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Title: Highly Selective Synthesis of Catalytically Active Monodisperse Rhodium Nanocubes

Abstract

Synthesis of monodisperse and shape-controlled colloidal inorganic nanocrystals (NCs) is of increasing scientific interest and technological significance. Recently, shape control of Pt, Pd, Ag, Au, and Rh NCs has been obtained by tuning growth kinetics in various solution-phase approaches, including modified polyol methods, seeded growth by polyol reduction, thermolysis of organometallics, and micelle techniques. Control of reduction kinetics of the noble metal precursors and regulation of the relative growth rates of low-index planes (i.e. {l_brace}100{r_brace} and {l_brace}111{r_brace}) via selective adsorption of selected chemical species are two keys for achieving shape modification of noble metal NCs. One application for noble metal NCs of well-defined shape is in understanding how NC faceting (determines which crystallographic planes are exposed) affects catalytic performance. Rh NCs are used in many catalytic reactions, including hydrogenation, hydroformylation, hydrocarbonylation, and combustion reactions. Shape manipulation of Rh NCs may be important in understanding how faceting on the nanoscale affects catalytic properties, but such control is challenging and there are fewer reports on the shape control of Rh NCs compared to other noble metals. Xia and coworkers obtained Rh multipods exhibiting interesting surface plasmonic properties by a polyol approach. The Somorjai and Tilley groups synthesized crystalline Rh multipods, cubes, hornsmore » and cuboctahedra, via polyol seeded growth. Son and colleagues prepared catalytically active monodisperse oleylamine-capped tetrahedral Rh NCs for the hydrogenation of arenes via an organometallic route. More recently, the Somorjai group synthesized sizetunable monodisperse Rh NCs using a one-step polyol technique. In this Communication, we report the highly selective synthesis of catalytically active, monodisperse Rh nanocubes of < 10 nm by a seedless polyol method. In this approach, Br{sup -} ions from trimethyl(tetradecyl)ammonium bromide (TTAB) effectively stabilize the {l_brace}100{r_brace} faces of Rh NCs, and induce the evolution of nanocubes (Scheme 1). For a typical synthesis, 0.2 mmol RhCl{sub 3} hydrate, 1 mmol TTAB, and 4 mmol poly(vinylpyrrolidone) (PVP, Mw = 24,000), were added to 20 ml ethylene glycol at room temperature. The stock solution was heated to 80 C and purged for 20 min while stirring, producing a dark brown solution. The flask was then heated to 185 C and maintained at this temperature for 1.5 h under an Ar atmosphere. When the reaction was complete, an excess of acetone was added to the solution at room temperature to precipitate the nanocubes. The Rh nanocubes were separated by centrifugation and washed twice by precipitation/dissolution with ethanol/hexanes.« less

Authors:
; ; ; ; ; ; ;
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
Chemical Sciences Division
OSTI Identifier:
957035
Report Number(s):
LBNL-1229E
Journal ID: ISSN 0002-7863; TRN: US201002%%909
DOE Contract Number:  
DE-AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Journal of American Chemical Society
Additional Journal Information:
Journal Volume: 130; Related Information: Journal Publication Date: 2008; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
37; ACETONE; ADSORPTION; BROMIDES; CARBONYLATION; CASKS; CENTRIFUGATION; COMBUSTION; GLYCOLS; HYDROGENATION; KINETICS; MODIFICATIONS; PERFORMANCE; REGULATIONS; RHODIUM; SHAPE; STIRRING; SYNTHESIS; TUNING

Citation Formats

Zhang, Y, Grass, M E, Kuhn, J N, Tao, F, Habas, S E, Huang, W, Yang, P, and Somorjai, G A. Highly Selective Synthesis of Catalytically Active Monodisperse Rhodium Nanocubes. United States: N. p., 2009. Web.
Zhang, Y, Grass, M E, Kuhn, J N, Tao, F, Habas, S E, Huang, W, Yang, P, & Somorjai, G A. Highly Selective Synthesis of Catalytically Active Monodisperse Rhodium Nanocubes. United States.
Zhang, Y, Grass, M E, Kuhn, J N, Tao, F, Habas, S E, Huang, W, Yang, P, and Somorjai, G A. Sat . "Highly Selective Synthesis of Catalytically Active Monodisperse Rhodium Nanocubes". United States. https://www.osti.gov/servlets/purl/957035.
@article{osti_957035,
title = {Highly Selective Synthesis of Catalytically Active Monodisperse Rhodium Nanocubes},
author = {Zhang, Y and Grass, M E and Kuhn, J N and Tao, F and Habas, S E and Huang, W and Yang, P and Somorjai, G A},
abstractNote = {Synthesis of monodisperse and shape-controlled colloidal inorganic nanocrystals (NCs) is of increasing scientific interest and technological significance. Recently, shape control of Pt, Pd, Ag, Au, and Rh NCs has been obtained by tuning growth kinetics in various solution-phase approaches, including modified polyol methods, seeded growth by polyol reduction, thermolysis of organometallics, and micelle techniques. Control of reduction kinetics of the noble metal precursors and regulation of the relative growth rates of low-index planes (i.e. {l_brace}100{r_brace} and {l_brace}111{r_brace}) via selective adsorption of selected chemical species are two keys for achieving shape modification of noble metal NCs. One application for noble metal NCs of well-defined shape is in understanding how NC faceting (determines which crystallographic planes are exposed) affects catalytic performance. Rh NCs are used in many catalytic reactions, including hydrogenation, hydroformylation, hydrocarbonylation, and combustion reactions. Shape manipulation of Rh NCs may be important in understanding how faceting on the nanoscale affects catalytic properties, but such control is challenging and there are fewer reports on the shape control of Rh NCs compared to other noble metals. Xia and coworkers obtained Rh multipods exhibiting interesting surface plasmonic properties by a polyol approach. The Somorjai and Tilley groups synthesized crystalline Rh multipods, cubes, horns and cuboctahedra, via polyol seeded growth. Son and colleagues prepared catalytically active monodisperse oleylamine-capped tetrahedral Rh NCs for the hydrogenation of arenes via an organometallic route. More recently, the Somorjai group synthesized sizetunable monodisperse Rh NCs using a one-step polyol technique. In this Communication, we report the highly selective synthesis of catalytically active, monodisperse Rh nanocubes of < 10 nm by a seedless polyol method. In this approach, Br{sup -} ions from trimethyl(tetradecyl)ammonium bromide (TTAB) effectively stabilize the {l_brace}100{r_brace} faces of Rh NCs, and induce the evolution of nanocubes (Scheme 1). For a typical synthesis, 0.2 mmol RhCl{sub 3} hydrate, 1 mmol TTAB, and 4 mmol poly(vinylpyrrolidone) (PVP, Mw = 24,000), were added to 20 ml ethylene glycol at room temperature. The stock solution was heated to 80 C and purged for 20 min while stirring, producing a dark brown solution. The flask was then heated to 185 C and maintained at this temperature for 1.5 h under an Ar atmosphere. When the reaction was complete, an excess of acetone was added to the solution at room temperature to precipitate the nanocubes. The Rh nanocubes were separated by centrifugation and washed twice by precipitation/dissolution with ethanol/hexanes.},
doi = {},
journal = {Journal of American Chemical Society},
issn = {0002-7863},
number = ,
volume = 130,
place = {United States},
year = {2009},
month = {2}
}