Co2Mo6S8 Catalyzes Nearly Exclusive Electrochemical Nitrate Conversion to Ammonia with Enzyme-like Activity.

Electrocatalytic nitrate to ammonia conversion is a key reaction for energy and environmental sustainability. This reaction involves complex multi electron and proton transfer steps, and is impeded by the lack of catalyst for promoting both reactivity and ammonia selectivity. Here, we demonstrate active motifs based on the Chevrel phase Co2Mo6S8 exhibit an enzyme-like high turnover frequency of ∼95.1 s-1 for nitrate electroreduction to ammonia. We reveal strong synergy of multiple binding sites on this catalyst, such that the ligand effect of Co steers Had* toward hydrogenation other than hydrogen evolution, the ensemble effect of Co, and the spatial confinement effect that promote the full hydrogenation of NOx to ammonia without N-N coupling. The catalyst exhibits almost exclusive ammonia conversion with a Faradaic efficiency of 97.1% and ammonia yielding rate of 115.5 mmol·gcat-1·h-1 in neutral electrolytes. The high activity was also confirmed in electrolytes with dilute nitrate and high chloride concentrations.

Quasi-Solid Sulfur Conversion for Energetic All-Solid-State Na-S Battery.

The high theoretical energy density (1274 Wh kg-1) and high safety enable the all-solid-state Na-S batteries with great promise for stationary energy storage system. However, the uncontrollable solid-liquid-solid multiphase conversion and its associated sluggish polysulfides redox kinetics pose a great challenge in tunning the sulfur speciation pathway for practical Na-S electrochemistry. Herein, we propose a new design methodology for matrix featuring separated bi-catalytic sites that control the multi-step polysulfide transformation in tandem and direct quasi-solid reversible sulfur conversion during battery cycling. It is revealed that the N, P heteroatom hotspots are more favorable for catalyzing the long-chain polysulfides reduction, while PtNi nanocrystals manipulate the direct and full Na2S4 to Na2S low-kinetic conversion during discharging. The electrodeposited Na2S on strongly coupled PtNi and N, P-codoped carbon host is extremely electroreactive and can be readily recovered back to S8 without passivation of active species during battery recharging, which delivers a true tandem electrocatalytic quasi-solid sulfur conversion mechanism. Accordingly, stable cycling of the all-solid-state soft-package Na-S pouch cells with an attractive specific capacity of 876 mAh gS -1 and a high energy of 608 Wh kgcathode -1 (172 Wh kg-1, based on the total mass of cathode and anode) at 60 °C are demonstrated.

Bidirectional Tandem Electrocatalysis Manipulated Sulfur Speciation Pathway for High-Capacity and Stable Na-S Battery.

The sluggish polysulfide redox kinetics and the uncontrollable sulfur speciation pathway, leading to serious shuttling effect and high activation barrier associated with sulfur cathode. We describe here the use of core-shell structured composite matrixes containing abundant catalytic sites for nearly fully reversible cycling of sulfur cathodes for Na-S batteries. The bidirectional tandem electrocatalysis provide successive reversible conversion of both long- and short-chain polysulfides, whereas Fe2 O3 accelerates Na2 S8 /Na2 S6 to Na2 S4 conversion and the redox-active Fe(CN)6 4- -doped polypyrrole shell catalyzes Na2 S4 reduction to Na2 S. The electrochemically reactive Na2 S can be readily charged back to sulfur with minimal overpotential. Simultaneously, stable cycling of Na-S pouch cell with a high reversible capacity of 696 mAh g-1 is also demonstrated. The bidirectional confined tandem catalysis renders the manipulation of sulfur redox electrochemistry for practical Na-S cells.

Elastic NaxMoS2-Carbon-BASE Triple Interface Direct Robust Solid-Solid Interface for All-Solid-State Na-S Batteries.

The developments of all-solid-state sodium batteries are severely constrained by poor Na-ion transport across incompatible solid-solid interfaces. We demonstrate here a triple NaxMoS2-carbon-BASE nanojunction interface strategy to address this challenge using the ß″-Al2O3 solid electrolyte (BASE). Such an interface was constructed by adhering ternary Na electrodes containing 3 wt % MoS2 and 3 wt % carbon on BASE and reducing contact angles of molten Na to ∼45°. The ternary Na electrodes exhibited twice improved elasticity for flexible deformation and intimate solid contact, whereas NaxMoS2 and carbon synergistically provide durable ionic/electronic diffusion paths, which effectively resist premature interface failure due to loss of contact and improved Na stripping utilization to over 90%. Na metal hosted via triple junctions exhibited much smaller charge-transfer resistance and 200 h of stable cycling. The novel interface architecture enabled 1100 mAh/g cycling of all-solid-state Na-S batteries when using advanced sulfur cathodes with Na-ion conductive PEO10-NaFSI binder and NaxMo6S8 redox catalytic mediator.

LixNiO/Ni Heterostructure with Strong Basic Lattice Oxygen Enables Electrocatalytic Hydrogen Evolution with Pt-like Activity.

The low-cost hydrogen production from water electrolysis is crucial to the deployment of sustainable hydrogen economy but is currently constrained by the lack of active and robust electrocatalysts from earth-abundant materials. We describe here an unconventional heterostructure composed of strongly coupled Ni-deficient LixNiO nanoclusters and polycrystalline Ni nanocrystals and its exceptional activities toward the hydrogen evolution reaction (HER) in aqueous electrolytes. The presence of lattice oxygen species with strong Brønsted basicity is a significant feature in such heterostructure, which spontaneously split water molecules for accelerated Volmer H-OH dissociation in neutral and alkaline HER. In combination with the intimate LixNiO and Ni interfacial junctions that generate localized hotspots for promoted hydride coupling and hydrogen desorption, the catalysts produce hydrogen at a current density of 10 mA cm-2 under overpotentials of only 20, 50, and 36 mV in acidic, neutral, and alkaline electrolytes, respectively, making them among the most active Pt-free catalysts developed thus far. In addition, such heterostructures also exhibited superior activity toward the hydrogen oxidation reaction in alkaline electrolytes.

Realizing the full potential of insertion anodes for Mg-ion batteries through the nanostructuring of Sn.

Magnesium is of great interest as a replacement for lithium in next-generation ion-transfer batteries but Mg-metal anodes currently face critical challenges related to the formation of passivating layers during Mg-plating/stripping and anode-electrolyte-cathode incompatibilities. Alternative anode materials have the potential to greatly extend the spectrum of suitable electrolyte chemistries but must be systematically tailored for effective Mg(2+) storage. Using analytical (scanning) transmission electron microscopy ((S)TEM) and ab initio modeling, we have investigated Mg(2+) insertion and extraction mechanisms and transformation processes in ß-SnSb nanoparticles (NPs), a promising Mg-alloying anode material. During the first several charge-discharge cycles (conditioning), the ß-SnSb particles irreversibly transform into a porous network of pure-Sn and Sb-rich subparticles, as Mg ions replace Sn atoms in the SnSb lattice. After electrochemical conditioning, small Sn particles/grains (<33 ± 20 nm) exhibit highly reversible Mg-storage, while the Sb-rich domains suffer substantial Mg trapping and contribute little to the system performance. This result strongly indicates that pure Sn can act as a high-capacity Mg-insertion anode as theoretically predicted, but that its performance is strongly size-dependent, and stable nanoscale Sn morphologies (<40 nm) are needed for superior, reversible Mg-storage and fast system kinetics.

Highly active electrolytes for rechargeable Mg batteries based on a [Mg2(µ-Cl)2](2+) cation complex in dimethoxyethane.

A novel [Mg2(µ-Cl)2](2+) cation complex, which is highly active for reversible Mg electrodeposition, was identified for the first time in this work. This complex was found to be present in electrolytes formulated in dimethoxyethane (DME) through dehalodimerization of non-nucleophilic MgCl2 by reacting with either Mg salts (such as Mg(TFSI)2, TFSI = bis(trifluoromethane)sulfonylimide) or Lewis acid salts (such as AlEtCl2 or AlCl3). The molecular structure of the cation complex was characterized by single crystal X-ray diffraction, Raman spectroscopy and NMR. The electrolyte synthesis process was studied and rational approaches for formulating highly active electrolytes were proposed. Through control of the anions, electrolytes with an efficiency close to 100%, a wide electrochemical window (up to 3.5 V) and a high ionic conductivity (>6 mS cm(-1)) were obtained. The understanding of electrolyte synthesis in DME developed in this work could bring significant opportunities for the rational formulation of electrolytes of the general formula [Mg2(µ-Cl)2][anion]x for practical Mg batteries.

Highly reversible Mg insertion in nanostructured Bi for Mg ion batteries.

Rechargeable magnesium batteries have attracted wide attention for energy storage. Currently, most studies focus on Mg metal as the anode, but this approach is still limited by the properties of the electrolyte and poor control of the Mg plating/stripping processes. This paper reports the synthesis and application of Bi nanotubes as a high-performance anode material for rechargeable Mg ion batteries. The nanostructured Bi anode delivers a high reversible specific capacity (350 mAh/gBi or 3430 mAh/cm(3)Bi), excellent stability, and high Coulombic efficiency (95% initial and very close to 100% afterward). The good performance is attributed to the unique properties of in situ formed, interconnected nanoporous bismuth. Such nanostructures can effectively accommodate the large volume change without losing electric contact and significantly reduce diffusion length for Mg(2+). Significantly, the nanostructured Bi anode can be used with conventional electrolytes which will open new opportunities to study Mg ion battery chemistry and further improve its properties.

Significantly improved long-cycle stability in high-rate Li-S batteries enabled by coaxial graphene wrapping over sulfur-coated carbon nanofibers.

Long-term instability of Li-S batteries is one of their major disadvantages compare to other secondary batteries. The reasons for the instability include dissolution of polysulfide intermediates and mechanical instability of the electrode film caused by volume changes during charging/discharging cycles. In this paper, we report a novel graphene-sulfur-carbon nanofibers (G-S-CNFs) multilayer and coaxial nanocomposite for the cathode of Li-S batteries with increased capacity and significantly improved long-cycle stability. Electrodes made with such nanocomposites were able to deliver a reversible capacity of 694 mA h g(-1) at 0.1C and 313 mA h g(-1) at 2C, which are both substantially higher than electrodes assembled without graphene wrapping. More importantly, the long-cycle stability was significantly improved by graphene wrapping. The cathode made with G-S-CNFs with a initial capacity of 745 mA h g(-1) was able to maintain ~273 mA h g(-1) even after 1500 charge-discharge cycles at a high rate of 1C, representing an extremely low decay rate (0.043% per cycle after 1500 cycles). In contrast, the capacity of an electrode assembled without graphene wrapping decayed dramatically with a 10 times high rate (~0.40% per cycle after 200 cycles). These results demonstrate that the coaxial nanocomposites are of great potential as the cathode for high-rate rechargeable Li-S batteries. Such improved rate capability and cycle stability could be attributed to the unique coaxial architecture of the nanocomposite, in which the contributions from graphene and CNFs enable electrodes with improved electrical conductivity, better ability to trap soluble the polysulfides intermediate and accommodate volume expansion/shrinkage of sulfur during repeated charge/discharge cycles.

Synergistic effects from graphene and carbon nanotubes enable flexible and robust electrodes for high-performance supercapacitors.

Flexible and lightweight energy storage systems have received tremendous interest recently due to their potential applications in wearable electronics, roll-up displays, and other devices. To manufacture such systems, flexible electrodes with desired mechanical and electrochemical properties are critical. Herein we present a novel method to fabricate conductive, highly flexible, and robust film supercapacitor electrodes based on graphene/MnO(2)/CNTs nanocomposites. The synergistic effects from graphene, CNTs, and MnO(2) deliver outstanding mechanical properties (tensile strength of 48 MPa) and superior electrochemical activity that were not achieved by any of these components alone. These flexible electrodes allow highly active material loading (71 wt % MnO(2)), areal density (8.80 mg/cm(2)), and high specific capacitance (372 F/g) with excellent rate capability for supercapacitors without the need of current collectors and binders. The film can also be wound around 0.5 mm diameter rods for fabricating full cells with high performance, showing significant potential in flexible energy storage devices.

Direct optical imaging of graphene in vitro by nonlinear femtosecond laser spectral reshaping.

Nonlinear optical microscopy, based on femtosecond laser spectral reshaping, characterized and imaged graphene samples made from different methods, both on slides and in a biological environment. This technique clearly discriminates between graphene flakes with different numbers of layers and reveals the distinct nonlinear optical properties of reduced graphene oxide as compared to mechanically exfoliated or chemical vapor deposition grown graphene. The nonlinearity makes it applicable to scattering samples (such as tissue) as opposed to previous methods, such as transmission. This was demonstrated by high-resolution imaging of breast cancer cells incubated with graphene flakes.

Anode-free Na metal batteries developed by nearly fully reversible Na plating on the Zn surface.

The anode-free battery architecture has recently emerged as a promising platform for lithium and sodium metal batteries as it not only offers the highest possible energy density, but also eliminates the need for handling hazardous metal electrodes during cell manufacturing. However, such batteries usually suffer from much faster capacity decay and are much more sensitive to even trace levels of irreversible side reactions on the anode, especially for the more reactive Na metal. This work systematically investigates electrochemical interfaces for Na plating and stripping and describes the use of the Zn surface to develop nearly fully reversible Na anodes with 1.0 M NaPF6 in a diglyme-based electrolyte. The high performance includes consistently higher than 99.9% faradaic efficiencies for a wide range of cycling currents between 0.5 and 10 mA cm-2, much more stable interfacial resistance and nearly no formation of mossy Na after 500 cycles compared with conventional Al and Cu surfaces. This improved reversibility was further confirmed under lean electrolyte conditions with a wide range of electrolyte concentrations and cycling temperatures and can be attributed to the strong interfacial binding and intrinsic sodiophilic properties of the Zn surface with Na, which not only ensured uniform Na plating but also eliminated most side reactions that would otherwise cause electrolyte depletion. As a result, full cells assembled with Na-free Zn foil and a high capacity Na3V2(PO4)3 cathode delivered ∼90% capacity retention for 100 cycles, higher than the 73% retention of Cu foils and much higher than the 39% retention of Al foils. This work provides new approaches to enable stable cycling of anode-free batteries and contribute to their applications in practical devices.

Branching phenomena in nanostructure synthesis illuminated by the study of Ni-based nanocomposites.

Branching phenomena are ubiquitous in both natural and artificial crystallization processes. The branched nanostructures' emergent properties depend upon their structures, but their structural tunability is limited by an inadequate understanding of their formation mechanisms. Here we developed an ensemble of Nickel-Based nano-Composites (NBCs) to investigate branching phenomena in solution-phase synthesis with precision and in depth. NBCs of 24 morphologies, including dots, core@shell dots, hollow shells, clusters, polyhedra, platelets, dendrites, urchins, and dandelions, were synthesized through systematic adjustment of multiple synthesis parameters. Relationships between the synthesis parameters and the resultant morphologies were analyzed. Classical or non-classical models of nucleation, nascent growth, 1D growth, 2D growth, 3D reconstruction, aggregation, and carburization were defined individually and then integrated to provide a holistic view of the formation mechanism of branched NBCs. Finally, guidelines were extracted and verified to guide the rational solution-phase syntheses of branched nanomaterials with emergent biological, chemical, and physical properties for potential applications in immunology, catalysis, energy storage, and optics. Demonstrating a systematic approach for deconvoluting the formation mechanism and enhancing the synthesis tunability, this work is intended to benefit the conception, development, and improvement of analogous artificial branched nanostructures. Moreover, the progress on this front of synthesis science would, hopefully, deepen our understanding of branching phenomena in nature.

Polymeric coatings on silver nanoparticles hinder autoaggregation but enhance attachment to uncoated surfaces.

The propensity of silver nanoparticles (AgNPs) having two different polymer coatings (poly(vinylpyrrolidone), PVP, or gum arabic, GA) to aggregate, or to deposit to a reference surface (silica), was explored as a basis for differentiating the effect of surface coating on the stability of nanoparticles in aggregation and in deposition. Surface polymeric coatings stabilize nanoparticles against aggregation as shown by either an increased critical coagulation concentration as for PVP-coated AgNPs (AgPVP) or the absence of observable aggregation even at a high ionic strength as for GA-coated AgNPs (AgGA). In experiments of AgNPs deposition in a silica porous medium, dissimilar surfaces favored deposition, such as the case where polymer coatings were present on the AgNPs but were absent on the porous medium. The increased affinity of the AgNPs for the porous medium in this case may be explained by a shifted contact frontier where electrical double layer interaction is weaker. When coating polymers were introduced to the porous medium and allowed to preadsorb to the silica surfaces, the attachment efficiencies for both the AgPVP and AgGA were reduced due to steric and electrosteric stabilization, respectively. The results suggest that polymeric coatings that are usually deemed as stabilizers (as they indeed are in the case of autoaggregation) might not necessarily stabilize nanoparticles against deposition unless the collector surfaces are also coated with polymer.

Size-controlled dissolution of organic-coated silver nanoparticles.

The solubility of Ag NPs can affect their toxicity and persistence in the environment. We measured the solubility of organic-coated silver nanoparticles (Ag NPs) having particle diameters ranging from 5 to 80 nm that were synthesized using various methods, and with different organic polymer coatings including poly(vinylpyrrolidone) and gum arabic. The size and morphology of Ag NPs were characterized by transmission electron microscopy (TEM). X-ray absorption fine structure (XAFS) spectroscopy and synchrotron-based total X-ray scattering and pair distribution function (PDF) analysis were used to determine the local structure around Ag and evaluate changes in crystal lattice parameters and structure as a function of NP size. Ag NP solubility dispersed in 1 mM NaHCO(3) at pH 8 was found to be well correlated with particle size based on the distribution of measured TEM sizes as predicted by the modified Kelvin equation. Solubility of Ag NPs was not affected by the synthesis method and coating as much as by their size. Based on the modified Kelvin equation, the surface tension of Ag NPs was found to be ∼1 J/m(2), which is expected for bulk fcc (face centered cubic) silver. Analysis of XAFS, X-ray scattering, and PDFs confirm that the lattice parameter, a, of the fcc crystal structure of Ag NPs did not change with particle size for Ag NPs as small as 6 nm, indicating the absence of lattice strain. These results are consistent with the finding that Ag NP solubility can be estimated based on TEM-derived particle size using the modified Kelvin equation for particles in the size range of 5-40 nm in diameter.

Activation of MoS2 monolayer electrocatalysts via reduction and phase control in molten sodium for selective hydrogenation of nitrogen to ammonia.

Electrochemical nitrogen fixation under ambient conditions is promising for sustainable ammonia production but is hampered by high reaction barrier and strong competition from hydrogen evolution, leading to low specificity and faradaic efficiency with existing catalysts. Here we describe the activation of MoS2 in molten sodium that leads to simultaneous formation of a sulfur vacancy-rich heterostructured 1T/2H-MoS x monolayer via reduction and phase transformation. The resultant catalyst exhibits intrinsic activities for electrocatalytic N2-to-NH3 conversion, delivering a faradaic efficiency of 20.5% and an average NH3 rate of 93.2 µg h-1 mgcat -1. The interfacial heterojunctions with sulfur vacancies function synergistically to increase electron localization for locking up nitrogen and suppressing proton recombination. The 1T phase facilitates H-OH dissociation, with S serving as H-shuttling sites and to stabilize . The subsequently couple with nearby N2 and NH x intermediates bound at Mo sites, thus greatly promoting the activity of the catalyst. First-principles calculations revealed that the heterojunction with sulfur vacancies effectively lowered the energy barrier in the potential-determining step for nitrogen reduction, and, in combination with operando spectroscopic analysis, validated the associative electrochemical nitrogen reduction pathway. This work provides new insights on manipulating chalcogenide vacancies and phase junctions for preparing monolayered MoS2 with unique catalytic properties.

High-Energy and Stable Subfreezing Aqueous Zn-MnO2 Batteries with Selective and Pseudocapacitive Zn-Ion Insertion in MnO2.

One major challenge of aqueous Zn-MnO2 batteries for practical applications is their unacceptable performance below freezing temperatures. Here the use of simple Zn(ClO4 )2 aqueous electrolytes is described for all-weather Zn-MnO2 batteries even down to -60 °C. The symmetric, bulky ClO4 - anion effectively disrupts hydrogen bonds between water molecules and provides intrinsic ion diffusion even while frozen, and enables ≈260 mAh g-1 on MnO2 cathodes at -30 °C . It is identified that subfreezing cycling shifts the reaction mechanism on the MnO2 cathode from unstable H+ insertion to predominantly pseudocapacitive Zn2+ insertion, which converts MnO2 nanofibers into complicated zincated MnOx that are largely disordered and appeared as crumpled paper sheets. The Zn2+ insertion at -30 °C is faster and much more stable than at 20 °C, and delivers ≈80% capacity retention for 1000 cycles without Mn2+ additives. In addition, simple Zn(ClO4 )2 electrolyte also enables a nearly fully reversible and dendrite-free Zn anode at -30 °C with ≈98% Coulombic efficiency. Zn-MnO2 prototypes with an experimentally verified unit energy density of 148 Wh kg-1 at a negative-to-positive ratio of 1.5 and an electrolyte-to-capacity ratio of 2.0 are further demonstrated.

Deposition of silver nanoparticles in geochemically heterogeneous porous media: predicting affinity from surface composition analysis.

The transport of uncoated silver nanoparticles (AgNPs) in a porous medium composed of silica glass beads modified with a partial coverage of iron oxide (hematite) was studied and compared to that in a porous medium composed of unmodified glass beads (GB). At a pH lower than the point of zero charge (PZC) of hematite, the affinity of AgNPs for a hematite-coated glass bead (FeO-GB) surface was significantly higher than that for an uncoated surface. There was a linear correlation between the average nanoparticle affinity for media composed of mixtures of FeO-GB and GB collectors and the relative composition of those media as quantified by the attachment efficiency over a range of mixing mass ratios of the two types of collectors, so that the average AgNPs affinity for these media is readily predicted from the mass (or surface) weighted average of affinities for each of the surface types. X-ray photoelectron spectroscopy (XPS) was used to quantify the composition of the collector surface as a basis for predicting the affinity between the nanoparticles for a heterogeneous collector surface. A correlation was also observed between the local abundances of AgNPs and FeO on the collector surface.

More than the ions: the effects of silver nanoparticles on Lolium multiflorum.

Silver nanoparticles (AgNPs) are increasingly used as antimicrobial additives in consumer products and may have adverse impacts on organisms when they inadvertently enter ecosystems. This study investigated the uptake and toxicity of AgNPs to the common grass, Lolium multiflorum. We found that root and shoot Ag content increased with increasing AgNP exposures. AgNPs inhibited seedling growth. While exposed to 40 mg L(-1) GA-coated AgNPs, seedlings failed to develop root hairs, had highly vacuolated and collapsed cortical cells and broken epidermis and rootcap. In contrast, seedlings exposed to identical concentrations of AgNO(3) or supernatants of ultracentrifuged AgNP solutions showed no such abnormalities. AgNP toxicity was influenced by total NP surface area with smaller AgNPs (6 nm) more strongly affecting growth than did similar concentrations of larger (25 nm) NPs for a given mass. Cysteine (which binds Ag(+)) mitigated the effects of AgNO(3) but did not reduce the toxicity of AgNP treatments. X-ray spectro-microscopy documented silver speciation within exposed roots and suggested that silver is oxidized within plant tissues. Collectively, this study suggests that growth inhibition and cell damage can be directly attributed either to the nanoparticles themselves or to the ability of AgNPs to deliver dissolved Ag to critical biotic receptors.

Design and synthesis of hierarchical MnO2 nanospheres/carbon nanotubes/conducting polymer ternary composite for high performance electrochemical electrodes.

For efficient use of metal oxides, such as MnO(2) and RuO(2), in pseudocapacitors and other electrochemical applications, the poor conductivity of the metal oxide is a major problem. To tackle the problem, we have designed a ternary nanocomposite film composed of metal oxide (MnO(2)), carbon nanotube (CNT), and conducting polymer (CP). Each component in the MnO(2)/CNT/CP film provides unique and critical function to achieve optimized electrochemical properties. The electrochemical performance of the film is evaluated by cyclic voltammetry, and constant-current charge/discharge cycling techniques. Specific capacitance (SC) of the ternary composite electrode can reach 427 F/g. Even at high mass loading and high concentration of MnO(2) (60%), the film still showed SC value as high as 200 F/g. The electrode also exhibited excellent charge/discharge rate and good cycling stability, retaining over 99% of its initial charge after 1000 cycles. The results demonstrated that MnO(2) is effectively utilized with assistance of other components (fFWNTs and poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) in the electrode. Such ternary composite is very promising for the next generation high performance electrochemical supercapacitors.