Efficient One-Pot Synthesis of Colloidal Zirconium Oxide Nanoparticles for High-Refractive-Index Nanocomposites

Liu, Chao; Hajagos, Tibor Jacob; Chen, Dustin; Chen, Yi; Kishpaugh, David; Pei, Qibing

doi:10.1021/acsami.6b00743

Cited by 49 publications

(43 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[216] Amines (benzylamine or long chain primary amines)a ct as reactants and capping agentsf or the shape controlled synthesis of metal oxide nanostructures. [217][218][219] The synthesis of facet controlled ZnO nanocrystalsw as achieved through the reaction of zinc acetate and benzylamine. [220] After coordination of benzylamine to Zn 2 + ,f ormingaZn(acetate) 2 -benzylamine complex,a minolysis between benzylamine and the acetate group occurred to form zinc hydroxidea nd N-benzylacetamide.…”

Section: Ester and Amide Eliminationsmentioning

confidence: 99%

“…Analogous to ester elimination is the amide elimination, involving aminolysis of metal carboxylates . Amines (benzylamine or long chain primary amines) act as reactants and capping agents for the shape controlled synthesis of metal oxide nanostructures . The synthesis of facet controlled ZnO nanocrystals was achieved through the reaction of zinc acetate and benzylamine .…”

Section: Chemical Formation Mechanismsmentioning

confidence: 99%

See 1 more Smart Citation

Mechanistic Aspects in the Formation, Growth and Surface Functionalization of Metal Oxide Nanoparticles in Organic Solvents

Deshmukh

Niederberger

2017

Chemistry A European J

101

112

View full text Add to dashboard Cite

The synthesis of metal oxide nanoparticles in organic solvents, so-called nonaqueous (or nonhydrolytic) processes represent powerful alternatives to aqueous approaches and have become an independent research field. 10 Years ago, when we published our first review on organic reaction pathways in nonaqueous sol-gel approaches, the number of examples was relatively limited. Nowadays, it is almost impossible to provide an exhaustive overview. Here we review the development of the last few years, without neglecting pioneering examples, which help to follow the historical development. The importance of a profound understanding of mechanistic aspects of nanoparticle crystallization and formation mechanisms can't be overestimated, when it comes to the design of rational synthesis concepts under minimization of trial-and-error experiments. The main reason for the progress in mechanistic understanding lies in the availability of characterization tools that make it possible to monitor chemical reactions from the dissolution of the precursor to the nucleation and growth of the nanoparticles, by ex situ methods involving sampling after different reaction times, but more and more also by in situ studies. After a short introduction to experimental aspects of nonaqueous sol-gel routes to metal oxide nanoparticles, we provide an overview of the main and basic organic reaction pathways in these approaches. Afterwards, we summarize the main characterization methods to study formation mechanisms, and then we discuss in great depth the chemical formation mechanisms of many different types of metal oxide nanoparticles. The review concludes with a paragraph on selected crystallization mechanisms reported for nonaqueous systems and a few illustrative examples of nonaqueous sol-gel concepts applied to surface chemistry.

show abstract

Section: Ester and Amide Eliminationsmentioning

confidence: 99%

Section: Chemical Formation Mechanismsmentioning

confidence: 99%

Mechanistic Aspects in the Formation, Growth and Surface Functionalization of Metal Oxide Nanoparticles in Organic Solvents

Deshmukh

Niederberger

2017

Chemistry A European J

101

112

View full text Add to dashboard Cite

show abstract

“…[36][37][38] Both the NC size 14,31,33 and crystal structure 39 can be tuned by varying the metal precursor. A variety of group 4 metal oxide NCs can also be synthesized in organic surfactants, including oleylamine 21,23 or tri-n-octylphosphine oxide (TOPO). For example, TiO2 and ZrO2 NCs were recently synthesized from a mixture of the corresponding metal halide and metal alkoxide in TOPO and heptadecane.…”

Section: Introductionmentioning

confidence: 99%

Stabilization of Colloidal Ti, Zr, and Hf Oxide Nanocrystals by Protonated Tri-n-octylphosphine Oxide (TOPO) and Its Decomposition Products

et al. 2017

View full text Add to dashboard Cite

Although TiO2, ZrO2 and HfO2 nanocrystals are often synthesized in tri-noctylphosphine oxide (TOPO), it is unclear whether TOPO also serves as ligand. Using liquid and solid state 1 H and 31 P nuclear magnetic resonance spectroscopy and X-ray fluorescence spectroscopy, we show that the nanocrystal surface is capped by several derivatives of TOPO. In the 31 P NMR spectrum, di-noctylphosphinate (δ = 57 ppm) and P,P'-(di-n-octyl) pyrophosphonate (δ = 20 ppm) are found coordinated to the nanocrystal. In addition, hydrogen chloride associates with the metal oxide nanocrystal surface and protonates TOPO. The resulting hydroxyl-tri-n-octylphosphonium, [HO-PR3] + , is tightly associated with the nanocrystal surface (δ(31 P) = 73 ppm) due to electrostatic interactions and hydrogen bonding. To simplify the complex surface composition, we exchange the original surface species for carboxylate or phosphonate ligands. The protonation of TOPO is an unexpected example of lyophilic ion pairing between an acidic metal oxide nanocrystal and a weakly basic ligand molecule that is formed in nonpolar solution. Our results contrast with the classically envisaged L-type binding motif of TOPO to surface metal ions. The generality of this stabilization mode and its relevance to catalysis is discussed.

show abstract

“…In lieu of zirconia alkoxides, Liu et al [136] recently developed an alternate approach using zirconium trifluoroacetate in oleylamine to annihilate the consequential impacts of the latter. The reaction mechanism followed an irreversible amidization-assisted sol-gel route as shown in Equation (3) with a yield >90%.…”

Section: Zirconia (Zro 2 ) Nanoparticlesmentioning

confidence: 99%

Nano-Doped Monolithic Materials for Molecular Separation

et al. 2017

View full text Add to dashboard Cite

Monoliths are continuous adsorbents that can easily be synthesised to possess tuneable meso-/macropores, convective fluid transport, and a plethora of chemistries for ligand immobilisation. They are grouped into three main classes: organic, inorganic, and hybrid, based on their chemical composition. These classes may also be differentiated by their unique morphological and physicochemical properties which are significantly relevant to their specific separation applications. The potential applications of monoliths for molecular separation have created the need to enhance their characteristic properties including mechanical strength, electrical conductivity, and chemical and thermal stability. An effective approach towards monolith enhancement has been the doping and/or hybridization with miniaturized molecular species of desirable functionalities and characteristics. Nanoparticles are usually preferred as dopants due to their high solid phase dispersion features which are associated with improved intermolecular adsorptive interactions. Examples of such nanomaterials include, but are not limited to, carbon-based, silica-based, gold-based, and alumina nanoparticles. The incorporation of these nanoparticles into monoliths via in situ polymerisation and/or post-modification enhances surface adsorption for activation and ligand immobilisation. Herein, insights into the performance enhancement of monoliths as chromatographic supports by nanoparticles doping are presented. In addition, the potential and characteristics of less common nanoparticle materials such as hydroxyapatite, ceria, hafnia, and germania are discussed. The advantages and challenges of nanoparticle doping of monoliths are also discussed.

show abstract

Efficient One-Pot Synthesis of Colloidal Zirconium Oxide Nanoparticles for High-Refractive-Index Nanocomposites

Cited by 49 publications

References 36 publications

Mechanistic Aspects in the Formation, Growth and Surface Functionalization of Metal Oxide Nanoparticles in Organic Solvents

Mechanistic Aspects in the Formation, Growth and Surface Functionalization of Metal Oxide Nanoparticles in Organic Solvents

Stabilization of Colloidal Ti, Zr, and Hf Oxide Nanocrystals by Protonated Tri-n-octylphosphine Oxide (TOPO) and Its Decomposition Products

Nano-Doped Monolithic Materials for Molecular Separation

Contact Info

Product

Resources

About