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fied access to highly active metal catalysts in a size range
close to or even below 1 nm.
(9) Jin, R. Atomically precise metal nanoclusters: Stable sizes and
optical properties. Nanoscale 2015, 7, 1549–1565.
(10) Wilcoxon, J. P.; Abrams, B. L. Synthesis, structure and prop-
erties of metal nanoclusters. Chem. Soc. Rev. 2006, 35, 1162–1194.
(
11) Lopez-Sanchez, J. A.; Dimitratos, N.; Hammond, C.; Brett, G.
L.; Kesavan, L.; White, S.; Miedziak, P.; Tiruvalam, R.; Jenkins, R.
L.; Carley, A. F.; Knight, D.; Kiely, C. J.; Hutchings, G. J. Facile
removal of stabilizer-ligands from supported gold nanoparticles.
Nature Chem. 2011, 3, 551 EP -.
ASSOCIATED CONTENT
The Supporting Information is available free of charge on the
ACS Publications website.
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12) Wang, Y.; Su, H.; Xu, C.; Li, G.; Gell, L.; Lin, S.; Tang, Z.;
Information on materials, synthetic procedures, measurements,
additional characterizations (photographs, UV/Vis, IR, XPS,
TGA, HR-TEM, HAADF-STEM, PXRD, NMR) (PDF)
Häkkinen, H.; Zheng, N. An intermetallic Au24Ag20 superatom
nanocluster stabilized by labile ligands. J. Am. Chem. Soc. 2015, 137,
4324–4327.
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13) Valden, M.; Lai, X.; Goodman, D. W. Onset of Catalytic Ac-
tivity of Gold Clusters on Titania with the Appearance of Nonmetallic
Properties. Science 1998, 281, 1647–1650.
(14) Cheng, N.; Stambula, S.; Wang, D.; Banis, M. N.; Liu, J.;
Riese, A.; Xiao, B.; Li, R.; Sham, T.-K.; Liu, L.-M.; Botton, G. A.;
Sun, X. Platinum single-atom and cluster catalysis of the hydrogen
evolution reaction. Nature Comm. 2016, 7, 13638 EP -.
AUTHOR INFORMATION
Corresponding Author
*
Notes
(
15) Schweinberger, F. F.; Berr, M. J.; Döblinger, M.; Wolff, C.;
The authors declare no competing financial interests.
Sanwald, K. E.; Crampton, A. S.; Ridge, C. J.; Jäckel, F.; Feldmann,
J.; Tschurl, M.; Heiz, U. Cluster size effects in the photocatalytic
hydrogen evolution reaction. J. Am. Chem. Soc. 2013, 135, 13262–
ACKNOWLEDGMENT
This work has been supported by the Deutsche Forschungsge-
meinschaft (DFG) via the cluster of excellence e-conversion
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3265.
16) Imaoka, T.; Kitazawa, H.; Chun, W.-J.; Omura, S.; Albrecht,
(
K.; Yamamoto, K. Magic number Pt13 and misshapen Pt12 clusters:
Which one is the better catalyst? J. Am. Chem. Soc. 2013, 135,
13089–13095.
(www.e-conversion.de; EXC 2089). The authors gratefully
acknowledge the support by the Operational Programme Re-
search, Development and Education – European Regional Devel-
opment Fund, Project No. CZ.02.1.01/0.0/0.0/15_003/0000416 of
the Ministry of Education, Youth and Sports of the Czech Repub-
lic. Part of the work was carried out with the support of CEITEC
Nano Research Infrastructure (ID LM2015041, MEYS CR, 2016–
(
17) Moon, H. R.; Lim, D.-W.; Suh, M. P. Fabrication of metal na-
noparticles in metal-organic frameworks. Chem. Soc. Rev. 2013, 42,
807–1824.
18) Esken, D.; Turner, S.; Lebedev, O. I.; van Tendeloo, G.;
1
(
Fischer, R. A. Au@ZIFs: Stabilization and Encapsulation of Cavity-
Size Matching Gold Clusters inside Functionalized Zeolite Imidazo-
late Frameworks, ZIFs. Chem. Mater. 2010, 22, 6393–6401.
2
019). We would like to thank Miguel Rivera-Torrente for con-
ducting in-situ IR measurements.
(
19) Dhakshinamoorthy, A.; Garcia, H. Catalysis by metal nano-
REFERENCES
particles embedded on metal-organic frameworks. Chem. Soc. Rev.
012, 41, 5262–5284.
(20) White, R. J.; Luque, R.; Budarin, V. L.; Clark, J. H.; Macquar-
rie, D. J. Supported metal nanoparticles on porous materials. Methods
2
(
1) Astruc, D.; Lu, F.; Aranzaes, J. R. Nanoparticles as recyclable
catalysts: The frontier between homogeneous and heterogeneous
catalysis. Angew. Chem. Int. Ed. 2005, 44, 7852–7872.
and applications. Chem. Soc. Rev. 2009, 38, 481–494.
(
21) Rösler, C.; Fischer, R. A. Metal–organic frameworks as hosts
(
2) Oliver-Meseguer, J.; Cabrero-Antonino, J. R.; Domínguez, I.;
for nanoparticles. CrystEngComm 2015, 17, 199–217.
Leyva-Pérez, A.; Corma, A. Small gold clusters formed in solution
give reaction turnover numbers of 10(7) at room temperature. Science
(22) Hermes, S.; Schröter, M.-K.; Schmid, R.; Khodeir, L.; Muhler,
M.; Tissler, A.; Fischer, R. W.; Fischer, R. A. Metal@MOF: Loading
of highly porous coordination polymers host lattices by metal organic
chemical vapor deposition. Angew. Chem. Int. Ed. 2005, 44, 6237–
2
012, 338, 1452–1455.
(3) Desireddy, A.; Conn, B. E.; Guo, J.; Yoon, B.; Barnett, R. N.;
Monahan, B. M.; Kirschbaum, K.; Griffith, W. P.; Whetten, R. L.;
Landman, U. Bigioni, T. P. Ultrastable silver nanoparticles. Nature
6
241.
23) Hermannsdörfer, J.; Friedrich, M.; Kempe, R. Colloidal size
(
2
013, 501, 399.
4) Heiz, U.; Sanchez, A.; Abbet, S.; Schneider, W.-D. Catalytic
effect and metal-particle migration in M@MOF/PCP catalysis. Chem-
istry 2013, 19, 13652–13657.
(
Oxidation of Carbon Monoxide on Monodispersed Platinum Clusters:
Each Atom Counts. J. Am. Chem. Soc. 1999, 121, 3214–3217.
(
24) Lu, G.; Li, S.; Guo, Z.; Farha, O. K.; Hauser, B. G.; Qi, X.;
Wang, Y.; Wang, X.; Han, S.; Liu, X.; DuChene, J. S.; Zhang, H.;
Zhang, Q.; Chen, X.; Ma, J.; Loo, S. C. J.; Wei, W. D.; Yang, Y.;
Hupp, J. T.; Huo, F. Imparting functionality to a metal–organic
framework material by controlled nanoparticle encapsulation. Nat.
Chem. 2012, 4, 310.
(
5) Lang, S. M.; Bernhardt, T. M. Gas phase metal cluster model
systems for heterogeneous catalysis. Phys. Chem. Chem. Phys. 2012,
4, 9255–9269.
6) Lei, Y.; Mehmood, F.; Lee, S.; Greeley, J.; Lee, B.; Seifert, S.;
1
(
Winans, R. E.; Elam, J. W.; Meyer, R. J.; Redfern, P. C.; Teschner,
D.; Schlögl, R.; Pellin, M. J.; Curtiss, L. A.; Vajda, S. Increased silver
activity for direct propylene epoxidation via subnanometer size ef-
fects. Science 2010, 328, 224–228.
(
25) Islamoglu, T.; Goswami, S.; Li, Z.; Howarth, A. J.; Farha, O.
K.; Hupp, J. T. Postsynthetic Tuning of Metal-Organic Frameworks
for Targeted Applications. Acc. Chem. Res. 2017, 50, 805–813.
(26) Fortea-Pérez, F. R.; Mon, M.; Ferrando-Soria, J.; Boronat, M.;
Leyva-Pérez, A.; Corma, A.; Herrera, J. M.; Osadchii, D.; Gascon, J.;
Armentano, D.; Pardo, E. The MOF-driven synthesis of supported
palladium clusters with catalytic activity for carbene-mediated chem-
istry. Nat. Mater. 2017, 16, 760.
(
7) Harding, D. J.; Fielicke, A. Platinum group metal clusters:
From gas-phase structures and reactivities towards model catalysts.
Chem. Eur. J. 2014, 20, 3258–3267.
(
8) Imaoka, T.; Kitazawa, H.; Chun, W.-J.; Yamamoto, K. Finding
the Most Catalytically Active Platinum Clusters With Low Atomicity.
Angew. Chem. Int. Ed. 2015, 54, 9810–9815.
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