General criteria for evaluating suitable polymer ligands for the synthesis of aluminum nanocrystals

Yu, Hui; Lu, Shaoyong; Gao, Huimin; Lu, Zhong‐Yuan; Liu, Kun

doi:10.1039/c9cc08476b

Cited by 10 publications

(8 citation statements)

References 37 publications

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“…Subsequently, there have been significant developments to better understand and control Al nanoparticle synthesis. [2][3][4]14,19,20 Electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectroscopies were used to clarify the mechanism of the reduction of alane precursors using TIP, as well as the mechanism underlying size control using solvent ratios (Figure 1A and 1B). 2 EPR allows for direct observation of the catalyst/alane reaction in situ, as many of the catalysts and intermediates are paramagnetic and, therefore, NMR inactive.…”

Section: ■ Synthesis Developmentmentioning

confidence: 99%

“…This method produced quality crystalline particles of varying shape, but the underlying mechanism controlling size was unknown. Subsequently, there have been significant developments to better understand and control Al nanoparticle synthesis. − ,,, …”

Section: Synthesis Developmentmentioning

confidence: 99%

“…Further developments of Al NC synthesis have focused on three main directions: alternate Al precursors, ligand-based control, ,, and alternate catalysts . In 2018, the first synthesis of anisotropic Al NCs was demonstrated.…”

Section: Synthesis Developmentmentioning

confidence: 99%

“…The use of thiol-terminated polymer ligands in the synthesis of Al NCs was also demonstrated (Figure B). , It was shown that cumyl dithiobenzoate-terminated polystyrene could be used to selectively stabilize the {100} facets on the NCs during growth, allowing for tunable shape control from octahedra to truncated cubes. As part of this work, density functional theory calculations were used to compare the adsorption energies of the ligand to different facets of Al.…”

Section: Synthesis Developmentmentioning

confidence: 99%

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Shining Light on Aluminum Nanoparticle Synthesis

et al. 2020

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Conspectus Aluminum in its nanostructured form is generating increasing interest because of its light-harvesting properties, achieved by excitation of its localized surface plasmon resonance. Compared to traditional plasmonic materials, the coinage metals Au and Ag, Al is far more earth-abundant and, therefore, more suitable for large-area applications or where cost may be an important factor. Its optical properties are far more flexible than either Au or Ag, supporting plasmon resonances that range from UV wavelengths, through the visible regime, and into the infrared region of the spectrum. However, the chemical synthesis of Al nanocrystals (NCs) of controlled size and shape has historically lagged far behind that of Au and Ag. This is partially due to the high reactivity of Al precursors, which react readily with O2, H2O, and many reagents used in traditional NC syntheses. The first chemical synthesis of Al NCs was demonstrated by Haber and Buhro in 1998, decomposing AlH3 using titanium isopropoxide (TIP), with a number of subsequent reports refining this protocol. The role of a catalyst in Al NC synthesis is, we believe, unique to this synthetic approach. In 2015, the first synthesis of size controlled Al NCs was published by our group. Since then, we have significantly advanced Al NC synthesis, postsynthetic modifications, and applications of Al nanoparticles (NPs)NCs with additional surface modificationsin chemical sensing and photocatalysis. Colloidal Al synthesis has its unique challenges, differing markedly from the far more familiar Au and Ag syntheses, which currently appears to present a de facto barrier to broader research activity in this field. The goal of this Account is to highlight developments in controlled synthesis of Al NCs and applications of Al NPs over the last five years. We outline techniques for successful Al NC synthesis and address some of the problems that may be encountered in this synthesis. A mechanistic understanding of AlH3 decomposition using TIP has been developed, while new directions have been discovered for synthetic control. Facet-binding ligands, alternate Al precursors, new titanium-based reduction catalysts, even solvent composition have all been shown to control reaction products while also opening doors to future developments. A variety of postsynthetic modifications to the Al NC native oxide surface, including polymer, MOF, and transition metal island coatings have been demonstrated for applications in molecular sensing and photocatalysis. In this Account, we hope to convey that Al synthesis is more accessible than generally perceived and to encourage new synthetic development based on underlying mechanisms controlling size and shape. High selectivity in particle faceting and twinning, implementation of seeded growth principles for monodisperse samples, and the demonstration of new, practical applications of Al nanoparticles remain primary challenges in the field. As Al nanoparticle synthesis is refined and new applications emerge, colloidal Al will become an acce...

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Section: ■ Synthesis Developmentmentioning

confidence: 99%

Section: Synthesis Developmentmentioning

confidence: 99%

Section: Synthesis Developmentmentioning

confidence: 99%

Section: Synthesis Developmentmentioning

confidence: 99%

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Shining Light on Aluminum Nanoparticle Synthesis

et al. 2020

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“…To test their chemical stabilities, the THF solutions of PCL and PEO (Figures 5d and 5e) were heated to 50°C and reacted with H 3 Al precursor for 30 min. 59 After the reaction, the THF solution of PCL became cloudy, yielding white gel-like precipitates, marked by the yellow circles in Figure 5d. Meanwhile, the reaction solution of PEO remained transparent, and no precipitates were observed (Figure 5e).…”

Section: Resultsmentioning

confidence: 99%

Poly(Ethylene Oxide) Mediated Synthesis of Sub-100-nm Aluminum Nanocrystals for Deep Ultraviolet Plasmonic Nanomaterials

Yang

et al. 2020

CCS Chem

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Aluminum nanocrystals (Al NCs) are sustainable plasmonic nanomaterials with unique localized surface plasmonic resonance (LSPR) in the ultraviolet (UV) region. Chemical synthesis of sub-100-nm Al NCs remains a considerable challenge due to the lack of effective ligands to control their growth. Here, we describe a precise size-controlled synthesis of small colloidal Al NCs (25-100 nm) with strong and tunable LSPR peak from 250 to 372 nm in the UV spectral region by the use of poly(ethylene oxide) (PEO) as a polydentate surface ligand. The LSPR band matched well with the numerical simulation results. Additionally, the molecular weight of the PEO played an essential role in tuning the size of Al NCs. The PEO showed a strong affinity with Al {111} crystal facets, resulting in octahedral-and prism-shaped Al NCs. Owing to the passive oxide layer generated on the surface of Al NCs, their LSPR peak positions showed negligible changes after storage in tetrahydrofuran for 4 months. The passivation layer also impeded the metal Al core to react with deionized water. Further, the use of biocompatible PEO ligand and the subsequent generation of the sub-100-nm size of the Al NCs pave a path for bioapplications of such NCs.

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Two‐Dimensional Polymer Networks Locking on Inorganic Nanoparticles

Tao

et al. 2023

Angewandte Chemie

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, singlelayer networks of covalently linked monomers, show perspectives as membranes and in electronics. However, 2D polymerization of monomers in orthogonal directions limited the formation of 2DPs on nanoparticles (NPs) with high surface curvatures. Here we propose a high-curvature 2D polymerization to form a single-layer 2DP network as a non-contacting ligand on the surface of NPs for their stabilization and functionalization. The high-curvature 2D polymerization of amphiphilic Gemini monomers was conducted in situ on surfaces of NPs with various sizes, shapes, and materials, forming highly cross-linked 2DPs. Selective etching of core-shell NPs led to 2DPs as a non-contact ligand of yolk-shell structures with excellent shape retention and high NPsurface accessibility. In addition, by copolymerization, the 2DP ligands can covalently link to other functional molecules. This work promotes the development of 2DPs on NPs for their functional modification.

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General criteria for evaluating suitable polymer ligands for the synthesis of aluminum nanocrystals

Abstract: This work proposes general criteria for evaluating suitable polymer ligands for shape- and size-controlled synthesis of Al nanocrystals.

Cited by 10 publications

References 37 publications

Shining Light on Aluminum Nanoparticle Synthesis

Shining Light on Aluminum Nanoparticle Synthesis

Poly(Ethylene Oxide) Mediated Synthesis of Sub-100-nm Aluminum Nanocrystals for Deep Ultraviolet Plasmonic Nanomaterials

Two‐Dimensional Polymer Networks Locking on Inorganic Nanoparticles

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