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An energy storage paradigm orthogonal to Li-ion battery chemistries can be conceptualized by employing anions as the primary charge carriers. F-ion conversion chemistries show promise but have limi...

The utilization of metallic anodes holds promise for unlocking high gravimetric and volumetric energy densities and is pivotal to the adoption of ‘beyond Li’ battery chemistries. Much of the promise of magnesium batteries stems from claims regarding their lower predilection for dendrite growth. Whilst considerable effort has been invested in the design of novel electrolytes and cathodes, detailed studies of Mg plating are scarce. Using galvanostatic electrodeposition of metallic Mg from Grignard reagents in symmetric Mg–Mg cells, we establish a phase map characterized by disparate morphologies spanning the range from fractal aggregates of 2D nanoplatelets to highly anisotropic dendrites with singular growth fronts and nanowires entangled in the form of mats. The effects of electrolyte concentration, applied current density, and coordinating ligands have been explored. The study demonstrates a complex range of electrodeposited morphologies including canonical dendrites with shear moduli conducive to penetration through typical polymeric separators. We further demonstrate a strategy for mitigating Mg dendrite formation based on the addition of molecular Lewis bases that promote nanowire growth through selective surface coordination.

The operation of a Li-ion battery involves a concerted sequence of mass and charge transport processes, which are underpinned by alternating dilation/contraction of the active electrode materials. Several Li-ion battery failure mechanisms can be directly traced to lattice-mismatch strain arising from local compositional heterogeneities. The mechanisms of chemo-mechanical coupling that effect phase separation and the resulting complex evolution of internal stress fields remain inadequately understood. This work employs X-ray microscopy techniques to image the evolution of composition and stress across individual bent V2O5 particles. Experimental findings show that lattice strain imposed by the deformation of an individual cathode particle profoundly modifies phase separation patterns, yielding striated Li-rich domains ensconced within a Li-poor matrix. Particle-level inhomogeneities compound across scales resulting in fracture and capacity fade. Coupled phase field modeling of the evolution of domains reveals that the observed patterns minimize the energetic costs incurred by the geometrically imposed strain gradients during lithiation of the material and illustrate that phase separation motifs depend sensitively on the particle geometry, dimensions, interfacial energetics, and lattice incommensurability. Sharp differences in phase separation patterns are observed between lithiation and delithiation. This work demonstrates the promise of strain-engineering and particle geometry to deterministically control phase separation motifs such as to minimize accumulated stresses and mitigate important degradation mechanisms.

V2O5 is of interest as a Mg intercalation electrode material for Mg batteries, both in its thermodynamically stable layered polymorph (α-V2O5) and in its metastable tunnel structure (ζ-V2O5). However, such oxide cathodes typically display poor Mg insertion/removal kinetics, with large voltage hysteresis. Herein, we report the synthesis and evaluation of nanosized (ca. 100 nm) ζ-V2O5 in Mg-ion cells, which displays significantly enhanced electrochemical kinetics compared to microsized ζ-V2O5. This effect results in a significant boost in stable discharge capacity (130 mA h g-1) compared to bulk ζ-V2O5 (70 mA h g-1), with reduced voltage hysteresis (1.0 V compared to 1.4 V). This study reveals significant advancements in the use of ζ-V2O5 for Mg-based energy storage and yields a better understanding of the kinetic limiting factors for reversible magnesiation reactions into such phases.

Significance The function of cathode materials is determined by factors transcending decades of length scales, spanning the range from the crystal structure and composition of the compound to the dimensions and morphologies of the particles, their connectivity with other particles and with the conductive matrix, and their spatial location relative to the electrolyte–electrode interface. Mitigating the constraints and degradation mechanisms that limit cathode materials from realizing their full potential requires careful consideration of the electrode structure spanning multiple length scales. In this work, we explore an intriguing concept: For the same exact composition (V 2 O 5 ), can the atomic connectivity be altered to stabilize a metastable polymorph that provides access to an entirely distinctive cation insertion and diffusion mechanism?

Significance The function of cathode materials is determined by factors transcending decades of length scales, spanning the range from the crystal structure and composition of the compound to the dimensions and morphologies of the particles, their connectivity with other particles and with the conductive matrix, and their spatial location relative to the electrolyte–electrode interface. Mitigating the constraints and degradation mechanisms that limit cathode materials from realizing their full potential requires careful consideration of the electrode structure spanning multiple length scales. In this work, we explore an intriguing concept: For the same exact composition (V2O5), can the atomic connectivity be altered to stabilize a metastable polymorph that provides access to an entirely distinctive cation insertion and diffusion mechanism?, Substantial improvements in cycle life, rate performance, accessible voltage, and reversible capacity are required to realize the promise of Li-ion batteries in full measure. Here, we have examined insertion electrodes of the same composition (V2O5) prepared according to the same electrode specifications and comprising particles with similar dimensions and geometries that differ only in terms of their atomic connectivity and crystal structure, specifically two-dimensional (2D) layered α-V2O5 that crystallizes in an orthorhombic space group and one-dimensional (1D) tunnel-structured ζ-V2O5 crystallized in a monoclinic space group. By using particles of similar dimensions, we have disentangled the role of specific structural motifs and atomistic diffusion pathways in affecting electrochemical performance by mapping the dynamical evolution of lithiation-induced structural modifications using ex situ scanning transmission X-ray microscopy, operando synchrotron X-ray diffraction measurements, and phase-field modeling. We find the operation of sharply divergent mechanisms to accommodate increasing concentrations of Li-ions: a series of distortive phase transformations that result in puckering and expansion of interlayer spacing in layered α-V2O5, as compared with cation reordering along interstitial sites in tunnel-structured ζ-V2O5. By alleviating distortive phase transformations, the ζ-V2O5 cathode shows reduced voltage hysteresis, increased Li-ion diffusivity, alleviation of stress gradients, and improved capacity retention. The findings demonstrate that alternative lithiation mechanisms can be accessed in metastable compounds by dint of their reconfigured atomic connectivity and can unlock substantially improved electrochemical performance not accessible in the thermodynamically stable phase.

Low-cost and scalable superhydrophobic coating methods provide viable approaches for energy-efficient separation of immiscible liquid/liquid mixtures. A scalable photopolymerization method is developed to functionalize porous substrates with a hybrid coating of tetrapodal ZnO (T-ZnO) and polymethacrylate, which exhibits simultaneous superhydrophobicity and superoleophilicity. Here, T-ZnO serves dual purposes by (i) initiating radical photopolymerization during the fabrication process through a hole-mediated pathway and (ii) providing a hierarchical surface roughness to amplify wettability characteristics and suspend liquid droplets in the metastable Cassie-Baxter regime. Photopolymerization provides a means to finely control the conversion and spatial distribution of the formed polymer, whilst allowing for facile large-area fabrication and potential coating on heat-sensitive substrates. Coated stainless-steel meshes and filter papers with desired superhydrophobic/superoleophilic properties exhibit excellent performance in separating stratified oil/water, oil/ionic-liquid, and water/ionic-liquid mixtures as well as water-in-oil emulsions. The hybrid coating demonstrates desired mechanical robustness and chemical resistance for their long-term application in large-scale energy-efficient separation of immiscible liquid/liquid mixtures.

Rare-earth scheelites represent a diverse family of compounds with multiple degrees of freedom, which enables the incorporation of a wide range of lanthanide color centers. Precise positioning of quantum objects is attainable by the choice of alkali cations and lattice connectivity of polyanion units. Herein, we report the structure-dependent energy transfer and lattice coupling of optical transitions in La3+- and Dy3+-containing scheelite-type double and quadruple molybdates NaLa1-xDyx(MoO4)2 and Na5La1-xDyx(MoO4)4. X-ray excitation of La3+ core states generates excited-state electron-hole pairs, which, upon thermalizing across interconnected REO8 polyhedra in double molybdates, activate a phonon-coupled excited state of Dy3+. A pronounced luminescence band is observed corresponding to optical cooling of the lattice upon preferential radiative relaxation from a "hot" state. In contrast, combined X-ray absorption near-edge structure and X-ray-excited optical luminescence studies reveal that such a lattice coupling mechanism is inaccessible in quadruple molybdates with a greater separation of La3+-Dy3+ centers.

Automatized object identification and feature analysis of experimental image data are indispensable for data-driven material science; deep-learning-based segmentation algorithms have been shown to be a promising technique to achieve this goal. However, acquiring high-resolution experimental images and assigning labels in order to train such algorithms is challenging and costly in terms of both time and labor. In the present work, we apply synthetic images, which resemble the experimental image data in terms of geometrical and visual features, to train state-of-art deep learning-based Mask R-CNN algorithms to segment vanadium pentoxide (V2O5) nanowires, a canonical cathode material, within optical intensity-based images from spectromicroscopy. The performance evaluation demonstrates that even though the deep learning model is trained on pure synthetically generated structures, it can segment real optical intensity-based spectromicroscopy images of complex V2O5 nanowire structures in overlapped particle networks, thus providing reliable statistical information. The model can further be used to segment nanowires in scanning electron microscopy (SEM) images, which are fundamentally different from the training dataset known to the model. The proposed methodology of using a purely synthetic dataset to train the deep learning model can be extended to any optical intensity-based images of variable particle morphology, extent of agglomeration, material class, and beyond., 12 pages, 12 figures

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 HfV

Summary The decarbonization of heavy industry and the emergence of renewable energy technologies are inextricably linked to access to mineral resources. As such, there is an urgent need to develop benchmarked assessments of the role of critical elements in reducing greenhouse gas emissions. Here, we explore the role of vanadium in decarbonizing construction by serving as a microalloying element and enabling the energy transition as the primary component of flow batteries used for grid-level storage. We estimate that vanadium has enabled an avoided environmental burden totaling 185 million metric tons of CO2 on an annual basis. A granular analysis estimates savings for China and the European Union at 1.15% and 0.18% of their respective emissions, respectively. Our results highlight the role of critical metals in developing low-carbon infrastructure while underscoring the need for holistic assessments to inform policy interventions that mitigate supply chain risks., Graphical abstract, Highlights • Enabling the energy transition and deep decarbonization hinges on strategic minerals • The versatility of vanadium chemistries enables technologies that lower CO2 emissions • In structural applications, vanadium enables a greater economy of materials use • Vanadium redox flow batteries balance the intermittency of wind and solar power, Energy resources; Energy sustainability; Materials science; Materials chemistry; Energy materials

Processing, storing, and transmitting information accounts for ∼10% of global energy use; projections suggest that computational energy demands will be 10× higher than the projected global energy supply by 2040. Realizing solid-state analogs of neural circuitry, using ‘neuromorphic’ materials, holds promise for enabling a new energy-efficient computing paradigm. The metal–insulator transitions (MITs) of electron-correlated transition-metal oxides provide an attractive vector for achieving large conductance switching with minimal energy dissipation. Here, we review current understanding of the mechanisms underpinning electronic instabilities, discuss methods for modulation of spiking behavior through tuning of atomistic and electronic structure, and highlight the need for establishing deterministic and independent control of transformation characteristics such as switching magnitude, energy thresholds, heat dissipation, hysteresis, and dynamics of relaxation.

Achieving the efficacious and rapid separation of mixed water/oil streams has emerged as a fundamental imperative in order to facilitate extraction of fossil fuels by methods such as cyclic steam s...

Increased adoption of engineered aluminum alloys in vehicular components is imperative for automotive lightweighting, but such alloys are oftentimes prone to degradation upon exposure to corrosive ...

The design of a chemical synthesis often relies on a combination of chemical intuition and Edisonian trial-and-error methods. Such methods are not just inefficient but inherently limited in their a...

Microbial and emerging chemical contaminants are unwanted constituents in reclaimed wastewater, due to the health concerns of using the water for agricultural irrigation, aquifer recharges, and potable water. Removal of these contaminants is required but it is currently challenging, given that there is no simple treatment technology to effectively remove the mixture of these contaminants. This study examined the effectiveness of ZnO-assisted photocatalytic degradation of several constituents, including 1,4-dioxane, trihalomethanes (THMs), triclosan (TCS), triclocarban (TCC), antibiotic resistant bacteria (ARB) and antibiotic resistant genes (ARGs), under low intensity of UV exposure. E. coli with an ARGs-carrying circular plasmid (pUC19) was used as a model antibiotic resistant bacterium. Our results show that commercial zinc oxide (C-ZnO) assisted photodegradation of 1,4-dioxane, and dehalogenation of THMs, TCS, and TCC, while tetrapodal zinc oxide (T-ZnO) enhanced the dehalogenation of TCS and TCC. Additionally, T-ZnO assisted the photocatalytic inactivation of the E. coli within 6 h and caused structural changes in the plasmid DNA (pUC19) with additional UV exposure, resulting in non-functional AGR-containing plasmids. These results also suggest that higher UV dose is required not only to inactivate ARB but also to damage ARGs in the ARB in order to decrease risks in promoting ARB population in the environment. Overall, our results implicated that, under low UV intensity, ZnO-assisted photocatalysis is a promising alternative to simultaneously remove biological and emerging chemical contaminants in treated wastewater for safe reuse.

Ionic compounds wherein lanthanide cations are arrayed alongside anions adopt a wide range of crystal structures as a result of the variation of ionic radii and electronic configurations across the lanthanide series. Owing to the constricted nature of 4f orbitals, local coordination environments and structural preferences in such compounds are primarily dictated by electrostatic interactions and steric considerations with the primary driving force being the minimization of the crystal lattice energy. In this review, we examine a broad class of dianionic rare-earth compounds, lanthanide oxyhalides that present a multidimensional design space for tuning of functional properties by dint of the possibilities for extensive alloying on cationic and anionic sublattices; the considerable span of ionic radii and hardness across the lanthanide series and down the halide group, respectively; a large tolerance window for point defects such as oxide and halide vacancies; as well as multiple accessible polymorphs. In addition to their structural versatility, control over functional properties is accessible based on alteration of microstructure and surface chemistry. Synthetic strategies for accessing atomistic, nanoscale, and mesoscale control are discussed using illustrative examples placing particular emphasis on non-hydrolytic sol—gel processes that provide access to well-defined solid-solution nanocrystals. The reactivity and post-synthetic modification of these compounds is further delineated. Methods for defining color centers within these compounds, cooperativity of the optical response of the color centers with the host lattice (determined by overlap integrals specific to each structure type and the polarization and ligand field effects of different halide ions) and adjacent color centers (reliant on energy transfer schema), and their practical application in phosphors are further detailed. Mechanisms facilitating down- and up-conversion of energy absorbed from incident electromagnetic radiation or high-energy particles are delineated with particular emphasis on X-ray and electron-beam excitation. The accessible energy conversion mechanisms, efficacious radiative recombination channels, and opportunities for systematically tuning color through compositional modulation have led to the emergence of these materials as potential candidates for phosphors. These materials have potential applications in solid-state lighting, radiation detection, and as the active elements of imaging devices. The tolerance towards large concentrations of anion vacancies and the facile diffusivity of anions in these compounds further underpins the function of lanthanide oxyhalides as ion conductors, gas sensors, and heterogeneous catalysts. Increasing interest has focused on utilization of well-defined color centers for quantum information science and multiplexed sensing in biological systems. Such applications require additional control of the positioning of dopant atoms and understanding of their interactions with the host lattice and other dopant atoms.

Metastable materials that represent excursions from thermodynamic minima are characterized by distinctive structural motifs and electronic structure, which frequently underpins new function. The binary oxides of hafnium present a rich diversity of crystal structures and are of considerable technological importance given their high dielectric constants, refractory characteristics, radiation hardness, and anion conductivity; however, high-symmetry tetragonal and cubic polymorphs of HfO2 are accessible only at substantially elevated temperatures (1720 and 2600 °C, respectively). Here, we demonstrate that the core–shell arrangement of VO2 and amorphous HfO2 promotes outwards oxygen diffusion along an electropositivity gradient and yields an epitaxially matched V2O3/HfO2 interface that allows for the unprecedented stabilization of the metastable cubic polymorph of HfO2 under ambient conditions. Free-standing cubic HfO2, otherwise accessible only above 2600 °C, is stabilized by acid etching of the vanadium oxide core. In contrast, interdiffusion under oxidative conditions yields the negative thermal expansion material HfV2O7. Variable temperature powder X-ray diffraction demonstrate that the prepared HfV2O7 exhibits pronounced negative thermal expansion in the temperature range between 150 and 700 °C. The results demonstrate the potential of using epitaxial crystallographic relationships to facilitate preferential nucleation of otherwise inaccessible metastable compounds.

Owing to their enormous capacities, Li-S batteries have emerged as a prime candidate for economic and sustainable energy storage. Still, potential mechanics-based issues exist that must be addressed: lithiation of sulfur produces an enormous volume expansion (~ 80%). In other high capacity electrodes, large expansions generate considerable stresses that can lead to mechanical damage and capacity fading. However, the mechanics of electrochemical cycling of sulfur is fundamentally distinct from other systems due to solid-to-liquid, liquid-to-liquid, and liquid-to-solid phase transformations, and thus remains poorly understood. To this end, we measure the evolution of stresses in composite sulfur cathodes during electrochemical cycling and link these stresses to structural evolution. We observe that nucleation and growth of solid lithium-sulfur phases induces significant stresses, including irreversible stresses from structural rearrangements during the first cycle. However, subsequent cycles show highly reversible elastic mechanics, thereby demonstrating strong potential for extended cycling in practical applications.

Covalently networked polymers offer desirable non-crystallinity and mechanical strength for solid polymer electrolytes (SPEs), but the chemically active cross-links involved in their construction could deteriorate the compatibility with high-energy cathode materials that are electrophilic and/or in the charged state. Herein we reveal a strong dependence of cyclability of such cathodes on the reactivity of covalently networked SPEs and demonstrate a polymer design that renders these SPEs chemically inert. We designed and synthesized two hybrid networks, both with polyethylene oxide as the cation conducting component and polyhedral oligomeric silsesquioxane as the branch point, but respectively use alkylamino and chemically inert triazole groups as cross-links. All-solid-state cells using the alkylamino-containing SPE underwent rapid degradation while cells using triazole SPEs showed stable cycling.

Negative-emissions technologies to capture atmospheric greenhouse gases are urgently needed to achieve ambitious global emissions targets and limit the catastrophic long-term effects of climate change. This Voices asks: do you feel there are any misconceptions or myths surrounding the goal of achieving negative emissions and how it is discussed in the literature? For this field to move forward, how should negative emissions be conceptualized across disciplines?

V2O5 is of interest as a Mg intercalation electrode material for Mg batteries, both in its thermodynamically stable layered polymorph (α-V2O5) and in its metastable tunnel structure (ζ-V2O5). However, such oxide cathodes typically display poor Mg insertion/removal kinetics, with large voltage hysteresis. Herein, we report the synthesis and evaluation of nanosized (ca. 100 nm) ζ-V2O5 in Mg-ion cells, which displays significantly enhanced electrochemical kinetics compared to microsized ζ-V2O5. This effect results in a significant boost in stable discharge capacity (130 mA h g-1) compared to bulk ζ-V2O5 (70 mA h g-1), with reduced voltage hysteresis (1.0 V compared to 1.4 V). This study reveals significant advancements in the use of ζ-V2O5 for Mg-based energy storage and yields a better understanding of the kinetic limiting factors for reversible magnesiation reactions into such phases.

The manuscript presents a detailed analysis of embodied energy and carbon footprint reduction enabled by microalloying of steel, thereby providing a rich global perspective of the (outsized) role of chemical elements added in trace concentrations on the overall footprint of the construction industry. As such, the manuscript addresses an important and timely topic at the intersection of materials criticality, structural performance, life cycle assessment, and policy interventions. The United Nations estimates that the worldwide energy consumption of buildings accounts for 30—40% of global energy production, underlining the importance of the judicious selection of construction materials. Much effort has focused on the use of high-strength low-alloy steels in reinforcement bars whose economy of materials use is predicated upon improved yield strengths in comparison to low-carbon steels. While microalloying is known to allow for reduced steel consumption, a sustainability analysis in terms of embodied energy and CO 2 has not thus far been performed. Here we calculate the impact of supplanting lower grade reinforcement bars with higher strength vanadium microalloyed steels on embodied energy and carbon footprint. We find that the increased strength of vanadium microalloyed steel translates into substantial material savings over mild steel thus reducing the total global fossil carbon footprint by as much as 0.385%. A more granular analysis pegs savings for China and the European Union at 1.01 and 0.19%, respectively, of their respective emissions.

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 and electronic structure. Transformation barriers between polytypes can be tuned through compositional modification, generally in an immutable manner. Continuous, stimulus-driven modulation of phase stabilities remains a significant challenge. Utilizing the metal-insulator transition of VO

Data-driven approaches have brought about a revolution in manufacturing; however, challenges persist in their applications to synthetic strategies. Their application to the deterministic navigation of reaction trajectories to stabilize crystalline solids with precise composition, atomic connectivity, microstructural dimensionality, and surface structure remains a frontier in inorganic materials research. The design of synthetic methodologies for the preparation of inorganic materials is often inefficient in terms of exploration of potentially vast design spaces spanning multiple process variables, reaction sequences, as well as structural parameters and reactivities of precursors and structure-directing agents. Reported synthetic methods are further limited in terms of the insight they provide into underlying chemical and physical principles. The recent surge in interest in accelerating the discovery of new materials can be considered as an opportunity to re-evaluate our approach to materials synthesis, and for considering new frameworks for exploration that are systematic and strategic in approach. Herein, we outline with the help of several illustrative examples, the challenges, opportunities, and limitations of data-driven synthesis design. The account collates discussion of design-of-experiments sampling methods, machine learning modeling, and active learning to develop experimental workflows that accelerate the experimental navigation of synthetic landscapes.

The diffusion pathways of Li-ions as they traverse cathode structures in the course of insertion reactions underpin many questions fundamental to the functionality of Li-ion batteries. Much current knowledge derives from computational models or the imaging of lithiation behavior at larger length scales; however, it remains difficult to experimentally image Li-ion diffusion at the atomistic level. Here, by using topochemical Li-ion insertion and extraction to induce single-crystal-to-single-crystal transformations in a tunnel-structured V2 O5 polymorph, coupled with operando powder X-ray diffraction, we leverage single-crystal X-ray diffraction to identify the sequence of lattice interstitial sites preferred by Li-ions to high depths of discharge, and use electron density maps to create a snapshot of ion diffusion in a metastable phase. Our methods enable the atomistic imaging of Li-ions in this cathode material in kinetic states and provide an experimentally validated angstrom-level 3D picture of atomic pathways thus far only conjectured through DFT calculations.

ConspectusThe development of efficient solar energy conversion to augment other renewable energy approaches is one of the grand challenges of our time. Water splitting, or the disproportionation of H2O into energy-dense fuels, H2 and O2, is undoubtedly a promising strategy. Solar water splitting involves the concerted transfer of four electrons and four protons, which requires the synergistic operation of solar light harvesting, charge separation, mass and charge transport, and redox catalysis processes. It is unlikely that individual materials can mediate the entire sequence of charge and mass transport as well as energy conversion processes necessary for photocatalytic water splitting. An alternative approach, emulating the functioning of photosynthetic systems, involves the utilization of hybrid systems wherein different components perform the various functions required for solar water splitting. The design of such hybrid systems requires the multiple components to operate in lockstep with optimal ther...

The significant heat loss and severe thermal fluctuations inherent in steam-assisted gravity drainage (SAGD) and cyclic steam stimulation (CSS) impose considerable constraints on well cementing. In order to obtain better energy efficiency and mechanical robustness, there is considerable interest in the development of low-thermal-conductivity cement that can provide a combination of enhanced thermal insulation and mechanical resilience upon thermal cycling. However, the current palette of thermal cements is exceedingly sparse. In this article, we illustrate a method for decreasing the thermal conductivity of cement by inclusion of hydroxyethylcellulose-functionalized halloysite nanotubes. Halloysite/hydroxyethylcellulose inclusions offer an abundance of disparate interfaces and void space that can effectively scatter phonons, thereby bringing about a pronounced reduction of thermal conductivity. The microstructure of the nanocomposite cementitious matrix is strongly modified even as the compositional profile remains essentially unaltered. Modified cement nanocomposites incorporating halloysite nanotubes along with hydroxyethylcellulose in a 8:1 ratio with an overall loading of 2 wt.% exhibit the lowest measured thermal conductivity of 0.212 ± 0.003 W/m.K, which is substantially reduced from the thermal conductivity of unmodified cement (1.252 W/m.K). The ability to substantially decrease thermal conductivity without deleterious modification of mechanical properties through alteration of microstructure, inclusion of encapsulated void spaces, and introduction of multiple phonon-scattering interfaces suggests an entirely new approach to oilwell cementing based on the design of tailored nanocomposites.

In a recently published paper in Chem, Zhu, Zhang, Yan, and colleagues unlock diffusion pathways for potassium ions within a double-layered V2O5 structure and demonstrate a potassium-ion battery with unprecedented performance characteristics including an average voltage of 3.2 V, an initial capacity of 131 mAh·g−1, and rapid charge/discharge capabilities even at high rates. The study serves as a remarkable illustration of the utility of mining metastable phase space to identify structural motifs that allow for mitigation of the diffusion challenges plaguing larger cations.

Fenestration elements that enable spectrally selective dynamic modulation of the near-infrared region of the electromagnetic spectrum are of great interest as a means of decreasing the energy consumption of buildings by adjusting solar heat gain in response to external temperature. The binary vanadium oxide VO2 exhibits a near-room-temperature insulator–metal electronic transition accompanied by a dramatic modulation of the near-infrared transmittance. The low-temperature insulating phase is infrared transparent but blocks infrared transmission upon metallization. There is considerable interest in harnessing the thermochromic modulation afforded by VO2 in nanocomposite thin films. However, to prepare a viable thermochromic film, the visible-light transmittance must be maintained as high as possible while maximizing thermochromic modulation in the near-infrared region of the electromagnetic spectrum, which necessitates the development of high-crystalline-quality VO2 nanocrystals of the optimal particle siz...

Lead halide perovskites are a versatile class of semiconductors that provide considerable opportunities for tunability of absorption maxima, exciton binding energies, and band gaps as a function of composition and dimensional confinement. Considerable attention has focused on the design and synthesis of related frameworks with reduced structural dimensionality that provide an expanded palette of optical transitions with varying degrees of exciton localization. In this work, we demonstrate the ligand-mediated navigation of the cesium—lead—bromine ternary phase diagram demarcating distinctive regimes wherein 3D CsPbBr3 and 0D Cs4PbBr6 nanocrystals can be stabilized. The denticity, steric bulk, and concentration of aliphatic amine ligands strongly modifies the supersaturation of lead monomers, scaling proportionately to their complexation coefficients and ability to form ordered passivating ligand shells. The added ligands strongly alter the trajectory of nucleation and growth processes, stabilizing either P...

The known crystal structures of solids often correspond to the most thermodynamically stable arrangement of atoms. Yet, oftentimes there exist a richly diverse set of alternative structural arrangements that lie at only slightly higher energies and can be stabilized under specific constraints (temperature, pressure, alloying, point defects). Such metastable phase space holds tremendous opportunities for nonequilibrium structural motifs and distinctive chemical bonding and ultimately for the realization of novel function. In this Feature Article, we explore the challenges with the prediction, stabilization, and utilization of metastable polymorphs. We review synthetic strategies that allow for trapping of such states of matter under ambient temperature and pressure including topochemical modification of more complex crystal structures; dimensional confinement wherein surface energy differentials can alter bulk phase stabilities; templated growth exploiting structural homologies with molecular precursors; i...

The conversion and numerical amplification of X-ray photons to visible light is at the heart of numerous technological applications spanning the range from X-ray detectors and scintillators to radiographic medical imaging devices. The need for increased sensitivity and spatial resolution to reduce radiation exposure and provide better differentiation of specimens presenting an X-ray contrast has been a strong driving force in the search for novel X-ray phosphors. However, the current palette of X-ray phosphors is rather sparse. The development of color tunable phosphors necessitates the incorporation of multiple dopants, which in turn interact through complex sensitization mechanisms that are poorly understood for high-energy excitation. In this work, we describe the stabilization of multiply alloyed LaOCl nanocrystals incorporating Tb3+ cations in conjunction with either divalent or trivalent europium ions, yielding phosphors emitting in the blue–green and green–red regions of the electromagnetic spectru...

The invention of rechargeable batteries has dramatically changed our landscapes and lives, underpinning the explosive worldwide growth of consumer electronics, ushering in an unprecedented era of electric vehicles, and potentially paving the way for a much greener energy future. Unfortunately, current battery technologies suffer from a number of challenges, e.g., capacity loss and failure upon prolonged cycling, limited ion diffusion kinetics, and a rather sparse palette of high-performing electrode materials. Here, we discuss the origins of diffusion limitations in oxide materials using V2O5 as a model system. In particular, we discuss constrictions in ionic conduction pathways, narrow energy dispersion of conduction band states, and the stabilization and self-trapping of polarons as local phenomena that have substantial implications for introducing multiscale compositional and phase heterogeneities. Strategies for mitigating such limitations are discussed such as reducing diffusion path lengths and the ...

The steam-assisted gravity-drainage (SAGD) method has emerged as among the leading methods of enhanced oil recovery and is predicated on the injection of steam within the wellbore followed by extraction of emulsions of viscous oil and water. The emulsions are stabilized by endogenous surfactants, necessitating extensive processing such as addition of chemical de-emulsifiers and slow gravity-based separation methods. Here, we show that a hierarchically textured membrane exhibiting orthogonal wettability, specifically, superoleophilic but superhydrophobic behavior, allows for effective separation of the water and viscous oil fractions of SAGD emulsions. The membrane is constructed by integrating ZnO nanotetrapods onto stainless steel meshes using a conformal amorphous SiO2 layer and is both mechanically resilient and thermally robust. The intrinsic surface energy characteristics of the ZnO tetrapods as well as their three-dimensional texture when arrayed atop the stainless steel mesh substrates contribute t...

Summary The Li-ion paradigm of battery technology is constrained by the monovalency of the Li ion. A straightforward solution is to transition to multivalent-ion chemistries, where Mg 2+ is the most obvious candidate because of its size and mass. The realization of Mg batteries has faced myriad obstacles, including a sparse selection of cathode materials demonstrating the ability to reversibly insert divalent ions. Here, we provide evidence of reversible topochemical and electrochemical insertion of Mg 2+ into a metastable one-dimensional polymorph of V 2 O 5 up to a capacity of 0.33 Mg 2+ per formula unit. An electrochemical capacity of 90 mA hr g −1 was retained after 100 cycles with an average operating potential of 1.65 V versus Mg 2+ /Mg 0 . Not only does ζ-V 2 O 5 represent a rare addition to the pantheon of functional Mg battery cathode materials, but it is also distinctive in exhibiting a combination of high stability, high specific capacity, and moderately high operating voltage.

As the quest toward novel materials proceeds, improved characterization technologies are needed. In particular, the atomic thickness in graphene and other 2D materials renders some conventional technologies obsolete. Characterization technologies at wafer level are needed with enough sensitivity to detect strain in order to inform fabrication. In this work, NEXAFS spectroscopy was combined with simulations to predict lattice parameters of graphene grown on copper and further transferred to a variety of substrates. The strains associated with the predicted lattice parameters are in agreement with experimental findings. The approach presented here holds promise to effectively measure strain in graphene and other 2D systems at wafer levels to inform manufacturing environments.

The insertion of Li-ions within cathode materials during the discharging of a battery oftentimes brings about one or more structural transformations. The spatiodynamic propagation of phase transformations within a matrix of particles is determined by highly localized intercalation phenomena rather than the global voltage profile. Multiscale inhomogeneities resulting from variations in electrode reactions strongly influence the proportion of actively intercalating electrode materials, define local “hot-spots” wherein the current is greatly amplified during charge/discharge processes, and consequently dictate localized energy dissipation profiles. Multiphasic domains further give rise to localized stress gradients that can induce electrode degradation. However, a clear picture of chemical and stress inhomogeneities remains to be developed for most cathode materials. Here we demonstrate compositional striping modulations between Li-rich and Li-poor domains along the edges of individual nanowires of Li-ion-intercalated V2O5 based on analysis of hyperspectral X-ray microscopy data. Analysis of scanning transmission X-ray microscopy data using singular value decomposition and principal component analysis provides a means to map compositional inhomogenieties across individual nanowires and ensembles of nanowires alike. The compositional maps are further transformed to stress and strain maps, which depict the localization of tensile stress and strain within individual nanowires of LixV2O5. The core–shell and compositional striping modulations manifested here and the resulting strain gradients point to the need to design cathode materials and electrode architectures to mitigate such pronounced local inhomoegeneities in Li-ion intercalation and diffusion.

Summary Fluoride-ion batteries are an attractive energy storage concept analogous to lithium-ion batteries but feature an inverted paradigm where anions are the principal charge carriers. Insertion hosts that can reversibly insert fluoride ions at room temperature are exceedingly sparse. Here, we report that topochemical insertion of fluoride ions in FeSb2O4 involves Fe2+/Fe3+ redox but is mediated by multi-center synergies between iron and antimony centers. Separation of the redox center from the p-block coordination site alleviates structural strain by enabling compensatory contraction and expansion of FeO6 and SbO3 polyhedra, respectively. p-block electron lone pairs play a critical role in weakening anion-lattice interactions, enabling reversible fluoride-ion diffusion across microns. The results illuminate the key principle that interactions traceable to stereoactive lone pairs can be used to mediate anion-lattice interactions and suggest that anion insertion hosts can be designed by pairing redox-active transition metals with p-block cations bearing stereochemically active electron lone pairs.

The unique mechanical properties and transport features of grain boundaries (GBs) in polycrystalline materials have been widely investigated. However, studies which focus on the unique chemo-mechanics phenomena resulting from GBs’ are exceedingly sparse. In this work, a thermodynamically consistent framework has been developed to explore the multi-physics coupling between mechanics and species diffusion. Constitutive laws for the bulk and the across-GB interaction laws have been derived for large deformations from the system free energies. A chemo-mechanically coupled cohesive zone model is developed which takes into account mode-dependent fracture properties in the presence of GBs. Polycrystalline LiNi x Mn y Co z O 2 (NMC) particles and Li x V 2 O 5 nanowires haveueen selected to demonstrate the impact of GBs on the modeled and observed chemo-mechanics. The model has been implemented in the open-source finite element (FE) package MOOSE. Simulation results indicate that the chemical process and the mechanical degradation go hand-in–hand, where enhanced intergranular chemical inhomogeneities weaken the mechanical strength of the GBs, while damage to the GBs affects or even block transport across the GB. Furthermore, experimentally observed characteristics of chemo-mechanical degradation, e.g., chemical “hot-spots” and surface layer delamination can be accurately predicted by the model.

A continuous increase in the global demand for liquid fuels has led to increased reliance on unconventional sources of fossil fuels such as bitumen. The extraction, midstream transportation, and ultimate processing of heavy oils presents a distinctive set of challenges. For example, the high viscosity of bitumen poses a challenge to its transportation through conventional transportation systems such as pipelines. Conventional approaches to address the challenging rheological properties of bitumen involve dilution of bitumen with natural gas condensates, addition of surfactants, ultrasonic heating, thermal jacketing of pipelines, and high pump pressures. These solutions require considerable investments in infrastructure, frequent inspection and maintenance, and pose a risk of spillage to vulnerable environments. As such, much interest has focused on the design of solid-state transportation methodologies. In this article, we propose a viable and safe transportation alternative wherein bitumen is reconfigured such that the droplets of lighter fractions of bitumen (saturates, aromatics, resins) are encapsulated within conformal shells of asphaltenes. The tendency of asphaltenes to aggregate has been exploited to obtain cross-linked shells without requiring the use of extraneous chemical additives. Thermally mediated crosslinking of the asphaltenes shells allow the microcapsules to hold their form and result in the emergence of mechanical strength. The stress-withstanding abilities and velocity impact resistance of these microcapsules have been studied to establish their viability for industrial use, and demonstrate that microcapsules with diameters of ca. 1.25 mm can withstand stresses as high as 576 kN/m2. Since the bitumen microcapsules have been formulated by simply reconfiguring the intrinsic components of bitumen, they can be readily fluidized by mechanical means to recover the encapsulated lighter fractions. The solid microcapsules demonstrate the viability of solid-state transportation of bitumen via roadways or marine tankers, thereby mitigating a primary impediment to the utilization of viscous oils.