Colloidal Synthesis of Carbon Dot-ZnSe Nanoplatelet Van der Waals Heterostructures for Boosting Photocatalytic Generation of Methanol-Storable Hydrogen.

Methanol is not only a promising liquid hydrogen carrier but also an important feedstock chemical for chemical synthesis. Catalyst design is vital for enabling the reactions to occur under ambient conditions. This study reports a new class of van der Waals heterojunction photocatalyst, which is synthesized by hot-injection method, whereby carbon dots (CDs) are grown in situ on ZnSe nanoplatelets (NPLs), i.e., metal chalcogenide quantum wells. The resultant organic-inorganic hybrid nanoparticles, CD-NPLs, are able to perform methanol dehydrogenation through CH splitting. The heterostructure has enabled light-induced charge transfer from the CDs into the NPLs occurring on a sub-nanosecond timescale, with charges remaining separated across the CD-NPLs heterostructure for longer than 500 ns. This resulted in significantly heightened H2 production rate of 107 µmole·g-1·h-1 and enhanced photocurrent density up to 34 µA cm-2 at 1 V bias potential. EPR and NMR analyses confirmed the occurrence of α-CH splitting and CC coupling. The novel CD-based organic-inorganic semiconductor heterojunction is poised to enable the discovery of a host of new nano-hybrid photocatalysts with full tunability in the band structure, charge transfer, and divergent surface chemistry for guiding photoredox pathways and accelerating reaction rates.

Evaluation of the X-ray/EUV Nanolithography Facility at AS through wavefront propagation simulations.

Synchrotron light sources can provide the required spatial coherence, stability and control to support the development of advanced lithography at the extreme ultraviolet and soft X-ray wavelengths that are relevant to current and future fabricating technologies. Here an evaluation of the optical performance of the soft X-ray (SXR) beamline of the Australian Synchrotron (AS) and its suitability for developing interference lithography using radiation in the 91.8 eV (13.5 nm) to 300 eV (4.13 nm) range are presented. A comprehensive physical optics model of the APPLE-II undulator source and SXR beamline was constructed to simulate the properties of the illumination at the proposed location of a photomask, as a function of photon energy, collimation and monochromator parameters. The model is validated using a combination of experimental measurements of the photon intensity distribution of the undulator harmonics. It is shown that the undulator harmonics intensity ratio can be accurately measured using an imaging detector and controlled using beamline optics. Finally, the photomask geometric constraints and achievable performance for the limiting case of fully spatially coherent illumination are evaluated.

2D Ferromagnetic M3GeTe2 (M = Ni/Fe) for Boosting Intermediates Adsorption toward Faster Water Oxidation.

In this work, 2D ferromagnetic M3GeTe2 (MGT, M = Ni/Fe) nanosheets with rich atomic Te vacancies (2D-MGTv) are demonstrated as efficient OER electrocatalyst via a general mechanical exfoliation strategy. X-ray absorption spectra (XAS) and scanning transmission electron microscope (STEM) results validate the dominant presence of metal-O moieties and rich Te vacancies, respectively. The formed Te vacancies are active for the adsorption of OH* and O* species while the metal-O moieties promote the O* and OOH* adsorption, contributing synergistically to the faster oxygen evolution kinetics. Consequently, 2D-Ni3GeTe2v exhibits superior OER activity with only 370 mV overpotential to reach the current density of 100 mA cm-2 and turnover frequency (TOF) value of 101.6 s-1 at the overpotential of 200 mV in alkaline media. Furthermore, a 2D-Ni3GeTe2v-based anion-exchange membrane (AEM) water electrolysis cell (1 cm2) delivers a current density of 1.02 and 1.32 A cm-2 at the voltage of 3 V feeding with 0.1 and 1 m KOH solution, respectively. The demonstrated metal-O coordination with abundant atomic vacancies for ferromagnetic M3GeTe2 and the easily extended preparation strategy would enlighten the rational design and fabrication of other ferromagnetic materials for wider electrocatalytic applications.

Stabilizing Cobalt-free Li-rich Layered Oxide Cathodes through Oxygen Lattice Regulation by Two-phase Ru Doping.

The application of Li-rich layered oxides is hindered by their dramatic capacity and voltage decay on cycling. This work comprehensively studies the mechanistic behaviour of cobalt-free Li1.2 Ni0.2 Mn0.6 O2 and demonstrates the positive impact of two-phase Ru doping. A mechanistic transition from the monoclinic to the hexagonal behaviour is found for the structural evolution of Li1.2 Ni0.2 Mn0.6 O2, and the improvement mechanism of Ru doping is understood using the combination of in operando and post-mortem synchrotron analyses. The two-phase Ru doping improves the structural reversibility in the first cycle and restrains structural degradation during cycling by stabilizing oxygen (O2- ) redox and reducing Mn reduction, thus enabling high structural stability, an extraordinarily stable voltage (decay rate <0.45 mV per cycle), and a high capacity-retention rate during long-term cycling. The understanding of the structure-function relationship of Li1.2 Ni0.2 Mn0.6 O2 sheds light on the selective doping strategy and rational materials design for better-performance Li-rich layered oxides.

Tailoring the microenvironment in Fe-N-C electrocatalysts for optimal oxygen reduction reaction performance.

Fe-N-C electrocatalysts, comprising FeN4 single atom sites immobilized on N-doped carbon supports, offer excellent activity in the oxygen reduction reaction (ORR), especially in alkaline solution. Herein, we report a simple synthetic strategy for improving the accessibility of FeN4 sites during ORR and simultaneously fine-tuning the microenvironment of FeN4 sites, thus enhancing the ORR activity. Our approach involved a simple one-step pyrolysis of a Fe-containing zeolitic imidazolate framework in the presence of NaCl, yielding a hierarchically porous Fe-N-C electrocatalyst containing tailored FeN4 sites with slightly elongated Fe-N bond distances and reduced Fe charge. The porous carbon structure improved mass transport during ORR, whilst the microenvironment optimized FeN4 sites benefitted the adsorption/desorption of ORR intermediates. Accordingly, the developed electrocatalyst, possessing a high FeN4 site density (9.9 × 1019 sites g-1) and turnover frequency (2.26 s-1), delivered remarkable ORR performance with a low overpotential (a half-wave potential of 0.90 V vs. reversible hydrogen electrode) in 0.1 mol L-1 KOH.

Introducing 4s-2p Orbital Hybridization to Stabilize Spinel Oxide Cathodes for Lithium-Ion Batteries.

Oxides composed of an oxygen framework and interstitial cations are promising cathode materials for lithium-ion batteries. However, the instability of the oxygen framework under harsh operating conditions results in fast battery capacity decay, due to the weak orbital interactions between cations and oxygen (mainly 3d-2p interaction). Here, a robust and endurable oxygen framework is created by introducing strong 4s-2p orbital hybridization into the structure using LiNi0.5 Mn1.5 O4 oxide as an example. The modified oxide delivers extraordinarily stable battery performance, achieving 71.4 % capacity retention after 2000 cycles at 1 C. This work shows that an orbital-level understanding can be leveraged to engineer high structural stability of the anion oxygen framework of oxides. Moreover, the similarity of the oxygen lattice between oxide electrodes makes this approach extendable to other electrodes, with orbital-focused engineering a new avenue for the fundamental modification of battery materials.

Epitaxial growth of an atom-thin layer on a LiNi0.5Mn1.5O4 cathode for stable Li-ion battery cycling.

Transition metal dissolution in cathode active material for Li-based batteries is a critical aspect that limits the cycle life of these devices. Although several approaches have been proposed to tackle this issue, this detrimental process is not yet overcome. Here, benefitting from the knowledge developed in the semiconductor research field, we apply an epitaxial method to construct an atomic wetting layer of LaTMO3 (TM = Ni, Mn) on a LiNi0.5Mn1.5O4 cathode material. Experimental measurements and theoretical analyses confirm a Stranski-Krastanov growth, where the strained wetting layer forms under thermodynamic equilibrium, and it is self-limited to monoatomic thickness due to the competition between the surface energy and the elastic energy. Being atomically thin and crystallographically connected to the spinel host lattices, the LaTMO3 wetting layer offers long-term suppression of the transition metal dissolution from the cathode without impacting its dynamics. As a result, the epitaxially-engineered cathode material enables improved cycling stability (a capacity retention of about 77% after 1000 cycles at 290 mA g-1) when tested in combination with a graphitic carbon anode and a LiPF6-based non-aqueous electrolyte solution.

Validating the Electronic Structure of Vanadium Phosphate Cathode Materials.

Investigation of the electronic structure of contending battery electrode materials is an essential step for developing a detailed mechanistic understanding of charge-discharge properties. Herein, we use synchrotron soft X-ray absorption spectroscopy (XAS) in combination with complementary experiments and density functional theory calculations to map the electronic structure, band positioning, and band gap of prototype vanadium(III) phosphate cathode materials, Na3V2(PO4)3, Li3V2(PO4)3, and K3V3(PO4)4·H2O, for alkali-ion rechargeable batteries. XAS fluorescence yield and electron yield measurements reveal substantial variation in surface-to-bulk atomic structure, vanadium oxidation states, and density of oxygen hole states across all samples. We attribute this variation to an intrinsic alkali metal surface depletion identified across these alkali metal vanadium(III) phosphates. We propose that an alkali-depleted surface provides a beneficial interface with the bulk structure(s) that raises the Fermi level and improves surface charge transfer kinetics. Furthermore, we discuss how this effect can play a significant role in reducing the electronic and ionic diffusion limitations of alkali vanadium phosphates in alkali-ion rechargeable batteries. These findings clarify the electronic structure and properties of alkali metal vanadium phosphates and offer guidance on future strategies to improve vanadium phosphate battery performance.

A Simplified Method for Patterning Graphene on Dielectric Layers.

The large-scale formation of patterned, quasi-freestanding graphene structures supported on a dielectric has so far been limited by the need to transfer the graphene onto a suitable substrate and contamination from the associated processing steps. We report µm scale, few-layer graphene structures formed at moderate temperatures (600-700 °C) and supported directly on an interfacial dielectric formed by oxidizing Si layers at the graphene/substrate interface. We show that the thickness of this underlying dielectric support can be tailored further by an additional Si intercalation of the graphene prior to oxidation. This produces quasi-freestanding, patterned graphene on dielectric SiO2 with a tunable thickness on demand, thus facilitating a new pathway to integrated graphene microelectronics.

Mechanistic implications of Li-S cell function through modification of organo-sulfur cathode architectures.

Copolymeric organo-sulfur based electrodes provide a unique framework to explore and subsequently improve lithium-sulfur (Li-S) cells. There is a general difference in the way copolymers trap lithium during cell function compared to inorganic carbon-sulfur composites. Using a chain-like polyterpene copolymeric architecture involving the copolymerization of squalene monomer with sulfur (poly(S-r-squalene)), the first evidence for distinguishable differences in the entrapment of lithiated species, when using different copolymeric architectures, is provided. Investigation of poly(S-r-squalene) as an active cathode material via X-ray Absorption Near-Edge Structure (XANES) spectroscopy and high-resolution solid-state Nuclear Magnetic Resonance (NMR) reveal notable differences compared to previously studied poly(S-r-DIB) (proposed to have a less branched architecture) between the lithium environments present during electrochemistry that can be directly linked to the copolymeric structural features. Subtle but pertinent effects based on the copolymeric architecture related to the solid-electrolyte interphase (SEI) formed from the electrolytic components are also uncovered through these techniques. This work offers a comprehensive study on poly(S-r-squalene) and reveals that foundational inverse vulcanisation conditions such as choice of crosslinking monomer can dramatically impact lithium transport and SEI formation for the copolymeric electrode.

Bias-Polarity-Dependent Direct and Inverted Marcus Charge Transport Affecting Rectification in a Redox-Active Molecular Junction.

This paper describes the transition from the normal to inverted Marcus region in solid-state tunnel junctions consisting of self-assembled monolayers of benzotetrathiafulvalene (BTTF), and how this transition determines the performance of a molecular diode. Temperature-dependent normalized differential conductance analyses indicate the participation of the HOMO (highest occupied molecular orbital) at large negative bias, which follows typical thermally activated hopping behavior associated with the normal Marcus regime. In contrast, hopping involving the HOMO dominates the mechanism of charge transport at positive bias, yet it is nearly activationless indicating the junction operates in the inverted Marcus region. Thus, within the same junction it is possible to switch between Marcus and inverted Marcus regimes by changing the bias polarity. Consequently, the current only decreases with decreasing temperature at negative bias when hopping is "frozen out," but not at positive bias resulting in a 30-fold increase in the molecular rectification efficiency. These results indicate that the charge transport in the inverted Marcus region is readily accessible in junctions with redox molecules in the weak coupling regime and control over different hopping regimes can be used to improve junction performance.

Effect of Long- and Short-Range Disorder on the Oxygen Ionic Conductivity of Tm2(Ti2-xTmx)O7-x/2 "Stuffed" Pyrochlores.

The long-range average and short-range local structures in the Tm2(Ti2-xTmx)O7-x/2 (x = 0.00-0.67) series were studied using a combination of diffraction and spectroscopic techniques. The long-range average structure, established from synchrotron X-ray and neutron powder diffraction data, shows the development of multiphase regions from x = 0.134 and the formation of antisite cation disorder from x = 0.402. The crystal field splitting of the Ti4+ ions, as derived from the Ti L3-edge X-ray absorption near-edge structure (XANES) spectroscopy, decreases gradually from 2.17 to 1.92 eV with increasing Tm3+ content (x), reflecting the increase in coordination number from 6 to predominantly 7. This is consistent with a gradual evolution of the short-range local disorder from x = 0.00 to 0.67. These results suggest that local disorder develops gradually throughout the entire composition range, whereas changes in the long-range disorder occur more suddenly. Electrochemical impedance spectroscopic results show an increase in oxygen ionic conductivity at 1000 °C, by a factor of 4 upon doping at x = 0.268. This suggests that inducing small amounts of disorder into the pyrochlore structure, by stuffing, may lead to applications of this material as a solid electrolyte in solid-oxide fuel cells.

Outstanding Thermal Conductivity of Single Atomic Layer Isotope-Modified Boron Nitride.

Materials with high thermal conductivities (κ) are valuable to solve the challenge of waste heat dissipation in highly integrated and miniaturized modern devices. Herein, we report the first synthesis of atomically thin isotopically pure hexagonal boron nitride (BN) and its one of the highest κ among all semiconductors and electric insulators. Single atomic layer (1L) BN enriched with ^{11}B has a κ up to 1009 W/mK at room temperature. We find that the isotope engineering mainly suppresses the out-of-plane optical (ZO) phonon scatterings in BN, which subsequently reduces acoustic-optical scatterings between ZO and transverse acoustic (TA) and longitudinal acoustic phonons. On the other hand, reducing the thickness to a single atomic layer diminishes the interlayer interactions and hence umklapp scatterings of the out-of-plane acoustic (ZA) phonons, though this thickness-induced κ enhancement is not as dramatic as that in naturally occurring BN. With many of its unique properties, atomically thin monoisotopic BN is promising on heat management in van der Waals devices and future flexible electronics. The isotope engineering of atomically thin BN may also open up other appealing applications and opportunities in 2D materials yet to be explored.

Ablation in Externally Applied Electric and Magnetic Fields.

To harness light-matter interactions at the nano-/micro-scale, better tools for control must be developed. Here, it is shown that by applying an external electric and/or magnetic field, ablation of Si and glass under ultra-short (sub-1 ps) laser pulse irradiation can be controlled via the Lorentz force F = e E + e [ v × B ] , where v is velocity of charge e, E is the applied electrical bias and B is the magnetic flux density. The external electric E-field was applied during laser ablation using suspended micro-electrodes above a glass substrate with an air gap for the incident laser beam. The counter-facing Al-electrodes on Si surface were used to study debris formation patterns on Si. Debris was deposited preferentially towards the negative electrode in the case of glass and Si ablation. Also, an external magnetic field was applied during laser ablation of Si in different geometries and is shown to affect ripple formation.

Room temperature conductance switching in a molecular iron(iii) spin crossover junction.

Herein, we report the first room temperature switchable Fe(iii) molecular spin crossover (SCO) tunnel junction. The junction is constructed from [FeIII(qsal-I)2]NTf2 (qsal-I = 4-iodo-2-[(8-quinolylimino)methyl]phenolate) molecules self-assembled on graphene surfaces with conductance switching of one order of magnitude associated with the high and low spin states of the SCO complex. Normalized conductance analysis of the current-voltage characteristics as a function of temperature reveals that charge transport across the SCO molecule is dominated by coherent tunnelling. Temperature-dependent X-ray absorption spectroscopy and density functional theory confirm the SCO complex retains its SCO functionality on the surface implying that van der Waals molecule-electrode interfaces provide a good trade-off between junction stability while retaining SCO switching capability. These results provide new insights and may aid in the design of other types of molecular devices based on SCO compounds.

External Field-Controlled Ablation: Magnetic Field.

The femtosecond laser ablation of silicon amidst an externally applied magnetic field in different orientations was investigated with respect to the scanning direction and polarisation of the laser beam, by observation of ablation patterns and debris displacement in a range of fluences, magnetic fields strengths, and geometries. Ultra-short ∼ 230 fs laser pulses of 1030 nm wavelengths were utilised in the single and multi-pulse irradiation modes. Ablation with an externally applied magnetic B-field B e x t ≈ 0.15 T was shown to strongly affect debris formation and deposition. The mechanism of surface plasmon polariton (SPP) wave can explain the ablated periodic patterns observed with alignment along the magnetic field lines. The application potential of external field controlled ablation is discussed.

Elucidation of structures and lithium environments for an organo-sulfur cathode.

Composite organo-sulfur cathodes provide a unique platform for the realization of lithium-sulfur (Li-S) cells. However, difficulties arise in the interpretation of the function of these electrodes in Li-S cells and the role they play in suppressing the so-called 'shuttle effect'. This work focuses on monitoring in detail the structural evolution and lithium environments during charge-discharge cycles in a lithium half-cell of an organo-sulfur cathode, which was synthesised by inverse vulcanisation with 1,3-diisopropenylbenzene. For the first-time in organo-sulfur materials, high resolution solid state 7Li-1H and 13C-1H double resonance NMR spectroscopy coupled with X-ray absorption near-edge structure (XANES) and X-ray diffraction (XRD) are used to develop a detailed structural model of the cathode material and its lithium environments as a function of cycle number. This work provides the first experimental evidence via 2D NMR spectroscopy of distinct molecular proximities of the lithium species with respect to the sulfur, the organic skeleton and the electrolyte in the cathode material. This approach enables us to develop unparalleled understanding of the mechanisms of the high charge capacity of 607 mA h g-1, rationalising initial capacity drop and suppression of capacity fade with cycling. These results also show new possibilities on how to better understand electrode function to further increase the lithium capacities of organo-sulfur cathode materials, which can in turn lead to performance-enhanced Li-S cells.

Author Correction: Chemical nature of alkaline polyphosphate boundary film at heated rubbing surfaces.

A correction to this article has been published and is linked from the HTML and PDF versions of this paper. The error has been fixed in the paper.