoparticles
Adsorption
nanoparticles
adsorption
titanium
Titanium
X ray photoelectron spectroscopy
Ions
Rhodium
Alkalies
Carbon Monoxide
wheels
rhodium
Crystallites
Encapsulation
rutile
crystallites
Charge transfer

Keywords

  • Alkali promoter
  • LEIS
  • Potassium segregation
  • Rhodium
  • STM
  • Strong metal support interaction
  • TiO (1 1 0)
  • XPS

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

Cite this

Segregation of K and its effects on the growth, decoration, and adsorption properties of Rh nanoparticles on TiO 2(110). / Berkó, A.; Balázs, Nándor; Kassab, György; Óvári, L.

In: Journal of Catalysis, Vol. 289, 05.2012, p. 179-189.

Research output: Contribution to journalArticle

@article{087536f0f7354337a1e8dbd0f7de9b58,
title = "Segregation of K and its effects on the growth, decoration, and adsorption properties of Rh nanoparticles on TiO 2(110)",
abstract = "In order to understand the promoting mechanism of alkali additives, we have studied potassium overlayers on TiO 2(1 1 0). The surface was prepared by thermal segregation of K from the bulk to the surface above 750-800 K. The bulk diffusion of the Ti/O ions is required for the migration of large K ions inside the lattice. STM and LEIS revealed that segregated potassium forms small clusters of 1-2 nm on the surface, containing also oxygen. These clusters are located preferentially on the one-dimensional defect sites (Ti 2O 3 strings) of the (1 × 1) rutile surface and on the Ti 2O 3 rows of the (1 × n) reconstructed surfaces. According to XPS, the potassium on the surface after segregation at 1000 K is only partially ionized and the Ti 2p region is dominated by the Ti 4+ component. XPS and LEIS provided evidence of a very clear preference for the Rh clusters to grow near 300 K not on the potassium structures but on the potassium-free parts of titania surface. This finding may imply the absence of a direct contact between Rh and K at low Rh coverages. Nevertheless, evaporation of Rh on K/TiO 2(1 1 0) results in more cationic K sites, due to an electron transfer from K to Rh through titania. The decoration and encapsulation of Rh nanoparticles by TiO x proceed also in the presence of potassium. The capping layer does not contain potassium. At large Rh cluster sizes, the wheel-like structure of the cover layer could be identified with a structure found on top of Rh crystallites formed on the K-free titania surface. The presence of potassium stabilized CO on Rh nanoparticles, which is attributed to the indirect charge transfer from potassium structures to rhodium (long range effect).",
keywords = "Alkali promoter, LEIS, Potassium segregation, Rhodium, STM, Strong metal support interaction, TiO (1 1 0), XPS",
author = "A. Berk{\'o} and N{\'a}ndor Bal{\'a}zs and Gy{\"o}rgy Kassab and L. {\'O}v{\'a}ri",
year = "2012",
month = "5",
doi = "10.1016/j.jcat.2012.02.006",
language = "English",
volume = "289",
pages = "179--189",
journal = "Journal of Catalysis",
issn = "0021-9517",
publisher = "Academic Press Inc.",

}

TY - JOUR

T1 - Segregation of K and its effects on the growth, decoration, and adsorption properties of Rh nanoparticles on TiO 2(110)

AU - Berkó, A.

AU - Balázs, Nándor

AU - Kassab, György

AU - Óvári, L.

PY - 2012/5

Y1 - 2012/5

N2 - In order to understand the promoting mechanism of alkali additives, we have studied potassium overlayers on TiO 2(1 1 0). The surface was prepared by thermal segregation of K from the bulk to the surface above 750-800 K. The bulk diffusion of the Ti/O ions is required for the migration of large K ions inside the lattice. STM and LEIS revealed that segregated potassium forms small clusters of 1-2 nm on the surface, containing also oxygen. These clusters are located preferentially on the one-dimensional defect sites (Ti 2O 3 strings) of the (1 × 1) rutile surface and on the Ti 2O 3 rows of the (1 × n) reconstructed surfaces. According to XPS, the potassium on the surface after segregation at 1000 K is only partially ionized and the Ti 2p region is dominated by the Ti 4+ component. XPS and LEIS provided evidence of a very clear preference for the Rh clusters to grow near 300 K not on the potassium structures but on the potassium-free parts of titania surface. This finding may imply the absence of a direct contact between Rh and K at low Rh coverages. Nevertheless, evaporation of Rh on K/TiO 2(1 1 0) results in more cationic K sites, due to an electron transfer from K to Rh through titania. The decoration and encapsulation of Rh nanoparticles by TiO x proceed also in the presence of potassium. The capping layer does not contain potassium. At large Rh cluster sizes, the wheel-like structure of the cover layer could be identified with a structure found on top of Rh crystallites formed on the K-free titania surface. The presence of potassium stabilized CO on Rh nanoparticles, which is attributed to the indirect charge transfer from potassium structures to rhodium (long range effect).

AB - In order to understand the promoting mechanism of alkali additives, we have studied potassium overlayers on TiO 2(1 1 0). The surface was prepared by thermal segregation of K from the bulk to the surface above 750-800 K. The bulk diffusion of the Ti/O ions is required for the migration of large K ions inside the lattice. STM and LEIS revealed that segregated potassium forms small clusters of 1-2 nm on the surface, containing also oxygen. These clusters are located preferentially on the one-dimensional defect sites (Ti 2O 3 strings) of the (1 × 1) rutile surface and on the Ti 2O 3 rows of the (1 × n) reconstructed surfaces. According to XPS, the potassium on the surface after segregation at 1000 K is only partially ionized and the Ti 2p region is dominated by the Ti 4+ component. XPS and LEIS provided evidence of a very clear preference for the Rh clusters to grow near 300 K not on the potassium structures but on the potassium-free parts of titania surface. This finding may imply the absence of a direct contact between Rh and K at low Rh coverages. Nevertheless, evaporation of Rh on K/TiO 2(1 1 0) results in more cationic K sites, due to an electron transfer from K to Rh through titania. The decoration and encapsulation of Rh nanoparticles by TiO x proceed also in the presence of potassium. The capping layer does not contain potassium. At large Rh cluster sizes, the wheel-like structure of the cover layer could be identified with a structure found on top of Rh crystallites formed on the K-free titania surface. The presence of potassium stabilized CO on Rh nanoparticles, which is attributed to the indirect charge transfer from potassium structures to rhodium (long range effect).

KW - Alkali promoter

KW - LEIS

KW - Potassium segregation

KW - Rhodium

KW - STM

KW - Strong metal support interaction

KW - TiO (1 1 0)

KW - XPS

UR - http://www.scopus.com/inward/record.url?scp=84859784067&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84859784067&partnerID=8YFLogxK

U2 - 10.1016/j.jcat.2012.02.006

DO - 10.1016/j.jcat.2012.02.006

M3 - Article

VL - 289

SP - 179

EP - 189

JO - Journal of Catalysis

JF - Journal of Catalysis

SN - 0021-9517

ER -