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Abstract Electrochemical technologies add a unique dimension for ore refinement, representing tunable methods that can integrate with renewable energy sources and existing downstream process flows. However, the development of electrochemical extraction technologies has been impeded by the technological maturity of hydro- and pyro-metallurgy, as well as the electrical insulating properties of many metal oxide ores. The fabrication and use of carbon/insulating material composite electrodes has been a longstanding method to enable electrochemical activation. Here, using real hectorite ore, we employ this technical approach to fabricate hectorite-carbon black composite electrodes (HCCEs) and achieve electrochemical activation of hectorite. Anodic polarization results in lithium-ion release through a multi-step chemical and electrochemical mechanism that results in 50.7 ± 4.4% removal of lithium from HCCE, alongside other alkaline ions. This technical proof-of-concept study underscores that electrochemical activation of ores can facilitate lattice deterioration and ion removal from ores.

Abstract Metal-organic frameworks (MOFs) are highly attractive porous materials with applications spanning the fields of chemistry, physics, biology, and engineering. Their exceptional porosity and structural flexibility have led to widespread use in catalysis, separation, biomedicine, and electrochemistry. Currently, most MOFs are synthesized under equilibrium liquid-phase reaction conditions. Here we show a general and versatile non-equilibrium flame aerosol synthesis of MOFs, in which rapid kinetics of MOF formation yields two distinct classes of MOFs, nano-crystalline MOFs and amorphous MOFs. A key advantage of this far-from-equilibrium synthesis is integration of different metal cations within a single MOF phase, even when this is thermodynamically unfavorable. This can, for example, produce single-atom catalysts and bimetallic MOFs of arbitrary metal pairs. Moreover, we demonstrate that dopant metals (e.g., Pt, Pd) can be exsolved from the MOF framework by reduction, forming nanoclusters anchored on the MOF. A prototypical example of such a material exhibited outstanding performance as a CO oxidation catalyst. This general synthesis route opens new opportunities in MOF design and applications across diverse fields and is inherently scalable for continuous production at industrial scales.

Abstract MXene is investigated as an electrode material for different energy storage systems due to layered structures and metal‐like electrical conductivity. Experimental results show MXenes possess excellent cycling performance as anode materials, especially at large current densities. However, the reversible capacity is relatively low, which is a significant barrier to meeting the demands of industrial applications. This work synthesizes N‐doped graphene‐like carbon (NGC) intercalated Ti3C2Tx (NGC‐Ti3C2Tx) van der Waals heterostructure by an in situ method. The as‐prepared NGC‐Ti3C2Tx van der Waals heterostructure is employed as sodium‐ion and lithium‐ion battery electrodes. For sodium‐ion batteries, a reversible specific capacity of 305 mAh g−1 is achieved at a specific current of 20 mA g−1, 2.3 times higher than that of Ti3C2Tx. For lithium‐ion batteries, a reversible capacity of 400 mAh g−1 at a specific current of 20 mA g−1 is 1.5 times higher than that of Ti3C2Tx. Both sodium‐ion and lithium‐ion batteries made from NGC‐Ti3C2Tx shows high cycling stability. The theoretical calculations also verify the remarkable improvement in battery capacity within the NGC‐Ti3C2O2 system, attributed to the additional adsorption of working ions at the edge states of NGC. This work offers an innovative way to synthesize a new van der Waals heterostructure and provides a new route to improve the electrochemical performance significantly.

Abstract The Hume-Rothery rules governing solid-state miscibility limit the compositional space for new inorganic material discovery. Here, we report a non-equilibrium, one-step, and scalable flame synthesis method to overcome thermodynamic limits and incorporate immiscible elements into single phase ceramic nanoshells. Starting from prototype examples including (NiMg)O, (NiAl)Ox, and (NiZr)Ox, we then extend this method to a broad range of Ni-containing ceramic solid solutions, and finally to general binary combinations of elements. Furthermore, we report an “encapsulated exsolution” phenomenon observed upon reducing the metastable porous (Ni0.07Al0.93)Ox to create ultra-stable Ni nanoparticles embedded within the walls of porous Al2O3 nanoshells. This nanoconfined structure demonstrated high sintering resistance during 640 h of catalysis of CO2 reforming of methane, maintaining constant 96% CH4 and CO2 conversion at 800 °C and dramatically outperforming conventional catalysts. Our findings could greatly expand opportunities to develop novel inorganic energy, structural, and functional materials.

Inkjet printing is a more sustainable and scalable fabrication method than spin coating for producing perovskite solar cells (PSCs). Although spin-coated SnO2 has been intensively studied as an effective electron transport layer (ETL) for PSCs, inkjet-printed SnO2 ETLs have not been widely reported. Here, we fabricated inkjet-printed, solution-processed SnOx ETLs for planar PSCs. A champion efficiency of 17.55% was achieved for the cell using a low-temperature processed SnOx ETL. The low-temperature SnOx exhibited an amorphous structure and outperformed high-temperature crystalline SnO2. The improved performance was attributed to enhanced charge extraction and transport and suppressed charge recombination at ETL/perovskite interfaces, which originated from enhanced electrical and optical properties of SnOx, improved perovskite film quality, and well-matched energy level alignment between the SnOx ETL and the perovskite layer. Furthermore, SnOx was doped with Cu. Cu doping increased surface oxygen defects and upshifted energy levels of SnOx, leading to reduced device performance. A tunable hysteresis was observed for PSCs with Cu-doped SnOx ETLs, decreasing at first and turning into inverted hysteresis afterwards with increasing Cu doping level. This tunable hysteresis was related to the interplay between charge/ion accumulation and recombination at ETL/perovskite interfaces in the case of electron extraction barriers.

Weak interactions between substrates and the active site environment have been known to be vital in enzyme catalysis. Inspired by this, the authors synthesize hyper-crosslinked porous polymer-based catalysts with different H-bonds to enhance adsorption and modify the interfacial sites and reactivity.

Abstract Metal amides are attractive candidates for hydrogen storage due to their high volumetric and gravimetric hydrogen densities. However, the sluggish kinetics and competing side reactions during hydrogen uptake and release limit their practical use. Here, a novel nanoconfined Li2Mg(NH)2@reduced graphene oxide (rGO) composite is presented, which is fabricated using a melt‐infiltration method with a minimum weight penalty of only 2 wt.%. The presence of rGO ensures close contact between the active phases, effectively preventing aggregation during cycling process. As a result, the reversible capacity of Li2Mg(NH)2@rGO reaches 4.42 wt.%, with no capacity degradation observed after multiple cycling. Theoretical calculations show that rGO catalyzes the hydrogen bond cleavage at the Mg‐amide/Li hydride interface, leading to local dehydrogenation hotspots and significantly improves kinetics of dehydrogenation compared to the bulk counterpart. This study provides a promising strategy for designing metal imide‐based composites to overcome the kinetic limitations and improve their reversible hydrogen storage performance.

Layered double hydroxides (LDH) are ideal for charge storage, however, the sluggish reaction dynamics are obstacle to their development. Here, triggered by mismatching integration of Mn sites, the authors configure wrinkled Mn/NiCo-LDH with strains and defects, where promoted mass & charge transport behaviors are realized.

Abstract Two‐dimensional (2D) layered transition metal carbides/nitrides, called MXenes, are attractive alternative electrode materials for electrochemical energy storage. Owing to their metallic electrical conductivity and low ion diffusion barrier, MXenes are promising anode materials for sodium‐ion batteries (SIBs). Herein, we report on a new 2D carbonitride MXene, viz., Ti2C0.5N0.5Tx (Tx stands for surface terminations), and the only second carbonitride after Ti3CNTx so far. A new type of in situ HF (HCl/KF) etching condition was employed to synthesize multilayer Ti2C0.5N0.5Tx powders from Ti2AlC0.5N0.5. Spontaneous intercalation of tetramethylammonium followed by sonication in water allowed for large‐scale delamination of this new titanium carbonitride into 2D sheets. Multilayer Ti2C0.5N0.5Tx powders showed higher specific capacities and larger electroactive surface area than those of Ti2CTx powders. Multilayer Ti2C0.5N0.5Tx powders show a specific capacity of 182 mAh g−1 at 20 mA g−1, the highest among all reported MXene electrodes as SIBs with excellent cycling stability.

Layered boron compounds attract enormous interest in applications. This work reports first-principles calculations coupled with global optimization to show that the outer boron surface in MgB2 nanosheets undergo disordering and clustering, which is experimentally confirmed in synthesized MgB2 nanosheets.

Heavy metals and metalloids pose major threats to health and environmental ecosystems, thus systems for low-cost remediation are needed. Here the authors report the scalable design of a hydrogen-bonded organic–inorganic framework for selective removal of trace heavy metal ions from water.

The design of solution-processed thermoelectric nanomaterials with efficient, stable performance remains a challenge. Here, the authors report an in-situ doping method based on nanoscale interface engineering to realize n-type thermoelectric nanowires with high performance and stability.

Two-dimensional (2D) materials are uniquely suited for highly anisotropic thermal transport, which is important in thermoelectrics, thermal barrier coatings, and heat spreaders. Solution-processed 2D materials are attractive for simple, low-cost, and large-scale fabrication of devices on, virtually, any substrate. However, to date, there are only few reports with contrasting results on the thermal conductivity of graphene films, while thermal transport has been hardly measured for other types of solution-processed 2D material films. In this work, inkjet-printed graphene, h-BN and MoS2 films are demonstrated with thermal conductivities of ∼10 Wm−1K−1 and ∼0.3 Wm−1K−1 along and across the basal plane, respectively, giving rise to an anisotropy of ∼30, hardly dependent on the material type and annealing treatment. First-principles calculations indicate that portion of the phonon spectrum is cut-off by the quality of the thermal contact for transport along the plane, yet the ultra-low conductivity across the plane is associated with high-transmissivity interfaces. These findings can drive the design of highly anisotropic 2D material films for heat management applications.

In this perspective we compare plasmon-enhanced electrochemical conversion (PEEC) with photoelectrochemistry (PEC). PEEC is the oxidation or reduction of a reactant at the illuminated surface of a plasmonic metal (or other conductive material) while a potential bias is applied. PEC uses solar light to generate photoexcited electron-hole pairs to drive an electrochemical reaction at a biased or unbiased semiconductor photoelectrode. The mechanism of photoexcitation of charge carriers is different between PEEC and PEC. Here we explore how this difference affects the response of PEEC and PEC systems to changes in light, temperature, and surface morphology of the photoelectrode. : Catalysis; Theoretical Photochemistry; Engineering Subject Areas: Catalysis, Theoretical Photochemistry, Engineering

To realize the potential of soft hybrid (inorganic-organic) materials for thermoelectrics, the underlying transport-related physics must be understood. Here, the authors extend the Kang-Synder framework with experimental analysis to gain insight on the thermoelectric transport in hybrid materials.

Despite recent success in developing new covalent organic frameworks (COFs) materials, synthesis of chemically stable COFs still remains challenging. Here the authors demonstrate a facile strategy that transforms imine-linked COFs into robust porous aromatic frameworks by kinetically fixing the reversible imine linkage via an aza-Diels-Alder cycloaddition reaction.

Abstract Thermoelectric power generation can play a key role in a sustainable energy future by converting waste heat from power plants and other industrial processes into usable electrical power. Current thermoelectric devices, however, require energy intensive manufacturing processes such as alloying and spark plasma sintering. Here, we describe the fabrication of a p-type thermoelectric material, copper selenide (Cu2Se), utilizing solution-processing and thermal annealing to produce a thin film that achieves a figure of merit, ZT, which is as high as its traditionally processed counterpart, a value of 0.14 at room temperature. This is the first report of a fully solution-processed nanomaterial achieving performance equivalent to its bulk form and represents a general strategy to reduce the energy required to manufacture advanced energy conversion and harvesting materials.

Low thermal conductivities in nanomeshes have been attributed to both wave-like and particle-like behaviour of phonons. Here, the authors use periodicity-controlled silicon nanomeshes to show that the particle backscattering effect dominates for periodicities above 100 nm and temperatures above 14 K.

Laboratory chemical synthesis research typically lacks the preplanned hazard responses found in production-scale industrial laboratories. Chemical safety management is a known challenge in education-based facilities, which is concerning for academic and national laboratory environments working with inexperienced student researchers. At the Molecular Foundry, a U.S. Department of Energy (DOE) user facility, a chemical safety management form has been developed that follows DOE's Integrated Safety Management (ISM) process, which evaluates the risks and hazards associated with all forms of work. An ISM form for chemical synthesis is described here in detail. It is regularly used to guide chemical safety discussions between researchers and supervisors, to plan accident responses, and to establish triggers, at which point a reevaluation of the work is needed. The form makes it straightforward to know what limits researchers may work within and makes it clear which procedure changes will require a new safety assessment and discussion before work continues. The ISM form for synthesis is being successfully used in three fields of chemistry: Inorganic, Organic, and Biological. The form has also been adapted for liquid sample preparation in electron microscopy. Upper management, supervisors, students, and general users are engaged in this process. It is hoped that sharing this knowledge will enable educational institutions and other laboratories to develop similar methods to help researchers and supervisors understand the hazards as well as the working limits of any protocol, helping researchers to work more independently and safely within the laboratory.

Hydrogen fuel cell electric vehicles are poised to transform the automotive industry, but the lack of safe, high density solid state hydrogen storage solutions is stifling progress. Here, the authors develop a graphene oxide/magnesium nanocomposite which appears to overcome many of the existing challenges.

Nature Communications 7:10804 Article number 10804 (2016); Published 23 February 2016; Updated 18 March 2016 The financial support for this Article was not fully acknowledged. The Acknowledgements should have included the following: The authors gratefully acknowledge research support from the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Fuel Cell Technologies Office, under Contract No.

The carbon dioxide storage capacity of magnesium oxide (MgO) particles was examined as a function of particle size, shape, and surface area. Two types of MgO nanocrystals (5 nm spheres and 23 nm disks) were synthesized and compared against commercially available MgO (325 mesh/44 μm and 40 mesh/420 μm). The surface area of the four types of particles was determined by N2gas adsorption. Carbon dioxide capture was measured at 60 °C and 600 °C using thermogravimetric analysis, with results indicating enhanced CO2capacity correlating with increased surface area. [ABSTRACT FROM AUTHOR]

The question of the nature and stability of polar ordering in nanoscale ferroelectrics is examined with colloidal nanocrystals of germanium telluride (GeTe). We provide atomic-scale evidence for room-temperature polar ordering in individual nanocrystals using aberration-corrected transmission electron microscopy and demonstrate a reversible, size-dependent polar-nonpolar phase transition of displacive character in nanocrystal ensembles. A substantial linear component of the distortion is observed, which is in contrast with theoretical reports predicting a toroidal state. [ABSTRACT FROM AUTHOR]

Ambient energy harvesting has great potential to contribute to sustainable development and address growing environmental challenges. Converting waste energy from energy-intensive processes and systems (e.g. combustion engines and furnaces) is crucial to reducing their environmental impact and achieving net-zero emissions. Compact energy harvesters will also be key to powering the exponentially growing smart devices ecosystem that is part of the Internet of Things, thus enabling futuristic applications that can improve our quality of life (e.g. smart homes, smart cities, smart manufacturing, and smart healthcare). To achieve these goals, innovative materials are needed to efficiently convert ambient energy into electricity through various physical mechanisms, such as the photovoltaic effect, thermoelectricity, piezoelectricity, triboelectricity, and radiofrequency wireless power transfer. By bringing together the perspectives of experts in various types of energy harvesting materials, this Roadmap provides extensive insights into recent advances and present challenges in the field. Additionally, the Roadmap analyses the key performance metrics of these technologies in relation to their ultimate energy conversion limits. Building on these insights, the Roadmap outlines promising directions for future research to fully harness the potential of energy harvesting materials for green energy anytime, anywhere.