Apart from large surface areas, low activation energies are essential for efficient reactions, particularly in heterogeneous catalysis. Here, we show that not only the size of nanoparticles but also their detailed morphology can crucially affect reaction kinetics, as demonstrated for mass-selected, soft-landed, and oxidized cobalt clusters in a 6 nm to 18 nm size range. The method of reflection high-energy electron diffraction is extended to the quantitative determination of particle activation energies which is applied for repeated oxidation and reduction cycles at the same particles. We find unexpectedly small activation barriers for the reduction reaction of the largest particles studied, despite generally increasing barriers for growing sizes. We attribute these observations to the interplay of reaction-specific material transport with a size-dependent inner particle morphology.
REFERENCES
1.
M.
Haruta
, Gold Bull.
37
, 27
(2004
).2.
R.
Narayanan
and M. A.
El-Sayed
, Nano Lett.
4
, 1343
(2004
).3.
S.
Panigrahi
, S.
Basu
, S.
Praharaj
, S.
Pande
, S.
Jana
, A.
Pal
, S. K.
Ghosh
, and T.
Pal
, J. Phys. Chem. C
111
, 4596
(2007
).4.
M.
Chandra
and Q.
Xu
, J. Power Sources
168
, 135
(2007
).5.
M.
Valden
, S.
Pak
, X.
Lai
, and D. W.
Goodman
, Catal. Lett.
56
, 7
(1998
).6.
K.
Park
, D.
Lee
, A.
Rai
, D.
Mukherjee
, and M. R.
Zachariah
, J. Phys. Chem. B
109
, 7290
(2005
).7.
S. W.
Chung
, E. A.
Guliants
, C. E.
Bunker
, P. A.
Jelliss
, and S. W.
Buckner
, J. Phys. Chem. Solids
72
, 719
(2011
).8.
H. M.
Lu
and X. K.
Meng
, J. Phys. Chem. C
114
, 1534
(2010
).9.
B.
Tomić-Tucaković
, D.
Majstorović
, D.
Jelić
, and S.
Mentus
, Thermochim. Acta
541
, 15
(2012
).10.
C. P.
Vinod
, Catal. Today
154
, 113
(2010
).11.
Z.-j.
Wang
, S.
Skiles
, F.
Yang
, Z.
Yan
, and D. W.
Goodman
, Catal. Today
181
, 75
(2012
).12.
G. L.
Bezemer
, J. H.
Bitter
, H. P. C. E.
Kuipers
, H.
Oosterbeek
, J. E.
Holewijn
, X.
Xu
, F.
Kapteijn
, A. Jos
van Dillen
, and K. P.
de Jong
, J. Am. Chem. Soc.
128
, 3956
(2006
).13.
V.
Papaefthimiou
, T.
Dintzer
, V.
Dupuis
, A.
Tamion
, F.
Tournus
, A.
Hillion
, D.
Teschner
, M.
Hävecker
, A.
Knop-Gericke
, R.
Schlögl
, and S.
Zafeiratos
, ACS Nano
5
, 2182
(2011
).14.
A.
Khodakov
, J.
Lynch
, D.
Bazin
, B.
Rebours
, N.
Zanier
, B.
Moisson
, and P.
Chaumette
, J. Catal.
168
, 16
(1997
).15.
M.
Trépanier
, A. K.
Dalai
, and N.
Abatzoglou
, Appl. Catal., A
374
, 79
(2010
).16.
G.
Prieto
, A.
Martínez
, P.
Concepción
, and R.
Moreno-Tost
, J. Catal.
266
, 129
(2009
).17.
A.
Martínez
, C.
López
, F.
Márquez
, and I.
Díaz
, J. Catal.
220
, 486
(2003
).18.
M.
Mortimer
and P.
Taylor
, Chemical Kinetics and Mechanism
, The Molecular World
, Vol. 5
(Royal Society of Chemistry
, Cambridge, UK
, 2002
).19.
P. A.
Chernavskii
, G. V.
Pankina
, A. P.
Chernavskii
, N. V.
Peskov
, P. V.
Afanas’ev
, N. S.
Perov
, V. A.
Tennov
, and V. V.
Lunin
, Russ. J. Phys. Chem.
80
, 1475
(2006
).20.
M.
Martin
, U.
Koops
, and N.
Lakshmi
, Solid State Ionics
172
, 357
(2004
).21.
T.
Reitz
, P.
Lee
, K.
Czaplewski
, J.
Lang
, K.
Popp
, and H.
Kung
, J. Catal.
199
, 193
(2001
).22.
M. A.
Newton
, S. G.
Fiddy
, G.
Guilera
, B.
Jyoti
, and J.
Evans
, Chem. Commun.
2005
, 118
.23.
Y.
Liang
, Y.
Li
, H.
Wang
, J.
Zhou
, J.
Wang
, T.
Regier
, and H.
Dai
, Nat. Mater.
10
, 780
(2011
).24.
E. C.
Tyo
, C.
Yin
, M.
Di Vece
, Q.
Qian
, G.
Kwon
, S.
Lee
, B.
Lee
, J. E.
DeBartolo
, S.
Seifert
, R. E.
Winans
, R.
Si
, B.
Ricks
, S.
Goergen
, M.
Rutter
, B.
Zugic
, M.
Flytzani-Stephanopoulos
, Z. W.
Wang
, R. E.
Palmer
, M.
Neurock
, and S.
Vajda
, ACS Catal.
2
, 2409
(2012
).25.
H. P.
Klug
and L. E.
Alexander
, X-ray Diffraction Procedures for Polycrystalline and Amorphous Materials
, 2nd ed. (Wiley
, New York
, 1974
).26.
A.
Monshi
, World J. Nano Sci. Eng.
02
, 154
(2012
).27.
H.
Hartmann
, V. N.
Popok
, I.
Barke
, V. v.
Oeynhausen
, and K.-H.
Meiwes-Broer
, Rev. Sci. Instrum.
83
, 73304
(2012
).28.
A.
Perez
, P.
Melinon
, V.
Dupuis
, P.
Jensen
, B.
Prevel
, J.
Tuaillon
, L.
Bardotti
, C.
Martet
, M.
Treilleux
, M.
Broyer
, M.
Pellarin
, J. L.
Vaille
, B.
Palpant
, and J.
Lerme
, J. Phys. D: Appl. Phys.
30
, 709
(1997
).29.
W.
Harbich
, Philos. Mag.
79
, 1307
(1999
).30.
V. N.
Popok
, I.
Barke
, E. E.
Campbell
, and K.-H.
Meiwes-Broer
, Surf. Sci. Rep.
66
, 347
(2011
).31.
O.
Kitakami
, H.
Sato
, Y.
Shimada
, F.
Sato
, and M.
Tanaka
, Phys. Rev. B
56
, 13849
(1997
).32.
Y.
Yin
, R. M.
Rioux
, C. K.
Erdonmez
, S.
Hughes
, G. A.
Somorjai
, and A. P.
Alivisatos
, Science
304
, 711
(2004
).33.
D.-H.
Ha
, L. M.
Moreau
, S.
Honrao
, R. G.
Hennig
, and R. D.
Robinson
, J. Phys. Chem. C
117
, 14303
(2013
).34.
See supplementary material at http://dx.doi.org/10.1063/1.4930853 for additional RHEED data, Arrhenius plots, and AFM and TEM images.
35.
The 8 nm thin SiO2 membrane has very limited thermal conductivity; hence, the particle temperature on these substrates may be significantly lower compared to the supporting frame.
36.
A.
Kleibert
, A.
Voitkans
, and K.-H.
Meiwes-Broer
, Phys. Status Solidi B
247
, 1048
(2010
).37.
A.
Kleibert
, A.
Voitkans
, and K.-H.
Meiwes-Broer
, Phys. Rev. B
81
, 073412
(2010
).38.
J.
Richardson
, Appl. Catal., A
246
, 137
(2003
).39.
S.
Bartling
, C.
Yin
, I.
Barke
, K.
Oldenburg
, H.
Hartmann
, V.
von Oeynhausen
, M.-M.
Pohl
, K.
Houben
, E. C.
Tyo
, S.
Seifert
, P.
Lievens
, K.-H.
Meiwes-Broer
, and S.
Vajda
, ACS Nano
9
, 5984
(2015
).40.
S.
Sadasivan
, R. M.
Bellabarba
, and R. P.
Tooze
, Nanoscale
5
, 11139
(2013
).41.
A.
Cabot
, V. F.
Puntes
, E.
Shevchenko
, Y.
Yin
, L.
Balcells
, M. A.
Marcus
, S. M.
Hughes
, and A. P.
Alivisatos
, J. Am. Chem. Soc.
129
, 10358
(2007
).42.
R.
Nakamura
, D.
Tokozakura
, H.
Nakajima
, J.-G.
Lee
, and H.
Mori
, J. Appl. Phys.
101
, 074303
(2007
).43.
R.
Nakamura
, J.-G.
Lee
, H.
Mori
, and H.
Nakajima
, Philos. Mag.
88
, 257
(2008
).44.
E.
Sutter
and P.
Sutter
, J. Phys. Chem. C
116
, 20574
(2012
).45.
V. I.
Levitas
and H.
Attariani
, J. Phys. Chem. C
116
, 54
(2012
).47.
Q.-S.
Fu
, Y.-Q.
Xue
, Z.-X.
Cui
, and M.-F.
Wang
, J. Nanomater.
2014
, 1
.48.
P. A.
Chernavskii
, N. V.
Peskov
, A. V.
Mugtasimov
, and V. V.
Lunin
, Russ. J. Phys. Chem. B
1
, 394
(2007
).49.
D. J.
Young
, High Temperature Oxidation and Corrosion of Metals
, Elsevier Corrosion Series
Vol. 1
, 1st ed. (Elsevier
, Amsterdam, Boston, London
, 2008
).50.
N.
Bahlawane
, E. F.
Rivera
, K.
Kohse-Höinghaus
, A.
Brechling
, and U.
Kleineberg
, Appl. Catal., B
53
, 245
(2004
).51.
H.-Y.
Lin
and Y.-W.
Chen
, Mater. Chem. Phys.
85
, 171
(2004
).52.
K.
Nanda
, S.
Sahu
, and S.
Behera
, Phys. Rev. A
66
, 013208
(2002
).53.
C.
Yang
and S.
Li
, Phys. Rev. B
75
, 165413
(2007
).54.
M. A.
Shandiz
, A.
Safaei
, S.
Sanjabi
, and Z. H.
Barber
, Solid State Commun.
145
, 432
(2008
).55.
G.
Guisbiers
, Nanoscale Res. Lett.
5
, 1132
(2010
).56.
Z.
Cui
, H.
Duan
, Y.
Xue
, and P.
Li
, J. Nanopart. Res.
17
, 1
(2015
).57.
S.
Jia
, C.-H.
Hsia
, and D. H.
Son
, J. Phys. Chem. C
115
, 92
(2011
).58.
M.
Varón
, I.
Ojea-Jimenez
, J.
Arbiol
, L.
Balcells
, B.
Martínez
, and V. F.
Puntes
, Nanoscale
5
, 2429
(2013
).59.
B. V.
L’vov
and A. K.
Galwey
, J. Therm. Anal. Calorim.
110
, 601
(2012
).60.
Diffusion in Solid Metals and Alloys
, Landolt-Börnstein–Group III Condensed Matter
edited by H.
Mehrer
(Springer-Verlag
, Berlin/Heidelberg
, 1990
).61.
M.
Cardona
, P.
Fulde
, K. v.
Klitzing
, H.-J.
Queisser
, R.
Merlin
, H.
Störmer
, and H.
Mehrer
, Diffusion in Solids
(Springer Berlin
, Berlin
, 2007
), Vol. 155
.62.
W.
Sprengel
, Nanostructured Materials
(Elsevier
, 2007
), pp. 331
–364
.63.
F.
Bourgeois
, P.
Gergaud
, H.
Renevier
, C.
Leclere
, and G.
Feuillet
, J. Appl. Phys.
113
, 13510
(2013
).64.
65.
B.
Albaalbaki
and R. J.
Hill
, Proc. R. Soc. A
468
, 3100
(2012
).66.
J.
He
, D.
Jing
, and G.
Vidali
, Phys. Chem. Chem. Phys.
16
, 3493
(2014
).67.
J. A.
Medford
, A. C.
Johnston-Peck
, and J. B.
Tracy
, Nanoscale
5
, 155
(2012
).© 2015 AIP Publishing LLC.
2015
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