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Shape-Controlled Synthesis of Palladium Nanocrystals
Shape-Controlled Synthesis of Palladium Nanocrystals
pubs.acs.org/NanoLett
© 2013 American Chemical Society 2276 dx.doi.org/10.1021/nl400893p | Nano Lett. 2013, 13, 2276−2281
Nano Letters Letter
Figure 1. (a) Schematic illustration showing the formation of Pd octahedrons and tetrahedrons, respectively, by using Na2PdCl4 and Pd(acac)2 as
the precursors for seed-mediated growth. (b−d) Typical TEM images of the Pd cuboctahedral seeds, octahedrons, and tetrahedrons. The insets
show the corresponding samples at a higher magnification with the scale bars being 5 nm. The 20 nm scale bar applies to all other images.
without the involvement of any reductant and stabilizer.7 microscopy (TEM) image of the as-obtained cuboctahedral
Huang and co-workers recently synthesized Pt tetrahedrons by seeds of Pd with a purity approaching 100%. The Pd
taking advantage of the selective capping effect of a peptide cuboctahedrons were enclosed by a mix of both {111} and
engineered with a specific sequence.8 Zheng and co-workers {100} facets on the surface.
and Yan and co-workers prepared Pd concave tetrahedrons and We conducted the seed-mediated growth of Pd nanocrystals
Pt−Pd tetrahedrons, respectively, by introducing formaldehyde by introducing different precursors into a polyol system
into a hydrothermal reaction.9 All of these studies were unable containing both the Pd seeds and PVP. In a typical synthesis,
to decipher the growth pathway that led to the formation of the Pd seeds and PVP were first dissolved in tetraethylene
tetrahedrons because it was essentially impossible to separate glycol (TTEG) at 140 °C under magnetic stirring. Here TTEG
the nucleation and growth steps in these one-pot syntheses. acted as both a solvent and a reductant while PVP served as a
Here we demonstrate that seed-mediated growth could be colloidal stabilizer. The two different Pd precursors, Na2PdCl4
used to obtain Pd nanocrystals with a tetrahedral or octahedral and Pd(acac)2, were dissolved in TTEG and then quickly
shape depending on the precursor. The use of presynthesized injected into the reaction mixtures with a pipet, respectively.
seeds with the same size, shape, crystallinity, surface capping The color of the solution was gradually darkened with time
agent, dispersion medium, and particle concentration allowed after the injection of both precursors, indicating that the
us to single out one specific parameter for study.10 As a model precursor compounds were reduced to Pd atoms by TTEG at
system, Pd cuboctahedrons of 5 nm in size were synthesized the used temperature. After 1 h, we obtained Pd nanocrystals
using a polyol method and then used as seeds for growth. with distinct shapes in the two syntheses conducted in parallel.
Except for the use of different precursors, all other experimental As shown by TEM image in Figure 1c, Pd octahedrons
conditions including temperature, reductant, solvent, and the enclosed by eight {111} facets were obtained in the presence of
concentrations of seeds/reagents were kept the same. When Na2PdCl4 as a precursor with an average edge length of 12.8 ±
Pd(acac)2 was used as a precursor, we obtained octahedrons, 1.3 nm. In comparison, Pd tetrahedrons enclosed by four {111}
truncated tetrahedrons, and then tetrahedrons at different facets were obtained under the same condition, except for the
stages of growth. In contrast, the same seeds only evolved into use of Pd(acac)2 as precursor (Figure 1d). The average edge
octahedrons with increasing sizes when we switched the length of the Pd tetrahedrons was 14.5 ± 1.0 nm. Clearly, the
precursor from Pd(acac)2 to Na2PdCl4. We also investigated difference in final shape for the Pd nanocrystals obtained
the mechanism responsible for the formation of Pd nanocryst- through the seed-mediated growth should be attributed to the
als with a tetrahedral shape and found that it was related to the different precursors involved since all other parameters,
much faster reduction rate of Pd(acac)2 relative to Na2PdCl4. including the seeds, temperature, reductant/solvent, and the
Figure 1a shows a schematic that compares the evolution concentrations of reagents, were kept the same.
pathways from single-crystal, cuboctahedral seeds of Pd to In order to understand how Pd nanocrystals with distinct
octahedral and tetrahedral nanocrystals when Na2PdCl4 and shapes were formed when the two different precursors were
Pd(acac)2 were used as the precursors, respectively. The Pd used, we analyzed the products sampled at different reaction
cuboctahedrons were 5 nm in size and synthesized by reducing times by TEM. In this case, aliquots were taken out from the
Na2PdCl4 with ethylene glycol as a solvent and reductant at 160 reaction mixture at different time points in the early stage (≤10
°C in the presence of poly(vinyl pyrrolidone) (PVP) as a min) of a standard synthesis after the introduction of Pd
stabilizer. Figure 1b shows a typical transmission electron precursor. Figure 2a−c shows TEM images and the
2277 dx.doi.org/10.1021/nl400893p | Nano Lett. 2013, 13, 2276−2281
Nano Letters Letter
Figure 2. TEM images of Pd nanocrystals obtained in the early stages of standard syntheses when (a−c) Na2PdCl4 and (d−f) Pd(acac)2 were used
as the precursors, respectively. (a,d) 0.5, (b,e) 1.5, and (c,f) 10 min. The insets show 3D models of the corresponding products obtained at different
time points. The 20 nm scale bar applies to all images.
Figure 3. Structural analyses of the Pd tetrahedrons and truncated tetrahedrons obtained in a standard synthesis: (a) HAADF-STEM image of a Pd
tetrahedron; (b) HAADF-STEM image of a Pd truncated tetrahedron; (c) typical TEM images of individual Pd truncated tetrahedrons at different
orientations; and (d) 3D models of truncated tetrahedrons at different orientations matching the TEM images in (c). The insets in (a) and (b) show
the corresponding FT patterns for the Pd tetrahedron and truncated tetrahedron.
corresponding three-dimensional (3D) models of the Pd energy of {100} facets relative to {111} facets.11 Once the
nanocrystals obtained at different time points when Na2PdCl4 nanocrystals were fully enclosed by {111} facets, the octahedral
was used as a precursor. At t = 0.5 min, Pd octahedrons with shape would not change any more with the increase of reaction
slight truncation at corners were observed. This result time, while the edge length gradually increased from 5.5 ± 0.5
confirmed that the growth was mainly limited to the ⟨100⟩ nm at t = 0.5 min to 6.7 ± 0.6 and 9.0 ± 0.8 nm for t = 1.5 and
directions in the initial stage due to the higher surface free 10 min, respectively.
2278 dx.doi.org/10.1021/nl400893p | Nano Lett. 2013, 13, 2276−2281
Nano Letters Letter
nanocrystals with shapes other than tetrahedrons were obtained corners/edges rather than the side faces of the Pd octahedron
in these cases. A similar observation was also reported by formed at the early stage owing to the higher surface energy of
Zheng and co-workers, where the stability of [PdI4]2− was these sites than the side faces. Then, the adatoms could migrate
found to be higher than Pd(acac)2 and the morphologies of Pd to the side faces through surface diffusion due to the relatively
nanocrystals generated by reducing Pd(acac)2 with DMF were high temperature used.14 When Pd(acac)2 was used as a
drastically varied with the addition of I−.12 It was also found precursor, the adatoms could only migrate to some of the eight
that [acac]− did not have any effect on the reaction kinetics side faces of an octahedron due to the fast reduction rate and
when Na2PdCl4 was used as a precursor, further suggesting the the relatively low concentration of available Pd2+ ions, resulting
stronger binding energy of Cl− with Pd2+ ions than [acac]−. In in the formation of a tetrahedral shape enclosed by four {111}
another experiment, we introduced Cl− into the reaction facets. In contrast, when the precursor was switched to
system at t = 1.5 min after most of the Pd(acac)2 had already Na2PdCl4, the slow reduction rate and the availability of Pd2+
been reduced. As shown in Supporting Information Figure S7, ions around a Pd octahedral seed at a relatively high
most of the nanocrystals in the products were still Pd concentration allowed them to migrate to all eight facets of
tetrahedrons. This result indicated that the ligand exchange the Pd seed, leading to the formation of a Pd octahedron.
between [acac]− and Cl− might occur on a slower time scale Taken together, we can conclude that it was the difference in
relative to the reduction of Pd(acac)2. As such, the growth reduction rate for Na2PdCl4 and Pd(acac)2 that led to the
pathway from octahedron to tetrahedron was not altered. formation of products with thermodynamically and kinetically
A tetrahedron can only be formed under a kinetically controlled shapes (i.e., octahedrons and tetrahedron), respec-
controlled condition because it has a much higher (1.3 times) tively.
surface area to volume ratio than an octahedron. As we In summary, we have demonstrated the effect of precursor on
discussed before, the newly formed Pd atoms resulting from the the reaction kinetics and thus growth pathway of a seed-
reduction of a Pd precursor tended to be deposited on the mediated synthesis. When Pd(acac)2 was used as a precursor,
{100} facets of a Pd cuboctahedral seed due to the difference in Pd cuboctahedral seeds could be directed to evolve into
surface free energy between the {100} and {111} facets. It is octahedrons, truncated tetrahedrons, and finally tetrahedrons as
worth noting that the edge length of the octahedrons obtained the reaction proceeded. In contrast, the same Pd seeds could
in the early stage of a synthesis involving Pd(acac)2 was only evolve into octahedrons when Na2PdCl4 was added into
relatively larger than the octahedrons obtained with Na2PdCl4 the reaction system as precursor. This study clearly
as the precursor (7.1 ± 0.5 nm vs 5.5 ± 0.5 nm at t = 0.5 min, demonstrates that nanocrystals enclosed by the same type of
as shown in Figure 2). This difference suggests that more facet but in different shapes could be obtained by manipulating
precursor had been reduced to Pd atoms and subsequently the reduction kinetics of a precursor. This work greatly
included into the Pd octahedrons for the case of Pd(acac)2 due advances our understanding of the growth mechanism for
to its faster reduction rate. This observation was consistent with nanocrystals with a tetrahedral shape. We believe this strategy
the ICP-MS data shown in Figure 4a. For the syntheses based upon the use of an appropriate precursor to manipulate
involving Pd(acac)2 and Na 2 PdCl 4 as the precursors, the reaction kinetics could also be extended to cover other
metals and even other types of inorganic materials.
■
respectively, the percentages of remaining Pd precursor in the
solutions were 22.9 and 79.1% at t = 0.5 min. As such, the Pd
atoms newly formed through the reduction of Pd(acac)2 would ASSOCIATED CONTENT
not be able to nucleate on all of the eight {111} facets of a Pd *
S Supporting Information
octahedron. Instead, only four of the eight {111} facets of an Experimental details and additional figures. This material is
available free of charge via the Internet at http://pubs.acs.org.
■
octahedron could be involved in the heterogeneous nucleation
and growth (as illustrated in Figure 1a and Figure S1 in the
Supporting Information). Once a cluster (or nucleus) of Pd AUTHOR INFORMATION
atoms had been created on a certain face of a seed, the Corresponding Author
reduction of precursor in the following step would preferen- *E-mail: younan.xia@bme.gatech.edu.
tially occur at this site rather than on other regions due to the Notes
lower energy barrier.13 The site-localized growth could be The authors declare no competing financial interest.
retained as long as the reduction rate is faster than the surface
diffusion rate of adatoms.14 Further growth of the four {111}
facets eventually resulted in the formation of Pd tetrahedrons.
■ ACKNOWLEDGMENTS
This work was supported in part by a grant from NSF (DMR-
In contrast, when Na2PdCl4 was used as a precursor, the 1215034) and startup funds from Georgia Institute of
availability of this precursor around a Pd octahedral seed at a Technology. Y.X. was partially supported by the World Class
relatively high concentration in the early stage of a synthesis University (WCU) program through the National Research
allowed the nucleation to occur on all eight facets of the Pd Foundation of Korea funded by the Ministry of Education,
seed. As a result, all of the eight {111} facets could undergo Science and Technology (R32-20031). As a jointly supervised
further growth, leading to the formation of Pd octahedrons Ph.D. student from Southwest University, Y.W. was also
with gradually increasing sizes. Even after the concentration of partially supported by a Fellowship from the China Scholarship
Pd2+ ions had dropped to a very low level at a later stage of the Council (CSC).
■
synthesis, the slow reduction rate of this precursor relative to
surface diffusion of adatoms still could not lead to localized REFERENCES
growth and thus formation of octahedrons.14 (1) (a) Jin, R.; Cao, Y.; Mirkin, C. A.; Kelly, K. L.; Schatz, G. C.;
The formation of a tetrahedron from an octahedron can also Zheng, J. G. Science 2001, 294, 1901. (b) Sun, Y.; Xia, Y. Science 2002,
be explained using another possible mechanism in which the 298, 2176. (c) Murphy, C. J.; Jana, N. R. Adv. Mater. 2002, 14, 80.
newly formed Pd atoms were preferentially deposited at the (d) Burda, C.; Chen, X.; Narayanan, R.; El-Sayed, M. A. Chem. Rev.
2005, 105, 1025. (e) Tao, A.; Sinsermsuksakul, P.; Yang, P. Nat.
Nanotechnol. 2007, 2, 435. (f) Anker, J. N.; Hall, W. P.; Lyandres, O.;
Shah, N. C.; Zhao, J.; Van Duyne, R. P. Nat. Mater. 2008, 7, 442.
(g) Wang, C.; Daimon, H.; Onodera, T.; Koda, T.; Sun, S. Angew.
Chem., Int. Ed. 2008, 47, 3588. (h) McEachran, M.; Keogh, D.;
Pietrobon, B.; Cathcart, N.; Gourevich, I.; Coombs, N.; Kitaev, V. J.
Am. Chem. Soc. 2011, 133, 8066. (i) Liu, X.; Wang, D.; Li, Y. Nano
Taday 2012, 7, 448.
(2) (a) Tao, A. R.; Habas, S.; Yang, P. Small 2008, 4, 310. (b) Xia, Y.;
Xiong, Y.; Lim, B.; Skrabalak, S. E. Angew. Chem., Int. Ed. 2009, 48, 60.
(3) (a) Zeng, J.; Zheng, Y.; Rycenga, M.; Tao, J.; Li, Z.-Y.; Zhang, Q.;
Zhu, Y.; Xia, Y. J. Am. Chem. Soc. 2010, 132, 8552. (b) Xia, X.; Zeng, J.;
Oetjen, L. K.; Li, Q.; Xia, Y. J. Am. Chem. Soc. 2012, 134, 1793.
(4) (a) Pietrobon, B.; McEachran, M.; Kitaev, V. ACS Nano 2009, 3,
21. (b) Langille, M. R.; Zhang, J.; Mirkin, C. A. Angew. Chem., Int. Ed.
2011, 50, 3543.
(5) (a) Zhang, Q.; Li, W.; Moran, C.; Zeng, J.; Chen, J.; Wen, L.-P.;
Xia, Y. J. Am. Chem. Soc. 2010, 132, 11372. (b) Xia, X.; Zeng, J.;
McDearmon, B.; Zheng, Y.; Li, Q.; Xia, Y. Angew. Chem., Int. Ed. 2011,
50, 12542. (c) Zhang, H.; Li, W.; Jin, M.; Zeng, J.; Yu, T.; Yang, D.;
Xia, Y. Nano Lett. 2011, 11, 898. (d) Xie, S.; Lu, N.; Xie, Z.; Wang, J.;
Kim, M. J.; Xia, Y. Angew. Chem., Int. Ed. 2012, 51, 10266.
(6) Ahmadi, T. S.; Wang, Z. L.; Green, T. C.; Henglein, A.; El-Sayed,
M. A. Science 1996, 272, 1924.
(7) Norimatsu, F. Y.; Mizokoshi, Y.; Mori, K.; Mizugaki, T.; Ebitani,
K.; Kaneda, K. Chem. Lett. 2006, 35, 276.
(8) Chiu, C.-Y.; Li, Y.; Ruan, L.; Ye, X.; Murray, C. B.; Huang, Y. Nat.
Chem. 2011, 3, 393.
(9) (a) Huang, X.; Tang, S.; Zhang, H.; Zhou, Z.; Zheng, N. J. Am.
Chem. Soc. 2009, 131, 13916. (b) Yin, A.-X.; Min, X.-Q.; Zhang, Y.-W.;
Yan, C.-H. J. Am. Chem. Soc. 2011, 133, 3816.
(10) (a) Jana, N. R.; Gearheart, L.; Murphy, C. J. Adv. Mater. 2001,
13, 1389. (b) Nikoobakht, B.; El-Sayed, M. A. Chem. Mater. 2003, 15,
1957. (c) Chen, Y.-H.; Hung, H.-H.; Huang, M. H. J. Am. Chem. Soc.
2009, 131, 9114. (d) Langille, M. R.; Personick, M. L.; Zhang, J.;
Mirkin, C. A. J. Am. Chem. Soc. 2012, 134, 14542.
(11) Vitos, L.; Ruban, A. V.; Skriver, H. L.; Kollár, J. Surf. Sci. 1998,
411, 186.
(12) Huang, X.; Zhang, H.; Guo, C.; Zhou, Z.; Zheng, N. Angew.
Chem., Int. Ed. 2009, 48, 4808.
(13) (a) Zeng, J.; Zhu, C.; Tao, J.; Jin, M.; Zhang, H.; Li, Z.-Y.; Zhu,
Y.; Xia, Y. Angew. Chem., Int. Ed. 2012, 51, 2354. (b) Zhu, C.; Zeng, J.;
Tao, J.; Johnson, M. C.; Schmidt-Krey, I.; Blubaugh, L.; Zhu, Y.; Gu,
Z.; Xia, Y. J. Am. Chem. Soc. 2012, 134, 15822. (c) Xia, X.; Xia, Y. Nano
Lett. 2012, 12, 6038.
(14) Xia, X.; Xie, S.; Liu, M.; Peng, H.-C.; Lu, N.; Wang, J.; Kim, M.
J.; Xia, Y. Proc. Natl. Acad. Sci. U.S.A. 2013, DOI: 10.1073/
pnas.1222109110.