skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Oxidative nucleation and growth of Janus-type MnOx-Ag and MnOx-AgI nanoparticles
Janus nanoparticles (NPs) containing two chemically distinct materials in one system are of great significance for catalysis in terms of harnessing catalytic synergies that are not exist in either component. We herein present a novel synthetic method of two Janus-type MnOx-Ag and MnOx-AgI NPs for efficient photochemical water oxidation. The synthesis of Janus-type MnOx-AgI NPs is based on the oxidative nucleation and growth of Ag domains on MnO first and the subsequent iodization of Ag. A mild and non-disruptive iodization strategy is developed to yield Janus MnOx-AgI NPs, in which converting Ag to AgI domains with iodomethane (CH3I) is achieved through the partial iodization. Simultaneously, Mn2+ species in the primary MnO octahedrons are oxidized during the growth of Ag NPs, leading to the formation of amorphous p-type MnOx domains. Therefore, as-resultant Janus-type MnOx-AgI NPs combining two semiconductors into an integrated nanostructure can be used as an efficient photocatalyst for visible light-driven water oxidation. Janus MnOx-AgI NPs show an expected photocatalytic activity even in the absence of Ru(bpy)3Cl2 as an electron mediator. This intriguing synthesis may open up a new opportunity to develop asymmetric nanostructures of two semiconductors that will potentially be efficient photocatalysts for solar-driven water splitting.  more » « less
Award ID(s):
1705566
PAR ID:
10104131
Author(s) / Creator(s):
; ; ; ; ; ; ;
Date Published:
Journal Name:
Nanoscale
ISSN:
2040-3364
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; ; ; ; ; ; et al (, Advanced Functional Materials)
    Abstract Here, a comprehensive study on the synthesis, characterization, and reactivity of grain‐boundary (GB)‐rich noble metal nanoparticle (NP) assemblies is presented. A facile and scalable synthesis of Pt, Pd, Au, Ag, and Rh NP assemblies is developed, in which NPs are predominantly connected via Σ3 (111) twin GBs, forming a network. Driven by water electrolysis, the random collisions and oriented attachment of colloidal NPs in solution lead to the formation of Σ3 (111) twin boundaries and some highly mismatched GBs. This synthetic method also provides convenient control over the GB density without altering the crystallite size or GB type by varying the NP collision frequency. The structural characterization reveals the presence of localized tensile strain at the GB sites. The ultrahigh activity of GB‐rich Pt NP assembly toward catalytic hydrogen oxidation in air is demonstrated, enabling room‐temperature catalytic hydrogen sensing for the first time. Finally, density functional theory calculations reveal that the strained Σ3(111) twin boundary facilitates oxygen dissociation, drastically enhancing the hydrogen oxidation rate via the dissociative pathway. This reported large‐scale synthesis of the Σ3 (111) twin GB‐rich structures enables the development of a broad range of high‐performance GB‐rich catalysts. 
    more » « less
  2. ; ; ; (, Energy Material Advances)
    Manganese dioxide (MnO 2 ) with different crystal structures has been widely investigated as the cathode material for Zn-ion batteries, among which spinel λ -MnO 2 is yet rarely reported because Zn-ion intercalation in spinel lattice is speculated to be limited by the narrow three-dimensional tunnels. In this work, we demonstrate that Zn-ion insertion in spinel lattice can be enhanced by reducing particle size and elucidate an intriguing electrochemical reaction mechanism dependent on particle size. Specifically, λ -MnO 2 nanoparticles (NPs, ~80 nm) deliver a high capacity of 250 mAh/g at 20 mA/g due to large surface area and solid-solution type phase transition pathway. Meanwhile, severe water-induced Mn dissolution leads to the poor cycling stability of NPs. In contrast, micron-sized λ -MnO 2 particles (MPs, ~0.9  μ m) unexpectedly undergo an activation process with the capacity continuously increasing over the first 50 cycles, which can be attributed to the formation of amorphous MnO x nanosheets in the open interstitial space of the MP electrode. By adding MnSO 4 to the electrolyte, Mn dissolution can be suppressed, leading to significant improvement in the cycling performance of NPs, with a capacity of 115 mAh/g retained at 1 A/g for over 500 cycles. This work pinpoints the distinctive impacts of the particle size on the reaction mechanism and cathode performance in aqueous Zn-ion batteries. 
    more » « less
  3. ; ; ; ; (, Angewandte Chemie International Edition)
    Abstract Polyelemental nanoparticles (PE NPs), those consisting of four or more elements, exhibit unique properties from synergistic compositional effects. Examples include high entropy alloys, high entropy intermetallics, and multiphase types, including Janus and core‐shell architectures. Although colloidal syntheses offer excellent structural control for mono‐ and bi‐elemental compositions, achieving the same control for PE NPs remains challenging. Here, this challenge is addressed with a NP conversion strategy wherein different types of PE NPs – including high entropy alloy, high entropy intermetallic, and multiphase Janus nanoparticles – are achieved through thermal transformation of readily synthesized colloidal core‐shell NPs. Through systematic variations in stoichiometry and metal identity to the core‐shell precursor NPs, along with atomistic simulations that probe phase stabilities, we deduce that the final mixing states of the various NPs are governed by the balance between the enthalpy and entropy of mixing. Moreover, our annealing method allows us to trap NPs at intermediate states of mixing, creating distinct surface ensembles that were evaluated as catalysts for the hydrogen evolution reaction. This study is the first, to our knowledge, to report colloidally derived precursor NPs enabling the synthesis of all types of PE NPs in a single process. This NP conversion strategy offers a general route to diverse PE NPs. 
    more » « less
  4. ; ; ; ; (, F1000Research)
    Background Nanoparticles (NPs) hold promise as alternatives to antibiotics in the fight against multi-drug-resistant bacteria. However, concerns about their cytotoxicity, particularly their effects on mammalian cells, must be thoroughly addressed to ensure therapeutic safety. Amphiphilic Janus NPs, which have segregated hydrophobic and polycationic ligands on two hemispheres, have previously been shown to exhibit potent antibacterial activity. Methods In this study, we evaluated the cytotoxicity of amphiphilic Janus NPs in immune and cancer cell lines. Cytotoxicity assays were performed to assess the effects of Janus NPs on cell viability and membrane integrity, with a particular focus on how internalization of the nanoparticles influenced cellular responses. Results The results revealed that both immune and cancer cells exhibited negligible cytotoxic effects when exposed to Janus NPs. However, phagocytic immune cells demonstrated greater susceptibility to membrane damage and viability loss, suggesting that internalization plays a significant role in nanoparticle-induced cytotoxicity. Conclusions Amphiphilic Janus NPs show great potential as highly effective antibacterial agents with minimal cytotoxicity. While immune cells may be more vulnerable to nanoparticle-induced damage due to their internalization capacity, these findings support the further investigation of Janus NPs for clinical applications. 
    more » « less
  5. ; ; ; (, Nanomaterials)
    Aluminum nanoparticles (Al NPs) are interesting for energetic and plasmonic applications due to their enhanced size-dependent properties. Passivating the surface of these particles is necessary to avoid forming a native oxide layer, which can degrade energetic and optical characteristics. This work utilized a radiofrequency (RF)-driven capacitively coupled argon/hydrogen plasma to form surface-modified Al NPs from aluminum trichloride (AlCl3) vapor and 5% silane in argon (dilute SiH4). Varying the power and dilute SiH4 flow rate in the afterglow of the plasma led to the formation of varying nanoparticle morphologies: Al–SiO2 core–shell, Si–Al2O3 core–shell, and Al–Si Janus particles. Scanning transmission electron microscopy with a high-angle annular dark-field detector (STEM-HAADF) and energy-dispersive X-ray spectroscopy (EDS) were employed for characterization. The surfaces of the nanoparticles and sample composition were characterized and found to be sensitive to changes in RF power input and dilute SiH4 flow rate. This work demonstrates a tunable range of Al–SiO2 core–shell nanoparticles where the Al-to-Si ratio could be varied by changing the plasma parameters. Thermal analysis measurements performed on plasma-synthesized Al, crystalline Si, and Al–SiO2 samples are compared to those from a commercially available 80 nm Al nanopowder. Core–shell particles exhibit an increase in oxidation temperature from 535 °C for Al to 585 °C for Al–SiO2. This all-gas-phase synthesis approach offers a simple preparation method to produce high-purity heterostructured Al NPs. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email