Palladium Nanoparticle Formation on TiO2(110) by Thermal Decomposition of Palladium(II) Hexafluoroacetylacetonate | Sciact - CRIS-system of Boreskov Institute of Catalysis

Palladium Nanoparticle Formation on TiO2(110) by Thermal Decomposition of Palladium(II) Hexafluoroacetylacetonate Full article

Journal

ACS Applied Materials and Interfaces
ISSN: 1944-8244 , E-ISSN: 1944-8252

Output data

Year: 2014, Volume: 6, Number: 16, Pages: 14702-14711 Pages count : 10 DOI: 10.1021/am504127k

Tags

atomic layer deposition, heterogeneous catalysis, nucleation delay, scanning tunneling microscopy, surface science, X-ray photoelectron spectroscopy

Authors

Gharachorlou Amir ¹ , Detwiler Michael D. ¹ , Nartova Anna V. ^1,2,3 , Lei Yu ⁴ , Lu Junling ⁴ , Elam Jeffrey W. ⁴ , Delgass W.Nicholas ¹ , Ribeiro Fabio H. ¹ , Zemlyanov Dmitry Y. ⁵

Affiliations

1	School of Chemical Engineering, Purdue University, West Lafayette, Indiana 47907, United States
2	Boreskov Institute of Catalysis, Novosibirsk 630090, Russia
3	Novosibirsk State University, Novosibirsk 630090, Russia
4	Energy Systems Division, Argonne National Laboratory, Argonne, Illinois 60439, United States
5	Birck Nanotechnology Center, Purdue University, West Lafayette, Indiana 47907, United States

Funding (1)

United States Department of Energy

DE-AC02-06CH11357

Palladium nanoparticles were synthesized by thermal decomposition of palladium(II) hexafluoroacetylacetonate (Pd(hfac)2), an atomic layer deposition (ALD) precursor, on a TiO2(110) surface. According to X-ray photoelectron spectroscopy (XPS), Pd(hfac)2 adsorbs on TiO2(110) dissociatively yielding Pd(hfac)(ads), hfac(ads), and adsorbed fragments of the hfac ligand at 300 K. A (2 × 1) surface overlayer was observed by scanning tunneling microscopy (STM), indicating that hfac adsorbs in a bidentate bridging fashion across two Ti 5-fold atoms and Pd(hfac) adsorbs between two bridging oxygen atoms on the surface. Annealing of the Pd(hfac)(ads) and hfac(ads) species at 525 K decomposed the adsorbed hfac ligands, leaving PdO-like species and/or Pd atoms or clusters. Above 575 K, the XPS Pd 3d peaks shift toward lower binding energies and Pd nanoparticles are observed by STM. These observations point to the sintering of Pd atoms and clusters to Pd nanoparticles. The average height of the Pd nanoparticles was 1.2 ± 0.6 nm at 575 K and increased to 1.7 ± 0.5 nm following annealing at 875 K. The Pd coverage was estimated from XPS and STM data to be 0.05 and 0.03 monolayers (ML), respectively, after the first adsorption/decomposition cycle. The amount of palladium deposited on the TiO2(110) surface increased linearly with the number of adsorption/decomposition cycles with a growth rate of 0.05 ML or 0.6 Å per cycle. We suggest that the removal of the hfac ligand and fragments eliminates the nucleation inhibition of Pd nanoparticles previously observed for the Pd(hfac)2 precursor on TiO2.

Gharachorlou A. , Detwiler M.D. , Nartova A.V. , Lei Y. , Lu J. , Elam J.W. , Delgass W.N. , Ribeiro F.H. , Zemlyanov D.Y.
Palladium Nanoparticle Formation on TiO2(110) by Thermal Decomposition of Palladium(II) Hexafluoroacetylacetonate
ACS Applied Materials and Interfaces. 2014. V.6. N16. P.14702-14711. DOI: 10.1021/am504127k WOS Scopus РИНЦ ANCAN OpenAlex

Submitted:	Jun 25, 2014
Accepted:	Aug 5, 2014
Published online:	Aug 14, 2014
Published print:	Aug 27, 2014

Web of science:	WOS:000341122000166
Scopus:	2-s2.0-84906807330
Elibrary:	23986743
Chemical Abstracts:	2014:1293673
Chemical Abstracts (print):	161:352694
OpenAlex:	W2027626377

DB	Citing
Web of science	40
Scopus	42
Elibrary	40
OpenAlex	44