Seed-Mediated Growth of Nearly Monodisperse Palladium Nanocubes with Controllable Sizes

Niu, Wenxin; Li, Zhiyuan; Shi, Lihong; Liu, Xiaoqing; Li, Haijuan; Han, Shuang; Chen, Jiuan; Xu, Guobao

doi:10.1021/cg8002433

Cited by 236 publications

(216 citation statements)

References 49 publications

(47 reference statements)

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“…Pd cubes with the size of ~30 nm were prepared using cetyltrimethylammonium bromide (CTAB) as a capping agent [24], whereas 10 nm and 7 nm Pd nanocubes were synthesised by two methods developed by Xia and co-workers using polyvinylpyrrolidone (PVP) [25,26].…”

Section: Methodsmentioning

confidence: 99%

Oxygen electroreduction on carbon-supported Pd nanocubes in acid solutions

Erikson

Lüsi

Sarapuu

et al. 2016

Electrochimica Acta

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Please cite this article as: Heiki Erikson, Madis Lüsi, Ave Sarapuu, Kaido Tammeveski, Jose Solla-Gullón, Juan M.Feliu, Oxygen electroreduction on carbon-supported Pd nanocubes in acid solutions, Electrochimica Acta http://dx.doi.org/10.1016/j.electacta. 2015.11.125 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. Oxygen electroreduction on carbon-supported Pd nanocubes in acid solutions Highlights• Carbon-supported Pd nanocubes of three different size and loading were prepared• The specific activity for oxygen reduction reaction is independent of Pd content• Pd nanocubes possess higher specific activity for ORR than spherical Pd nanoparticles• The ORR on carbon-supported Pd nanocubes proceed mainly via 4-electron pathway• Tafel behaviour of ORR on carbon-supported Pd nanocubes is similar to that of bulk Pd AbstractThe oxygen reduction reaction (ORR) was studied on carbon-supported cubic palladium nanoparticles of different sizes (~30 nm, ~10 nm and ~7 nm). Cetyltrimethylammonium bromide (CTAB) and polyvinylpyrrolidone (PVP) were used as capping agents to prepare the nanocubes and Pd content in the catalyst samples was 20 and 50 wt%. The surface morphology of the prepared materials was studied by transmission electron microscopy (TEM). The catalyst materials were electrochemically characterised by cyclic voltammetry and CO stripping experiments. The rotating disk electrode (RDE) method was employed for ORR studies in 0.5 M H 2 SO 4 and 0.1 M HClO 4 solutions. The ORR results revealed that the specific activity of cubic Pd nanoparticles is higher than that of spherical Pd particles and does not depend on the Pd content in the catalyst, but decreases with decreasing the size of Pd nanocubes. Mass activity of Pd nanocubes increased with decreasing the particle size. The ORR proceeds mainly via 4-electron pathway and the reaction mechanism is similar to that on bulk Pd.

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Section: Methodsmentioning

confidence: 99%

Oxygen electroreduction on carbon-supported Pd nanocubes in acid solutions

Erikson

Lüsi

Sarapuu

et al. 2016

Electrochimica Acta

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“…The recrystallization process involves the migration of atomic species on the two-dimensional surface of a nanocrystal, giving rise to reconstruction of the surface and thus shape. During this shape focusing process, bromide ions seem to play a significant role in promoting the formation of {100} facets by lowering their surface energy through the preferential chemisorption [25][26][27], and thus inducing evolution of the shape into a nanobar.…”

Section: Introductionmentioning

confidence: 99%

New insights into the growth mechanism and surface structure of palladium nanocrystals

et al. 2010

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This paper presents a systematic study of the growth mechanism for Pd nanobars synthesized by reducing Na 2 PdCl 4 with L-ascorbic acid in an aqueous solution in the presence of bromide ions as a capping agent. Transmission electron microscopy (TEM) and high-resolution TEM analyses revealed that the growth at early stages of the synthesis was dominated by particle coalescence, followed by shape focusing via recrystallization and further growth via atomic addition. We also investigated the detailed surface structure of the nanobars using aberration-corrected scanning TEM and found that the exposed {100} surfaces contained several types of defects such as an adatom island, a vacancy pit, and atomic steps. Upon thermal annealing, the nanobars evolved into a more thermodynamically favored shape with enhanced truncation at the corners. KEYWORDSPalladium, nanocrystals, growth, coalescence, surface evolution Metal nanocrystals have attracted growing attention due to their fascinating properties and invaluable applications in catalysis, photonics, sensing, and imaging [1][2][3]. The physicochemical properties of a metal nanocrystal are determined by a set of parameters such as shape, size, and composition. In particular, shape control of a metal nanocrystal can provide a versatile avenue for tailoring its catalytic activity and selectivity because shape determines the arrangements of atoms on the surface [4][5][6][7][8]. For example, it has been shown that Pd nanocubes bounded by {100} facets can provide a four-fold improvement in specific activity for the formic acid oxidation reaction as compared to Pd octahedra bounded by {111} facets [9]. An exquisite shape control of metal nanocrystals is therefore essential for the maximization of their activity and thus their performance in many catalytic and electrocatalytic applications.In order to achieve a high-level control over the shape of metal nanocrystals prepared in a solution phase, a fundamental understanding of nucleation and growth mechanisms is a prerequisite. In the classical models, nanocrystals have been considered to grow by atomic addition [10][11][12]. However, recent experimental and theoretical studies have shown that particle coalescence Nano Res (2010) 3: 180-188 DOI 10.1007/s12274-010-1021-5 Research Article † These two authors contributed equally to this work.Address correspondence to Younan Xia, xia@biomed.wustl.edu; Jingyue Liu, liuj@umsl.edu Nano Res (2010) 3: 180-188 181 can also play an important role in the growth process [13][14][15][16][17]. For instance, oriented attachment was proposed as a growth mechanism to account for the formation of aggregates, nanorods, or nanowires for various metals and metal oxides [18][19][20][21][22][23]. Using in situ transmission electron microscopy (TEM), Alivisatos and co-workers recently provided direct evidence for the involvement of particle coalescence in the growth of Pt nanocrystals [24]. Despite these studies, however, a detailed description of the growth process is still missing, especially for...

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“…On the other hand, it has been demonstrated that the facets on the surface of Pd nanocrystals can have a strong influence on catalytic properties. So far, a wide variety of Pd nanocrystals with different shapes including cubes, bars, octahedra, plates, icosahedra, and pentagonal rods have all been prepared by carefully controlling reaction conditions such as temperature, reductants, capping agents, and concentrations of reagents and ionic species [27][28][29][30][31][32][33][34][35][36][37][38]. Nanoscale cubes and bars of Pd enclosed by {100} facets have received particular attention because these facets have been demonstrated to have a higher catalytic activity than {111} facets in some important reactions such as CO oxidation [39][40][41][42][43][44][45].…”

mentioning

confidence: 99%

Synthesis of Pd nanocrystals enclosed by {100} facets and with sizes <10 nm for application in CO oxidation

et al. 2010

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The catalytic activity of noble-metal nanocrystals is mainly determined by their sizes and the facets exposed on the surface. For single crystals, it has been demonstrated that the Pd(100) surface is catalytically more active than both Pd(110) and Pd(111) surfaces for the CO oxidation reaction. Here we report the synthesis of Pd nanocrystals enclosed by {100} facets with controllable sizes in the range of 6-18 nm by manipulating the rate of reduction of the precursor. UV-vis spectroscopy studies indicate that the rate of reduction of Na 2 PdCl 4 can be controlled by adjusting the concentrations of Br -and Cl -ions added to the reaction mixture. Pd nanocrystals with different sizes were immobilized on ZnO nanowires and evaluated as catalysts for CO oxidation. We found that the activity of this catalytic system for CO oxidation showed a strong dependence on the nanocrystal size. When the size of the Pd nanocrystals was reduced from 18 nm to 6 nm, the maximum conversion rate was significantly enhanced by a factor of ~10 and the corresponding maximum conversion temperature was lowered by ~80 °C . KEYWORDS

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Seed-Mediated Growth of Nearly Monodisperse Palladium Nanocubes with Controllable Sizes

Cited by 236 publications

References 49 publications

Oxygen electroreduction on carbon-supported Pd nanocubes in acid solutions

Oxygen electroreduction on carbon-supported Pd nanocubes in acid solutions

New insights into the growth mechanism and surface structure of palladium nanocrystals

Synthesis of Pd nanocrystals enclosed by {100} facets and with sizes <10 nm for application in CO oxidation

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