Scalable strategies for the synthesis of well-defined copper metal and oxidenanocrystals

Lignier, Pascal; Bellabarba, Ronan M.; Tooze, Robert P.

doi:10.1039/c1cs15223h

Cited by 148 publications

(128 citation statements)

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“…[1][2][3][4][5][6][7][8][9][10][11] Their small sizes, generally reported between 1 and 100 nm, lead to unique physico-chemical properties between the bulk and molecular states, which vary greatly with small changes in NP size. For example, the catalytic properties of NPs are largely determined by the energy of the surface atoms, in turn controlled by the number of neighbouring atoms, dictated by their size, as well as the presence and nature of ligands or supports.…”

Section: Introductionmentioning

confidence: 99%

Single step synthesis of metallic nanoparticles using dihydroxyl functionalized ionic liquids as reductive agent

et al. 2013

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Section: Introductionmentioning

confidence: 99%

Single step synthesis of metallic nanoparticles using dihydroxyl functionalized ionic liquids as reductive agent

et al. 2013

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“…Furthermore, the preferential adsorption of organic (ligands, polymers, surfactants) or inorganic C under dihydrogen atmosphere (3 bar) following different addition rates of the metal precursor ([Co{N (SiMe 3 ) 2 } 2 (THF)]) to a solution of conventional ligands (hexadecylamine and lauric acid) at room temperature [23] (ions, gases) agents is an advanced strategy for the selective growth or etching of specific facets. This can result in sophisticated nanocrystals via well-controlled nucleation, growth and etching steps [1][2][3][4]. Finally, the precise engineering of ligand-nanocrystal interfaces in conventional solvents led to hybrid nanomaterials which exhibit specific properties such as selectivity control in catalysis [17,29,30] and air stability [4].…”

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confidence: 99%

“…This can result in sophisticated nanocrystals via well-controlled nucleation, growth and etching steps [1][2][3][4]. Finally, the precise engineering of ligand-nanocrystal interfaces in conventional solvents led to hybrid nanomaterials which exhibit specific properties such as selectivity control in catalysis [17,29,30] and air stability [4].…”

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confidence: 99%

“…the formation and evolution of a complex formed from the metal precursor and an organic additive, is crucial for controlling the final properties of the nanocrystals (Figs. 2 and 3) [4,[23][24][25][26][27][28]. Furthermore, the preferential adsorption of organic (ligands, polymers, surfactants) or inorganic C under dihydrogen atmosphere (3 bar) following different addition rates of the metal precursor ([Co{N (SiMe 3 ) 2 } 2 (THF)]) to a solution of conventional ligands (hexadecylamine and lauric acid) at room temperature [23] (ions, gases) agents is an advanced strategy for the selective growth or etching of specific facets.…”

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confidence: 99%

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Size Control of Monodisperse Metal Nanocrystals in Ionic Liquids

Lignier

2015

Ionic Liquids (ILs) in Organometallic Catalysis

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During the last decade, a great interest in the preparation of uniform nanocrystals has offered efficient synthetic strategies to precisely engineer metal, metal oxide and alloy at the nanoscale. Due to their physicochemical properties, ionic liquids (ILs) simultaneously demonstrated their potential in different areas such as nanocrystal synthesis, catalysis and energy. As a result, ionic liquids have been employed for the preparation of monodisperse nanocrystals and the control of their size. This chapter highlights the most promising methods for the synthesis of uniform nanocrystals in ionic liquids which act as a solvent, stabiliser, reducing agent and even precursor. As a result, successful preparations of nanoparticles in the presence of ILs are now available for both noble and earth-abundant elements such as gold, platinum, iridium, silver, palladium, ruthenium, rhodium, copper, nickel, cobalt and iron.The formation mechanisms of these nanocrystals are discussed as well as our mechanistic understanding in conventional organic and aqueous solvents. In addition, the IL approach is compared to leading methods in conventional solvents to make possible the identification of general principles for most metallic elements. By analogy with conventional solvents, these strategies can be adapted to the preparation of semiconductor nanocrystals. These achievements are going to drive the identification of relationships between the nature of ILs components, the physicochemical properties of ILs, the formation of nanocrystals in ILs and the resulting performances of these nano-objects.

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“…20,21 Like CuO nanocrystals, nitridation of Cu 2 O nanocrystals could also lead to Cu 3 N. Controlled syntheses (monodispersity, size, morphology) of Cu 2 O nanocrystals by electrodeposition, wet chemical, and solvothermal methods exist, along with reports on their surface, catalytic, and electrical properties. 20,22,23 An interesting feature of Cu 3 N is its documented decomposition upon heating or electron bombardment. For example, Cu 3 N thin films convert to CuO nanowire arrays by annealing in air.…”

Section: ■ Introductionmentioning

confidence: 99%

Preparation and Instability of Nanocrystalline Cuprous Nitride

et al. 2015

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Low-dimensional cuprous nitride (Cu 3 N) was synthesized by nitridation (ammonolysis) of cuprous oxide (Cu 2 O) nanocrystals using either ammonia (NH 3 ) or urea (H 2 NCONH 2 ) as the nitrogen source. The resulting nanocrystalline Cu 3 N spontaneously decomposes to nanocrystalline CuO in the presence of both water and oxygen from air at room temperature. Ammonia was produced in 60% chemical yield during Cu 3 N decomposition, as measured using the colorimetric indophenol method. Because Cu 3 N decomposition requires H 2 O and produces substoichiometric amounts of NH 3 >, we conclude that this reaction proceeds through a complex stoichiometry that involves the concomitant release of both N 2 and NH 3 . This is a thermodynamically unfavorable outcome, strongly indicating that H 2 O (and thus NH 3 production) facilitate the kinetics of the reaction by lowering the energy barrier for Cu3N decomposition. The three different Cu 2 O, Cu 3 N, and CuO nanocrystalline phases were characterized by a combination of optical absorption, powder Xray diffraction, transmission electron microscopy, and electronic density of states obtained from electronic structure calculations on the bulk solids. The relative ease of interconversion between these interesting and inexpensive materials bears possible implications for catalytic and optoelectronic applications. Disciplines Chemistry | Inorganic Chemistry CommentsReprinted (adapted) with permission from Inorganic Chemistry 54 (2015) ABSTRACT: Low-dimensional cuprous nitride (Cu 3 N) was synthesized by nitridation (ammonolysis) of cuprous oxide (Cu 2 O) nanocrystals using either ammonia (NH 3 ) or urea (H 2 NCONH 2 ) as the nitrogen source. The resulting nanocrystalline Cu 3 N spontaneously decomposes to nanocrystalline CuO in the presence of both water and oxygen from air at room temperature. Ammonia was produced in 60% chemical yield during Cu 3 N decomposition, as measured using the colorimetric indophenol method. Because Cu 3 N decomposition requires H 2 O and produces substoichiometric amounts of NH 3 , we conclude that this reaction proceeds through a complex stoichiometry that involves the concomitant release of both N 2 and NH 3 . This is a thermodynamically unfavorable outcome, strongly indicating that H 2 O (and thus NH 3 production) facilitate the kinetics of the reaction by lowering the energy barrier for Cu 3 N decomposition. The three different Cu 2 O, Cu 3 N, and CuO nanocrystalline phases were characterized by a combination of optical absorption, powder X-ray diffraction, transmission electron microscopy, and electronic density of states obtained from electronic structure calculations on the bulk solids. The relative ease of interconversion between these interesting and inexpensive materials bears possible implications for catalytic and optoelectronic applications.

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Scalable strategies for the synthesis of well-defined copper metal and oxidenanocrystals

Cited by 148 publications

References 73 publications

Single step synthesis of metallic nanoparticles using dihydroxyl functionalized ionic liquids as reductive agent

Single step synthesis of metallic nanoparticles using dihydroxyl functionalized ionic liquids as reductive agent

Size Control of Monodisperse Metal Nanocrystals in Ionic Liquids

Preparation and Instability of Nanocrystalline Cuprous Nitride

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