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Spin-crossover nanoparticles anchored on MoS2 layers for heterostructures with tunable strain driven by thermal or light-induced spin switching
by
Escorcia-Ariza Garin
,
Morant-Giner, Marc
,
Canet-Ferrer Josep
in
Composite materials
,
Crossovers
,
Heterostructures
2021
In the past few years, the effect of strain on the optical and electronic properties of MoS2 layers has attracted particular attention as it can improve the performance of optoelectronic and spintronic devices. Although several approaches have been explored, strain is typically externally applied on the two-dimensional material. In this work, we describe the preparation of a reversible ‘self-strainable’ system in which the strain is generated at the molecular level by one component of a MoS2-based composite material. Spin-crossover nanoparticles were covalently grafted onto functionalized layers of semiconducting MoS2 to form a hybrid heterostructure. Their ability to switch between two spin states on applying an external stimulus (light irradiation or temperature change) serves to generate strain over the MoS2 layer. A volume change accompanies this spin crossover, and the created strain induces a substantial and reversible change of the electrical and optical properties of the heterostructure.Spin-crossover nanoparticles have been covalently grafted onto a semiconducting MoS2 layer to form a self-strainable heterostructure. Under light or thermal stimulus, the nanoparticles switch between their high- and low-spin states, in which they have different volumes. This generates a reversible strain over the MoS2 layer and, in turn, alters the electrical and optical properties of the heterostructure.
Journal Article
Efficient, fast and reabsorption-free perovskite nanocrystal-based sensitized plastic scintillators
2020
The urgency for affordable and reliable detectors for ionizing radiation in medical diagnostics, nuclear control and particle physics is generating growing demand for scintillator devices combining efficient scintillation, fast emission lifetime, high interaction probability with ionizing radiation and mitigated reabsorption losses in large-volume/high-density detectors. To date, the simultaneous achievement of all such features is still an open challenge. Here we realize this regime with poly(methyl methacrylate) nanocomposites embedding CsPbBr3 perovskite nanocrystals as sensitizers for a conjugated organic dye featuring a large Stokes shift and a fast emission lifetime in the red spectral region. Complete energy transfer from the nanocrystals to the dye under both X-rays and α-particle excitation results in highly stable radioluminescence with an efficiency comparable to that of commercial-grade inorganic and plastic scintillators; an ~3.4 ns emission lifetime, competitive with fast lanthanide scintillators; and reabsorption-free waveguiding for long optical distances.Poly(methyl methacrylate) nanocomposites embedding CsPbBr3 perovskite nanocrystals can be used to simultaneously achieve optimized parameters in scintillator devices.
Journal Article
Depletable peroxidase-like activity of Fe3O4 nanozymes accompanied with separate migration of electrons and iron ions
2022
As pioneering Fe
3
O
4
nanozymes, their explicit peroxidase (POD)-like catalytic mechanism remains elusive. Although many studies have proposed surface Fe
2+
-induced Fenton-like reactions accounting for their POD-like activity, few have focused on the internal atomic changes and their contribution to the catalytic reaction. Here we report that Fe
2+
within Fe
3
O
4
can transfer electrons to the surface via the Fe
2+
-O-Fe
3+
chain, regenerating the surface Fe
2+
and enabling a sustained POD-like catalytic reaction. This process usually occurs with the outward migration of excess oxidized Fe
3+
from the lattice, which is a rate-limiting step. After prolonged catalysis, Fe
3
O
4
nanozymes suffer the phase transformation to γ-Fe
2
O
3
with depletable POD-like activity. This self-depleting characteristic of nanozymes with internal atoms involved in electron transfer and ion migration is well validated on lithium iron phosphate nanoparticles. We reveal a neglected issue concerning the necessity of considering both surface and internal atoms when designing, modulating, and applying nanozymes.
The mechanism of peroxidase-like Fe
3
O
4
nanozymes remains elusive. Here, the authors show the electron transfer mechanism of Fe(II) ions to regenerate surface Fe(II) and the related phase transformation and depletion of activity.
Journal Article
Supercrystal engineering of atomically precise gold nanoparticles promoted by surface dynamics
2023
The controllable packing of functional nanoparticles (NPs) into crystalline lattices is of interest in the development of NP-based materials. Here we demonstrate that the size, morphology and symmetry of such supercrystals can be tailored by adjusting the surface dynamics of their constituent NPs. In the presence of excess tetraethylammonium cations, atomically precise [Au25(SR)18]− NPs (where SR is a thiolate ligand) can be crystallized into micrometre-sized hexagonal rod-like supercrystals, rather than as face-centred-cubic superlattices otherwise. Experimental characterization supported by theoretical modelling shows that the rod-like crystals consist of polymeric chains in which Au25 NPs are held together by a linear SR–[Au(I)–SR]4 interparticle linker. This linker is formed by conjugation of two dynamically detached SR–[Au(I)–SR]2 protecting motifs from adjacent Au25 particles, and is stabilized by a combination of CH⋯π and ion-pairing interactions between tetraethylammonium cations and SR ligands. The symmetry, morphology and size of the resulting supercrystals can be systematically tuned by changing the concentration and type of the tetraalkylammonium cations.Gold nanoparticles typically exhibit hard-sphere-like assembly behaviour, but now the size, morphology and symmetry of crystals of Au25 nanoparticles have been tuned. The presence of excess tetraethylammonium cations has been shown to promote the one-dimensional assembly of the nanoparticles, which in turn form rod-like crystals, by stabilizing dynamically detached ligands from adjacent particles into interparticle linkers through CH⋯π and ion-pairing interactions.
Journal Article
Topological frustration induces unconventional magnetism in a nanographene
by
Beyer, Doreen
,
Shawulienu, Kezilebieke
,
Pignedoli, Carlo A
in
Antiferromagnetism
,
Carbon
,
Chemical synthesis
2020
The chemical versatility of carbon imparts manifold properties to organic compounds, where magnetism remains one of the most desirable but elusive1. Polycyclic aromatic hydrocarbons, also referred to as nanographenes, show a critical dependence of electronic structure on the topologies of the edges and the π-electron network, which makes them model systems with which to engineer unconventional properties including magnetism. In 1972, Erich Clar envisioned a bow-tie-shaped nanographene, C38H18 (refs. 2,3), where topological frustration in the π-electron network renders it impossible to assign a classical Kekulé structure without leaving unpaired electrons, driving the system into a magnetically non-trivial ground state4. Here, we report the experimental realization and in-depth characterization of this emblematic nanographene, known as Clar’s goblet. Scanning tunnelling microscopy and spin excitation spectroscopy of individual molecules on a gold surface reveal a robust antiferromagnetic order with an exchange-coupling strength of 23 meV, exceeding the Landauer limit of minimum energy dissipation at room temperature5. Through atomic manipulation, we realize switching of magnetic ground states in molecules with quenched spins. Our results provide direct evidence of carbon magnetism in a hitherto unrealized class of nanographenes6, and prove a long-predicted paradigm where topological frustration entails unconventional magnetism, with implications for room-temperature carbon-based spintronics7,8.Topological frustration in the π-electron network of the polycyclic aromatic hydrocarbon C38H18 yields unpaired electrons and a magnetically non-trivial ground state. Here, the authors synthesize this molecule, known as Clar’s goblet, on Au(111) and characterize the antiferromagnetic ground state with scanning tunnelling microscopy.
Journal Article
Cold welding of ultrathin gold nanowires
2010
The welding of metals at the nanoscale is likely to have an important role in the bottom-up fabrication of electrical and mechanical nanodevices. Existing welding techniques use local heating, requiring precise control of the heating mechanism and introducing the possibility of damage. The welding of metals without heating (or cold welding) has been demonstrated, but only at macroscopic length scales and under large applied pressures. Here, we demonstrate that single-crystalline gold nanowires with diameters between 3 and 10 nm can be cold-welded together within seconds by mechanical contact alone, and under relatively low applied pressures. High-resolution transmission electron microscopy and
in situ
measurements reveal that the welds are nearly perfect, with the same crystal orientation, strength and electrical conductivity as the rest of the nanowire. The high quality of the welds is attributed to the nanoscale sample dimensions, oriented-attachment mechanisms and mechanically assisted fast surface-atom diffusion. Welds are also demonstrated between gold and silver, and silver and silver, indicating that the technique may be generally applicable.
Near-perfect welds between gold nanowires can be created in seconds by mechanical contact alone.
Journal Article
Berry curvature memory through electrically driven stacking transitions
2020
In two-dimensional layered quantum materials, the stacking order of the layers determines both the crystalline symmetry and electronic properties such as the Berry curvature, topology and electron correlation
1
–
4
. Electrical stimuli can influence quasiparticle interactions and the free-energy landscape
5
,
6
, making it possible to dynamically modify the stacking order and reveal hidden structures that host different quantum properties. Here, we demonstrate electrically driven stacking transitions that can be applied to design non-volatile memory based on Berry curvature in few-layer WTe
2
. The interplay of out-of-plane electric fields and electrostatic doping controls in-plane interlayer sliding and creates multiple polar and centrosymmetric stacking orders. In situ nonlinear Hall transport reveals that such stacking rearrangements result in a layer-parity-selective Berry curvature memory in momentum space, where the sign reversal of the Berry curvature and its dipole only occurs in odd-layer crystals. Our findings open an avenue towards exploring coupling between topology, electron correlations and ferroelectricity in hidden stacking orders and demonstrate a new low-energy-cost, electrically controlled topological memory in the atomically thin limit.
A memory device is proposed that uses a dynamical modification of the stacking order of few-layer WTe
2
to encode information. The change in stacking modifies both the Berry curvature and the Hall transport, allowing two states to be distinguished.
Journal Article
Emulsion-oriented assembly for Janus double-spherical mesoporous nanoparticles as biological logic gates
by
Hung, Chin-Te
,
Wang, Shangfeng
,
Elzatahry, Ahmed
in
Assembly
,
Biomolecules
,
Chemical properties
2023
The ability of Janus nanoparticles to establish biological logic systems has been widely exploited, yet conventional non/uni-porous Janus nanoparticles are unable to fully mimic biological communications. Here we demonstrate an emulsion-oriented assembly approach for the fabrication of highly uniform Janus double-spherical MSN&mPDA (MSN, mesoporous silica nanoparticle; mPDA, mesoporous polydopamine) nanoparticles. The delicate Janus nanoparticle possesses a spherical MSN with a diameter of ~150 nm and an mPDA hemisphere with a diameter of ~120 nm. In addition, the mesopore size in the MSN compartment is tunable from ~3 to ~25 nm, while those in the mPDA compartments range from ~5 to ~50 nm. Due to the different chemical properties and mesopore sizes in the two compartments, we achieve selective loading of guests in different compartments, and successfully establish single-particle-level biological logic gates. The dual-mesoporous structure enables consecutive valve-opening and matter-releasing reactions within one single nanoparticle, facilitating the design of single-particle-level logic systems.Large biomolecules cannot be loaded into conventional Janus nanoparticles with small mesopores, preventing the establishment of efficient logic-gate systems in single Janus nanoparticles. Now, an emulsion-oriented assembly approach has been shown to fabricate Janus double-spherical nanoparticles with dual-tunable mesopores, enabling the design of various single-particle-level logic systems.
Journal Article
Investigating compatibilization of polyoxymethylene/styrene-butadiene-styrene immiscible blend through addition of hydroxylated graphene
by
Sadri, Seyed Alireza
,
Arefkhani, Mahdi
,
Abbasi, Mohammad
in
639/301/1023/303
,
639/638/455/303
,
639/638/455/957
2024
The main objective of this work was to use hydroxyl-functionalized graphene as a compatibilizer for an immiscible blend. A neat polyoxymethylene/styrene-butadiene-styrene binary blend was prepared at a constant ratio (80/20) and then was compounded with different loading amounts of hydroxyl-functionalized graphene (0.25, 0.5, 0.75, and 1 wt%). The formation of droplet-matrix morphology during blending was observed in microscopy images. A deep understanding of the compatibility was inspected through studying the mechanical, rheological, and microstructural properties. By inspecting the localization of nanoparticles, triple functions of hydroxyl-functionalized graphene as a compatibilizing/reinforcing/lubricating agent were elucidated. The mechanical properties showed that the best compatibility with the ultimate performance was related to the nanocomposite containing 0.25 wt%. Furthermore, the electrical conductivity of the prepared nanocomposites was investigated. Thermodynamic/kinetic studies showed the tendency of hydroxyl-functionalized graphene to disperse droplets, however as the loading value increases, the probability of its presence in the matrix also increases, creating conductive pathways for conductive purposes. The lowest resistance and highest volume of electrical conductivity (8.4 × 10
−6
S.cm
−1
) were shown by 1 wt% FG.
Journal Article
Large magnetic exchange coupling in rhombus-shaped nanographenes with zigzag periphery
2021
Nanographenes with zigzag edges are predicted to manifest non-trivial π-magnetism resulting from the interplay of concurrent electronic effects, such as hybridization of localized frontier states and Coulomb repulsion between valence electrons. This provides a chemically tunable platform to explore quantum magnetism at the nanoscale and opens avenues towards organic spintronics. The magnetic stability in nanographenes is thus far greatly limited by the weak magnetic exchange coupling, which remains below the room-temperature thermal energy. Here, we report the synthesis of large rhombus-shaped nanographenes with zigzag peripheries on gold and copper surfaces. Single-molecule scanning probe measurements show an emergent magnetic spin singlet ground state with increasing nanographene size. The magnetic exchange coupling in the largest nanographene (C70H22, containing five benzenoid rings along each edge), determined by inelastic electron tunnelling spectroscopy, exceeds 100 meV or 1,160 K, which outclasses most inorganic nanomaterials and survives on a metal electrode.Open-shell nanographenes are promising for quantum technologies, but their magnetic stability has remained limited by weak exchange coupling. Now, two large rhombus-shaped nanographenes with zigzag peripheries, one with 48 carbon atoms and the other with 70, have been synthesized on gold and copper surfaces. The 70-carbon compound exhibits a large magnetic exchange coupling exceeding 100 meV.
Journal Article