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Pt Nanoparticles - Overview

Pt Nanoparticles - Overview

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Published by Webb Norfleet
What do PtNPs do?
What do PtNPs do?

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Categories:Types, Research
Published by: Webb Norfleet on May 30, 2013
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Platinum nanomaterials
DOI: 10.1002/smll.200600015
Pt Nanoparticles Surfactant-Directed Assembled into Colloidal Spheres and usedas Substrates in Forming Pt Nanorods andNanowires**
 Jingyi Chen, Yujie Xiong, Yadong Yin, andYounan Xia*
One-dimensional (1D) nanostructures have been extensivelystudied in recent years because of their extraordinary prop-erties arising from reduction in both dimensionality andsize, as well as their potential applications in fabricatingnanoscale devices.
[1]
In spite of many successful demonstra-tions, it remains a grand challenge to produce large quanti-ties of 1D nanostructures from various noble metals, togeth-er with well-controlled dimensions and morphologies. Here,we demonstrate that Pt nanoparticles formed via polyol re-duction could be assembled into spherical aggregates underthe direction of sodium dodecyl sulfate (SDS) and thenserve as substrates to generate Pt nanorods and nanowires.Platinum has found widespread use in a range of appli-cations due to its unique physical and chemical properties.
[2]
For instance, it prevails as a major catalyst in many industri-al processes such as the synthesis of nitric acid, reduction of pollutant gases emitted from automobiles, oil cracking, andproton-membrane-exchange (PME) fuel cells.
[3]
A greatdeal of effort has been devoted to the preparation of Ptnanostructures via chemical protocols.
[4]
However, most of these previous studies have been limited to nanoparticles;only polycrystalline nanorods and nanotubes have recentlybeen prepared by templating against channels within porousmaterials,
[5]
Ag or Se nanowires,
[6]
and assemblies of organicsurfactants.
[7]
Although template-directed syntheses haveproven straightforward and versatile, they are restricted bya number of drawbacks that may include, for example, therequirement of template removal in order to generate pureproduct, the limited scope of morphological variation, andthe polycrystallinity usually associated with the product.In a recent study,
[8]
we discovered that the addition of asmall amount of an iron species (Fe
2
+
or Fe
3
+
) to the polyolprocess could significantly alter the reduction kinetics of aPt precursor and thus induce the formation of Pt nanorodscharacterized by uniform diameters and relatively highaspect ratios. We demonstrate here that the synthesis couldbe further modified to program the growth of such nanorodsinto nanowires with lengths
>
500 nm. Based on our previ-ous scanning electron microscopy (SEM) and transmissionelectron microscopy (TEM) studies of the reaction mecha-nism, Pt nanoparticles tended to aggregate into large colloi-dal spheres before the concentration of Pt atoms was re-duced to a certain level to facilitate highly anisotropicgrowth. When SDS was added as the directing agent, thespherical aggregates could be synthesized with much smallersizes. These spherical aggregates were sufficiently stable insolvents such as acetone, alcohol, and water, even under theapplication of sonication for up to 30 min. As a result, thesespherical aggregates could serve as substrates to grow Ptnanorods and nanowires through polyol reduction in thepresence of a trace amount of iron species. As a major ad-vantage over previous protocols, one might be able to usematerials less precious than Pt to form the substrates forgrowing Pt nanowires with controllable lengths.
[8d]
Figure 1 illustrates the two-step protocol that was de-signed to achieve a tight control over the formation of Ptnanorods and nanowires. In the first step, Pt nanoparticleswere formed and then assembled into spherical aggregateswhen H
2
PtCl
6
was reduced by ethylene glycol (EG) at110
8
C in the presence of SDS. Depending on the molarratio of H
2
PtCl
6
to SDS, the Pt nanoparticles were found toexist in different forms. When the molar ratio of H
2
PtCl
6
toSDS was lower than 1:1, the Pt nanoparticles were well-dis-persed as individual entities (product A in Figure 1). As themolar ratio was increased to 1:5, the Pt nanoparticles weredirected by SDS to further assemble into submicrometer-sized spheres (product B in Figure 1). These spherical aggre-gates could be separated from the reaction solution andwashed several times with ethanol and water. In the nextstep, these spherical aggregates were added to 4 mL of EGwith a trace amount of iron species. After heating at 110
8
Cin air for one hour to activate the surface layer of the aggre-gates, certain amounts of H
2
PtCl
6
/EG and PVP/EG (PVP:poly(vinyl pyrrolidone)) were then added dropwise to thereaction. Similar to our previous observations,
[8a]
the Pt
IV
species were reduced at an extremely slow rate, and the re-sultant Pt atoms started to nucleate and grow into uniform1D nanostructures on the surface of each aggregate (pro-duct C in Figure 1).Figure 2 shows TEM and SEM images of Pt nanostruc-tures corresponding to the products illustrated in Figure 1.Consistent with the schematic drawing, uniform sphericalaggregates of Pt nanoparticles could be synthesized underthe direction of SDS and further used as substrates to formPt nanorods and nanowires. Figure 2A shows a TEM imageof the Pt nanoparticles when the reduction of the Pt
IV
pre-
[*] J. Chen, Dr.Y. Xiong, Prof.Y. XiaDepartment of Chemistry, University of WashingtonSeattle, WA 98195-1700 (USA)Fax: ( 
+
1)206-685-8665E-mail: xia@chem.washington.eduDr. Y. YinThe Molecular FoundryLawrence Berkeley National LaboratoryBerkeley, CA 94720 (USA)[**] This work was supported in part by the NSF (DMR-0451788) anda fellowship from the David and Lucile Packard Foundation. Y.X.is a Camille Dreyfus Teacher Scholar. This work used the Nano-tech User Facility (NTUF) at the University of Washington, amember of the National Nanotechnology Infrastructure Network(NNIN) funded by the NSF. We also thank the Molecular Foundryat the Lawrence Berkeley National Laboratory for the HRTEManalysis.Supporting information for this article is available on the WWWunder http://www.small-journal.com or from the author.
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cursor was performed at a molar ratio of 1:1 for H
2
PtCl
6
toSDS. The inset gives a magnified TEM image of the nano-particles, which were roughly spherical in shape with amean diameter of 
%
5 nm.Figure 2B shows anSEM image of the productwhen the molar ratio of H
2
PtCl
6
to SDS was in-creased to 1:5. The upper-right inset shows a TEMimage of a single sphericalaggregate of 
%
200 nm indiameter, while the lower-left inset gives a magnifiedSEM image of the surfacelayer of this aggregate,confirming the presence of a dense array of Pt nano-particles
%
5 nm in size.The X-ray diffraction(XRD) pattern shown inFigure S1 (see SupportingInformation) indicates thatthe Pt in the spherical ag-gregates was crystallized ina face-centered cubic (fcc)structure similar to bulkPt. Note that similar spher-ical aggregates of Pt nano-particles were also ob-tained by increasing themolar ratio of H
2
PtCl
6
toSDS up to 1:35. Thesespherical aggregates couldbe prepared as stable sus-pensions in water or EGfor a month.Figure 2C shows anSEM image of the Pt struc-tures when the iron-medi-ated reduction was carriedout in air with the spheri-cal aggregates serving assubstrates. The final prod-uct contained submicrome-ter-sized objects of Ptnanoparticles whose sur-
A
faces had been covered bya dense array of uniformnanorods. Compared withour previous studies, theoverall size of these aggre-gates had been reduced bymore than five times. Bytaking advantage of thenucleation site on the sub-strate surface, it should bepossible to use much lessH
2
PtCl
6
to form the samequantity of Pt nanorods and nanowires. Since the nanowireswere loosely attached to the surface of substrate, they couldbe released via brief sonication without breaking the spheri-cal aggregates. Once free, the wires could be harvested by
Figure 1.
A schematic illustration of the two-step method used to form Pt nanorods/nanowires on the sur-face of a spherical aggregate of Pt nanoparticles. In the initial step, the spherical aggregate of Pt nanoparti-cles was synthesized by reducing [PtCl
6
]
2
À
ions in the presence of a high concentration of sodium dodecylsulfate (SDS). In the second step, this aggregate was used as a substrate to direct the formation of Pt nano-rods/nanowires.
Figure 2.
A) TEM image of well-dispersed Pt nanoparticles, and B) SEM image of spherical aggregates of Ptnanoparticles; both samples were prepared via polyol reduction at two different molar ratios betweenH
2
PtCl
6
and SDS: A) 1:1; B) 1:5. The inset in (A) shows a magnified image of the Pt nanoparticles whosemean diameter was approximately 5 nm. The insets in (B) show SEM (lower-left) and TEM (upper-right)images of a spherical aggregate of Pt nanoparticles, revealing the presence of a dense array of Pt nanoparti-cles on the surface. C) SEM image of Pt nanorods grown on the surfaces of spherical aggregates. D) TEMimage of Pt nanorods after they had been released from the surface by brief sonication. The inset in (D)gives a typical selective-area electron diffraction (SAED) pattern of the Pt nanorods, with the four ringsindexed to the {111}, {200}, {220}, and {311} planes. Note that several nanorods could grow from the sameseed of the Pt nanoparticle, resulting in a branched morphology.
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centrifugation and then redispersed in ethanol or waterwithout introducing additional surfactants. Figure 2D showsa typical TEM image of some Pt nanorods (
%
5 nm in diam-eter) obtained using this procedure. The inset shows a se-lected-area electron diffraction (SAED) pattern. The fourrings could be indexed to the {111}, {200}, {220}, and {311}planes of fcc Pt, respectively. It is clear that the Pt nanorodssynthesized using this method were crystallized with an fccstructure similar to the bulk solid.In another demonstration, we combined the two stepsinto one and performed the synthesis without separating theaggregates of Pt nanoparticles from the solution. More in-terestingly, we were able to control the length of the Ptnanorods and obtain long nanowires by controlling theamount of H
2
PtCl
6
sequentially added to the reaction. Fig-ure 3A shows an SEM image of the product when an ex-tremely small amount of H
2
PtCl
6
precursor (1 m
m
in finalconcentration) was added and reduced by EG under air inthe presence of a trace amount of iron species. Similar tothe product B shown in Figure 1, the surface of each aggre-gate was mainly covered by small Pt nanoparticles due to avery low concentration of the Pt precursor. AdditionalH
2
PtCl
6
was then introduced at two different concentrationsto the reaction (1 m
m
and 10 m
m
in final concentration) toobtain the products depicted in Figure 3B and C, respective-ly. Again, the concentra-tion of Pt atoms would begreatly reduced becausePt
0
could be oxidized backto Pt
II
by Fe
3
+
. The addi-tion of Pt atoms wasswitched to a highly aniso-tropic mode to form 1Dnanostructures on the sur-face of each aggregate. Fig-ure 3B shows an SEMimage of the Pt aggregateswhose surfaces were parti-ally covered by Pt nano-rods. Due to the relativelylow concentration oH
2
PtCl
6
, only a portion of these aggregates was cov-ered with dense arrays of Pt nanorods. Figure 3Cshows an SEM image of the Pt aggregates where allof their surfaces were cov-ered with Pt nanowires.Because the H
2
PtCl
6
pre-cursor existed in the solu-tion at a low concentrationfor a long period of time,the Pt atoms could growinto nanowires more than500 nm in length, as shownin Figure 3D. After synthe-sis, the Pt nanowires couldalso be separated from thesubstrates via a combination of brief sonication and centri-fugation.Figure 4A shows a TEM image of some long Pt nano-wires that were released from the sample shown in Fig-ure 3C. As mentioned above, the Pt nanowires were looselyattached to the surface of the substrate (i.e., the sphericalaggregate of Pt nanoparticles) and could be sonicated off and then collected by centrifugation and redispersed inwater or ethanol. Due to the small diameters of these nano-wires, it is highly possible to break the nanowires during thesonication process. The inset shows a typical SAED pattern.Figure 4B shows a high-resolution (HR) TEM image re-corded from the end of a single Pt nanowire, indicating thatthe nanowire grew along the
<
111
>
direction. The latticespacing between the {111} planes, 0.23 nm, is in agreementwith the value of the bulk crystal. Figure 4C shows aHRTEM image recorded from the bending part of a Ptnanowire, showing that the nanowire was still a single crys-tal. Both arms of the bending nanowire grew along the
<
111
>
direction, with an angle of 134
8
between the twoarms. Figure 4D shows a TEM image of an individual Ptnanowire that was more than 500 nm in length.In summary, we have synthesized Pt nanowires with con-trollable lengths by using spherical aggregates of Pt nano-particles as substrates and by adding different amounts of Pt
Figure 3.
A) SEM image of spherical aggregates of Pt nanoparticles that were obtained when an extremelysmall amount of H
2
PtCl
6
precursor (1 m
m
 ) was added and reduced by EG in air in the presence of a traceamount of iron species. B,C) SEM images of Pt nanostructures that were obtained by consecutively adding 1 mL of two different concentrations of Pt precursor to the reaction mixture without removing the product:B) 1 m
m
and C) 10 m
m
H
2
PtCl
6
, respectively. D) SEM image showing a magnified view of the long Pt nano-wires grown on the surface, as boxed in (C).
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