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The design of next-generation positive intercalation battery cathodes will leverage chemistry—mechanics—geometry coupling to mitigate stress, unlock more accessible storage capacity, and prolong cycle life.

A π-conjugated organic RMV3 molecule is stable and tunes reversibly (w/applied external electric field) the MoS2|RMV3 heterostructure band gap. Blue clouds: charge accumulation; red clouds: charge depletion. S: yellow; Mo: green; C: grey; H: white.

Ladder-type thiazole-fused S,N-heteroacenes with an extended π-conjugation consisting of six (SN6-Tz) and nine (SN9-Tz) fused aromatic rings have been synthesized and fully characterized.

Ge alloying enables independent control of forward and reverse metal–insulator transitions in VO2, enabling decoupling of transformation-temperature and hysteresis.

Lithium-ion batteries are yet to realize their full promise because of challenges in the design and construction of electrode architectures that allow for their entire interior volumes to be reversibly accessible for ion storage. Electrodes constructed from the same material and with the same specifications, which differ only in terms of dimensions and geometries of the constituent particles, can show surprising differences in polarization, stress accumulation and capacity fade. Here, using operando synchrotron X-ray diffraction and energy dispersive X-ray diffraction (EDXRD), we probe the mechanistic origins of the remarkable particle geometry-dependent modification of lithiation-induced phase transformations in V2O5 as a model phase-transforming cathode. A pronounced modulation of phase coexistence regimes is observed as a function of particle geometry. Specifically, a metastable phase is stabilized for nanometre-sized spherical V2O5 particles, to circumvent the formation of large misfit strains. Spatially resolved EDXRD measurements demonstrate that particle geometries strongly modify the tortuosity of the porous cathode architecture. Greater ion-transport limitations in electrode architectures comprising micrometre-sized platelets result in considerable lithiation heterogeneities across the thickness of the electrode. These insights establish particle geometry-dependent modification of metastable phase regimes and electrode tortuosity as key design principles for realizing the promise of intercalation cathodes. Designing electrode architectures for Li-ion batteries that can be reversibly accessible for ion storage can be challenging. Using operando techniques the mechanistic origin of lithiation-induced phase transformations in a V2O5 model cathode is now clarified.

A primary mode of failure of thin-film coatings is the mismatch in thermal expansion coefficients of the substrate and the coating, which results in accumulation of interfacial stresses and ultimately in film delamination. While much attention has been devoted to modulation of interfacial bonding to mitigate delamination, current strategies are constrained in their generalizability and have had limited success in imbuing resistance to prolonged thermal cycling. We demonstrate here the incorporation of rigid thermal expansion compensators within polymeric films as a generalizable strategy for minimizing thermal mismatch with the substrate. Nanostructures of the isotropic negative thermal expansion (NTE) material HfV2O7 have been prepared based on the reaction of nanoparticulate precursors. The NTE behavior, derived from transverse oxygen displacement within the cubic structure, has been examined using temperature-variant powder X-ray diffraction, Raman spectroscopy, electron microscopy, and selected-area electron diffraction measurements. HfV2O7 initially crystallizes in a 3 × 3 × 3 superlattice but undergoes phase transformations to stabilize a cubic structure that exhibits strong and isotropic NTE with a coefficient of thermal expansion (CTE) = -6.7 × 10-6 °C-1 across an extended temperature range of 130-700 °C. Incorporation of HfV2O7 in a high-temperature thermoset polybenzimidazole enables the reduction of compressive stress by 67.3% for a relatively small loading of 26.6 vol % HfV2O7. Based on a composite model, we demonstrate that HfV2O7 can reduce the thermal expansion coefficient of polymer nanocomposite films, even at low volume fractions, as a result of its substantially higher elastic modulus compared to the continuous polymer matrix. By changing the volume fraction of HfV2O7, the overall coefficients of thermal expansion of the film can be tuned to match a range of substrates, thereby mitigating thermal stresses and resolving a fundamental challenge for high-temperature composites and nanocomposite coatings.

Solar water splitting has emerged as an urgent imperative as hydrogen emerges as an increasingly important form of energy storage. g-C

Ladder-type thiazole-fused

Future-generation neuromorphic computing seeks to overcome the limitations of von Neumann architectures by colocating logic and memory functions, thereby emulating the function of neurons and synapses in the human brain. Despite remarkable demonstrations of high-fidelity neuronal emulation, the predictive design of neuromorphic circuits starting from knowledge of material transformations remains challenging. VO

Mixed anion compounds afford considerable compositional diversity and tunability of function. A challenging aspect of anion control of properties of periodic solids is to preserve the crystal lattice while substituting for different anions of widely varying size and hardness. Post-synthetic modification routes that place cations or anions in non-equilibrium configurations represent a promising means of decoupling composition and crystal structure and for accessing metastable solids; however, such methods remain relatively unexplored for anion placement. Here, we report the synthesis of LaOI nanocrystals by a non-hydrolytic sol-gel condensation reaction and their transformation into LaOBr, LaOCl, and LaOF nanocrystals along hard-soft-acid-base principles using post-synthetic metathesis reactions with ammonium halides. Anion displacement proceeds along halide planes preserving the tetragonal matlockite structure. Energy-variant X-ray excited optical luminesce signatures of alloyed Tb3+-ions serves as a sensitive quantum reporter of the preservation of the cation sublattice and hardening of the crystal structure upon anion replacement.

As a result of the depletion of conventional oil reserves and the unprecedented growth in world energy demand, increasing attention has focused on the extraction and utilization of unconventional o...

Elucidating the interactions between metal ions and dissolved organic matter and deciphering mechanisms for their mineralization in the aquatic environment are central to understanding the speciation, transport, and toxicity of nanoparticles (NPs). Herein, we examine the interactions between Ag+ and Au3+ ions in mixed solutions (χAg = 0.2, 0.5, and 0.8) in the presence of humic acids (HAs) under simulated sunlight; these conditions result in the formation of bimetallic Ag-Au NPs. A key distinction is that the obtained alloy NPs are compositionally and morphologically rather different from NPs obtained from thermally activated dark processes. Photoillumination triggers a distinctive plasmon-mediated process for HA-assisted reductive mineralization of ions to bimetallic alloy NPs which is not observed in its dark thermal reduction counterpart. The initial nucleation of bimetallic NPs is dominated by differences in the cohesive energies of Ag and Au crystal lattices, whereas the growth mechanisms are governed by the strongly preferred incorporation of Ag ions, which stems from their greater photoreactivity. The bimetallic NPs crystallize in shapes governed by the countervailing influence of minimizing free energy through the adoption of Wulff constructions and the energetic penalties associated with twin faults. As such, assessments of the stability and the potential toxic effects of bimetallic NPs arising from their possible existence in aquatic environments will depend sensitively on the origins of their formation.

It is urgently desired yet challenging to synthesize porous graphitic carbon (PGC) in a bottom-up manner while circumventing the need for high-temperature pyrolysis. Here we present an effective and scalable strategy to synthesize PGC through acid-mediated aldol triple condensation followed by low-temperature graphitization. The deliberate structural design enables its graphitization in situ in solution and at low pyrolysis temperature. The resulting material features ultramicroporosity characterized by a sharp pore size distribution. In addition, the pristine homogeneous composition of the reaction mixture allows for solution-processability of the material for further characterization and applications. Thin films of this PGC exhibit several orders of magnitude higher electrical conductivity compared to analogous control materials that are carbonized at the same temperatures. The integration of low-temperature graphitization and solution-processability not only allows for an energy-efficient method for the production and fabrication of PGC, but also paves the way for its wider employment in applications such as electrocatalysis, sensing, and energy storage., Porous graphitic carbon was synthesized through acid-mediated aldol triple condensation followed by low-temperature graphitization. The inherent thin film processability and the low temperature requirement of the synthesis enable various potential applications.

The construction industry bears a massive carbon footprint that is largely derived from the carbon-intensive nature of key structural materials. Microalloying of structural steel represents an underappreciated strategy for enabling greater economy of materials use and thus reducing carbon emissions. Policy implemented after the Sichuan Earthquake has mandated an increased use of vanadium steel, giving rise to an unintended (but welcome) benefit of substantial decarbonization of a major sector.

The structural rigidity of fused units in the polymer backbone, in addition to the resulting stabilizing effect of the quinoidal structure, and tunable electronic properties have played a key role in promoting highly-ordered π-stacking moieties, exhibiting promising charge carrier mobilities. The electron-deficient thiazole moiety shows high planarity and effective π–π stacking, which leads to the reduction in the energy levels of the highest occupied and lowest unoccupied molecular orbitals (HOMO/LUMO), and ideally enhances the electron charge mobility. Four heterocycle-based monomers BTzS, BTzSe, DTS, and DTG based on fused bithiazole and dithiophene units incorporated with sulfur, selenium, silicon, and germanium as the bridging atoms were synthesized and characterized. The monomers were copolymerized with the electron-rich alkylated thienylenevinylene (TV) unit to afford copolymers P1–P4. The thermal, optical, and electrochemical properties and crystallinity of the copolymers were thoroughly investigated. Extensive OFET device optimization using different solvents and annealing temperatures resulted in the best charge mobility of 0.09 cm2 V−1 s−1 for the electron-deficient bithiazole BTzS copolymer P1 and 0.36 cm2 V−1 s−1 for the DTS copolymer P3.

Through diversity of composition, sequence, and interfacial structure, hybrid materials greatly expand the palette of materials available to access novel functionality. The NSF Division of Materials Research recently supported a workshop (October 17–18, 2019) aiming to (1) identify fundamental questions and potential solutions common to multiple disciplines within the hybrid materials community; (2) initiate interfield collaborations between hybrid materials researchers; and (3) raise awareness in the wider community about experimental toolsets, simulation capabilities, and shared facilities that can accelerate this research. This article reports on the outcomes of the workshop as a basis for cross-community discussion. The interdisciplinary challenges and opportunities are presented, and followed with a discussion of current areas of progress in subdisciplines including hybrid synthesis, functional surfaces, and functional interfaces.

Summary Intercalation-induced phase transformations in Li-ion battery electrode materials give rise to multi-phase coexistence regimes within individual particles, generating significant lattice coherency strain across dynamically evolving interfaces. We demonstrate here that the lattice coherency strain can be alleviated by leveraging the coupling of electrochemistry, mechanics, and particle geometry to achieve controllable nucleation and deterministic ion transport. Here, we contrast singular kinks and continuous curvature as a means of enabling homogeneous lithiation without developing large stresses within a model cathode material, V2O5. The singular kink confirms that local curvature facilitates lithiation but also exacerbates lithiation inhomogeneities and elastic misfit strain. In contrast, the incorporation of continuous curvature enables homogeneous single-phase lithiation, mitigating lattice coherency strain. The studies provide a direct view of the coupling of mechanics and electrochemistry within crystalline electrodes and suggest that mesoscale architectures can help resolve key failure mechanisms limiting the performance of energy-storage systems without sacrificing charge/discharge kinetics.

The presence of H2O has been linked to enhancements in the reactivity of cathodes for Mg2+ electrochemistry. If the enhancements were mimicked by nonaqueous solvents, they could enable Mg batteries...

Metal–insulator transition materials such as VO2 have garnered much attention in the field of neuromorphic devices because of their nonlinear behavior and orders of magnitude scale property changes...

As a result of the increasing emphasis on accessing unconventional deposits of heavy oil and bitumen to meet global energy needs, there is an intense focus on addressing the rheological challenges ...

Solar fuel generation mediated by semiconductor heterostructures represents a promising strategy for sustainable energy conversion and storage. The design of semiconductor heterostructures for photocatalytic energy conversion requires the separation of photogenerated charge carriers in real space and their delivery to active catalytic sites at the appropriate overpotentials to initiate redox reactions. Operation of the desired sequence of light harvesting, charge separation, and charge transport events within heterostructures is governed by the thermodynamic energy offsets of the two components and their photoexcited charge-transfer reactivity, which determine the extent to which desirable processes can outcompete unproductive recombination channels. Here, we map energetic offsets and track the dynamics of electron transfer in MoS2/CdS architectures, prepared by interfacing two-dimensional MoS2 nanosheets with CdS quantum dots (QDs), and correlate the observed charge separation to photocatalytic activity in the hydrogen evolution reaction. The energetic offsets between MoS2 and CdS have been determined using hard and soft X-ray photoemission spectroscopy (XPS) in conjunction with density functional theory. A staggered type-II interface is observed, which facilitates electron and hole separation across the interface. Transient absorption spectroscopy measurements demonstrate ultrafast electron injection occurring within sub-5 ps from CdS QDs to MoS2, allowing for creation of a long-lived charge-separated state. The increase of electron concentration in MoS2 is evidenced with the aid of spectroelectrochemical measurements and by identifying the distinctive signatures of electron-phonon scattering in picosecond-resolution transient absorption spectra. Ultrafast charge separation across the type-II interface of MoS2/CdS heterostructures enables a high Faradaic efficiency of ∼99.4 ± 1.2% to be achieved in the hydrogen evolution reaction (HER) and provides a 40-fold increase in the photocatalytic activity of dispersed photocatalysts for H2 generation. The accurate mapping of thermodynamic driving forces and dynamics of charge transfer in these heterostructures suggests a means of engineering ultrafast electron transfer and effective charge separation to design viable photocatalytic architectures.

Transformations between different atomic configurations of a material oftentimes bring about dramatic changes in functional properties as a result of the simultaneous alteration of both atomistic a...