Spin Effect to Promote Reaction Kinetics and Overall Performance of Lithium-Sulfur Batteries under External Magnetic Field.

Lithium-sulfur batteries (LSBs) are still limited by the shuttle of lithium polysulfides (LiPS) and the slow Li-S reaction. Herein, we demonstrate that when using cobalt sulfide as a catalytic additive, an external magnetic field generated by a permanent magnet can significantly improve the LiPS adsorption ability and the Li-S reaction kinetics. More specifically, the results show both experimentally and theoretically how an electron spin polarization of Co ions reduces electron repulsion and enhances the degree of orbital hybridization, thus resulting in LSBs with unprecedented performance and stability. Under an external magnetic field, LSBs with 0.0084 % per cycle decay rate at 2 C during 8150 cycles are produced. Overall, this work not only demonstrates an effective strategy to promote LiPS adsorption and electrochemical conversion in LSBs at no additional energy cost but also enriches the application of the spin effect in the electrocatalysis fields.

Analysis of the interfacial characteristics of BiVO4/metal oxide heterostructures and its implication on their junction properties.

The formation of heterostructures has proven to be a viable way to achieve high photoelectrochemical water splitting efficiencies with BiVO4 based photoanodes. Especially, cobalt and nickel based oxides are suitable low cost contact materials. However, the exact role of these contact materials is not yet completely understood because of the difficulty to individually quantify the effects of surface passivation, charge carrier separation and catalysis on the efficiency of a heterostructure. In this study, we used photoelectron spectroscopy in combination with in situ thin film deposition to obtain direct information on the interface structure between polycrystalline BiVO4 and NiO, CoOx and Sn-doped In2O3 (ITO). Strong upwards band bending was observed for the BiVO4/NiO and BiVO4/CoOx interfaces without observing chemical changes in BiVO4, while limited band bending and reduction of Bi and V was observed while forming the BiVO4/ITO interface. Thus, the tunability of the Fermi level position within BiVO4 seems to be limited to a certain range. The feasibility of high upwards band bending through junctions with high work function (WF) compounds demonstrate that nickel oxide and cobalt oxide are able to enhance the charge carrier separation in BiVO4. Similar studies could help to identify whether new photoelectrode materials and their heterostructures would be suitable for photoelectrochemical water splitting.

Enhanced Activity and Acid pH Stability of Prussian Blue-type Oxygen Evolution Electrocatalysts Processed by Chemical Etching.

The development of upscalable oxygen evolving electrocatalysts from earth-abundant metals able to operate in neutral or acidic environments and low overpotentials remains a fundamental challenge for the realization of artificial photosynthesis. In this study, we report a highly active phase of heterobimetallic cyanide-bridged electrocatalysts able to promote water oxidation under neutral, basic (pH < 13), and acidic conditions (pH > 1). Cobalt-iron Prussian blue-type thin films, formed by chemical etching of Co(OH)1.0(CO3)0.5·nH2O nanocrystals, yield a dramatic enhancement of the catalytic performance toward oxygen production, when compared with previous reports for analogous materials. Electrochemical, spectroscopic, and structural studies confirm the excellent performance, stability, and corrosion resistance, even when compared with state-of-the-art metal oxide catalysts under moderate overpotentials and in a remarkably large pH range, including acid media where most cost-effective water oxidation catalysts are not useful. The origin of the superior electrocatalytic activity toward water oxidation appears to be in the optimized interfacial matching between catalyst and electrode surface obtained through this fabrication method.

Metal ions to control the morphology of semiconductor nanoparticles: copper selenide nanocubes.

Morphology is a key parameter in the design of novel nanocrystals and nanomaterials with controlled functional properties. Here, we demonstrate the potential of foreign metal ions to tune the morphology of colloidal semiconductor nanoparticles. We illustrate the underlying mechanism by preparing copper selenide nanocubes in the presence of Al ions. We further characterize the plasmonic properties of the obtained nanocrystals and demonstrate their potential as a platform to produce cubic nanoparticles with different composition by cation exchange.

Polarity assignment in ZnTe, GaAs, ZnO, and GaN-AlN nanowires from direct dumbbell analysis.

Aberration corrected scanning transmission electron microscopy (STEM) with high angle annular dark field (HAADF) imaging and the newly developed annular bright field (ABF) imaging are used to define a new guideline for the polarity determination of semiconductor nanowires (NWs) from binary compounds in two extreme cases: (i) when the dumbbell is formed with atoms of similar mass (GaAs) and (ii) in the case where one of the atoms is extremely light (N or O: ZnO and GaN/AlN). The theoretical fundaments of these procedures allow us to overcome the main challenge in the identification of dumbbell polarity. It resides in the separation and identification of the constituent atoms in the dumbbells. The proposed experimental via opens new routes for the fine characterization of nanostructures, e.g., in electronic and optoelectronic fields, where the polarity is crucial for the understanding of their physical properties (optical and electronic) as well as their growth mechanisms.

Cu2O-Cu@Titanium Surface with Synergistic Performance for Nitrate-to-Ammonia Electrochemical Reduction.

Transition metals, such as titanium (Ti) and copper (Cu) along with their respective metal oxides (TiO2, Cu2O, and CuO), have been widely studied as electrocatalysts for nitrate electrochemical reduction with important outcomes in the fields of denitrification and ammonia generation. Based on this, this work conducted an evaluation of a composite electrode that integrates materials with different intrinsic activities (i.e., Cu and Cu2O for higher activity for nitrate conversion; Ti for higher faradaic efficiency to ammonia) looking for potential synergistic effects in the direction of ammonia generation. The specific performance of single-metal and composite electrodes has shown a strong dependence on pH and nitrate concentration conditions. Faradaic efficiency to ammonia of 92% and productivities of 0.28 mmolNH3 ·cm-2·h-1 at 0.5 V vs reversible hydrogen electrode (RHE) values are achieved, demonstrating the implicit potential of this approach in comparison to direct N2RR with values in the order of µmolNH3 ·h-1·cm-2. Finally, the electrochemical rate constants (k) for Ti, Cu, and Cu2O-Cu/Ti disk electrodes were determined by the Koutecky-Levich analysis with a rotating disk electrode (RDE) in 3.02 × 10-6, 3.88 × 10-4, and 4.77 × 10-4 cm·s-1 demonstrating an apparent synergistic effect for selective NiRR to ammonia with a Cu2O-Cu/Ti electrode.

Hydrothermal Fabrication of Carbon-Supported Oxide-Derived Copper Heterostructures: A Robust Catalyst System for Enhanced Electro-Reduction of CO2 to C2 H4.

Anthropogenic CO2 can be converted to alternative fuels and value-added products by electrocatalytic routes. Copper-based catalysts are found to be the star materials for obtaining longer-chain carbon compounds beyond 2e- products. Herein, we report a facile hydrothermal fabrication of a highly robust electrocatalyst: in-situ grown heterostructures of plate-like CuO-Cu2 O on carbon black. Simultaneous synthesis of copper-carbon catalysts with varied amounts of copper was conducted to determine the optimum blend. It is observed that the optimum ratio and structure have aided in achieving the state of art faradaic efficiency for ethylene >45 % at -1.6 V vs. RHE at industrially relevant high current densities over 160 to 200 mA ⋅ cm-2 . It is understood that the in-situ modification of CuO to Cu2 O during the electrolysis is the driving force for the highly selective conversion of CO2 to ethylene through the *CO intermediates at the onset potentials followed by C-C coupling. The excellent distribution of Cu-based platelets on the carbon structure enables rapid electron transfer and enhanced catalytic efficiency. It is inferred that choosing the right composition of the catalyst by tuning the catalyst layer over the gas diffusion electrode can substantially affect the product selectivity and promote reaching the potential industrial scale.

Direct Operando Visualization of Metal Support Interactions Induced by Hydrogen Spillover During CO2 Hydrogenation.

The understanding of catalyst active sites is a fundamental challenge for the future rational design of optimized and bespoke catalysts. For instance, the partial reduction of Ce4+ surface sites to Ce3+ and the formation of oxygen vacancies are critical for CO2 hydrogenation, CO oxidation, and the water gas shift reaction. Furthermore, metal nanoparticles, the reducible support, and metal support interactions are prone to evolve under reaction conditions; therefore a catalyst structure must be characterized under operando conditions to identify active states and deduce structure-activity relationships. In the present work, temperature-induced morphological and chemical changes in Ni nanoparticle-decorated mesoporous CeO2 by means of in situ quantitative multimode electron tomography and in situ heating electron energy loss spectroscopy, respectively, are investigated. Moreover, operando electron energy loss spectroscopy is employed using a windowed gas cell and reveals the role of Ni-induced hydrogen spillover on active Ce3+ site formation and enhancement of the overall catalytic performance.

Cobalt-Iron Oxyhydroxide Obtained from the Metal Phosphide: A Highly Effective Electrocatalyst for the Oxygen Evolution Reaction at High Current Densities.

The development of high current density anodes for the oxygen evolution reaction (OER) is fundamental to manufacturing practical and reliable electrochemical cells. In this work, we have developed a bimetallic electrocatalyst based on cobalt-iron oxyhydroxide that shows outstanding performance for water oxidation. Such a catalyst is obtained from cobalt-iron phosphide nanorods that serve as sacrificial structures for the formation of a bimetallic oxyhydroxide through phosphorous loss concomitantly to oxygen/hydroxide incorporation. CoFeP nanorods are synthesized using a scalable method using triphenyl phosphite as a phosphorous precursor. They are deposited without the use of binders on nickel foam to enable fast electron transport, a highly effective surface area, and a high density of active sites. The morphological and chemical transformation of the CoFeP nanoparticles is analyzed and compared with the monometallic cobalt phosphide in alkaline media and under anodic potentials. The resulting bimetallic electrode presents a Tafel slope as low as 42 mV dec-1 and low overpotentials for OER. For the first time, an anion exchange membrane electrolysis device with an integrated CoFeP-based anode was tested at a high current density of 1 A cm-2, demonstrating excellent stability and Faradaic efficiency near 100%. This work opens up a way for using metal phosphide-based anodes for practical fuel electrosynthesis devices.

Improvement of carbon dioxide electroreduction by crystal surface modification of ZIF-8.

Metal-organic frameworks (MOFs) possess high CO2 adsorption properties and are considered to be a promising candidate for the electrochemical carbon dioxide reduction reaction (eCO2RR). However, their insufficient selectivity and current density constrain their further exploration in the eCO2RR. In this work, by introducing a very small proportion of 2,5-dihydroxyterephthalic acid (DOBDC) into ZIF-8, a surface modified ZIF-8-5% catalyst was synthesized by a post-modification method, exhibiting enhanced selectivity (from 56% to 79%) and current density (from -4 mA cm-2 to -10 mA m-2) compared to ZIF-8. Density functional theory (DFT) calculations further demonstrate that the boosted eCO2RR performance on ZIF-8-5% could be attributed to the improved formation of the *COOH intermediate stemming from successful DOBDC surface modification. This work opens a new path for improving the catalytic properties of MOFs via their surface modification.

Cu2ZnGeSe4 nanocrystals: synthesis and thermoelectric properties.

A synthetic route for producing Cu(2)ZnGeSe(4) nanocrystals with narrow size distributions and controlled composition is presented. These nanocrystals were used to produce densely packed nanomaterials by hot-pressing. From the characterization of the thermoelectric properties of these nanomaterials, Cu(2)ZnGeSe(4) is demonstrated to show excellent thermoelectric properties. A very preliminary adjustment of the nanocrystal composition has already resulted in a figure of merit of up to 0.55 at 450 °C.

Three-dimensional multiple-order twinning of self-catalyzed GaAs nanowires on Si substrates.

In this paper we introduce a new paradigm for nanowire growth that explains the unwanted appearance of parasitic nonvertical nanowires. With a crystal structure polarization analysis of the initial stages of GaAs nanowire growth on Si substrates, we demonstrate that secondary seeds form due to a three-dimensional twinning phenomenon. We derive the geometrical rules that underlie the multiple growth directions observed experimentally. These rules help optimizing nanowire array devices such as solar or water splitting cells or of more complex hierarchical branched nanowire devices.

High performance silicon electrode enabled by titanicone coating.

This paper presents the electrochemical performance and characterization of nano Si electrodes coated with titanicone (TiGL) as an anode for Li ion batteries (LIBs). Atomic layer deposition (ALD) of the metal combined with the molecular layer deposition (MLD) of the organic precursor is used to prepare coated electrodes at different temperatures with improved performance compared to the uncoated Si electrode. Coated electrodes prepared at 150 °C deliver the highest capacity and best current response of 1800 mAh g-1 at 0.1 C and 150 mAh g-1 at 20 C. This represented a substantial improvement compared to the Si baseline which delivers a capacity of 1100 mAh g-1 at 0.1 C but fails to deliver capacity at 20 C. Moreover, the optimized coated electrode shows an outstanding capacity of 1200 mAh g-1 at 1 C for 350 cycles with a capacity retention of 93%. The improved discharge capacity, electrode efficiencies, rate capability and electrochemical stability for the Si-based electrode presented in this manuscript are directly correlated to the optimized TiGL coating layer deposited by the ALD/MLD processes, which enhances lithium kinetics and electronic conductivity as demonstrated by equivalent circuit analysis of low frequency impedance data and conductivity measurements. The coating strategy also stabilizes SEI film formation with better Coulombic efficiencies (CE) and improves long cycling stability by reducing capacity lost.

Engineering the Interfacial Microenvironment via Surface Hydroxylation to Realize the Global Optimization of Electrochemical CO2 Reduction.

The adsorption and activation of CO2 on the electrode interface is a prerequisite and key step for electrocatalytic CO2 reduction reaction (eCO2 RR). Regulating the interfacial microenvironment to promote the adsorption and activation of CO2 is thus of great significance to optimize overall conversion efficiency. Herein, a CO2-philic hydroxyl coordinated ZnO (ZnO-OH) catalyst is fabricated, for the first time, via a facile MOF-assisted method. In comparison to the commercial ZnO, the as-prepared ZnO-OH exhibits much higher selectivity toward CO at lower applied potential, reaching a Faradaic efficiency of 85% at -0.95 V versus RHE. To the best of our knowledge, such selectivity is one of the best records in ZnO-based catalysts reported till date. Density functional theory calculations reveal that the coordinated surficial -OH groups are not only favorable to interact with CO2 molecules but also function in synergy to decrease the energy barrier of the rate-determining step and maintain a higher charge density of potential active sites as well as inhibit undesired hydrogen evolution reaction. Our results indicate that engineering the interfacial microenvironment through the introduction of CO2-philic groups is a promising way to achieve the global optimization of eCO2 RR via promoting adsorption and activation of CO2.

Phase Engineering of Defective Copper Selenide toward Robust Lithium-Sulfur Batteries.

The shuttling of soluble lithium polysulfides (LiPS) and the sluggish Li-S conversion kinetics are two main barriers toward the practical application of lithium-sulfur batteries (LSBs). Herein, we propose the addition of copper selenide nanoparticles at the cathode to trap LiPS and accelerate the Li-S reaction kinetics. Using both computational and experimental results, we demonstrate the crystal phase and concentration of copper vacancies to control the electronic structure of the copper selenide, its affinity toward LiPS chemisorption, and its electrical conductivity. The adjustment of the defect density also allows for tuning the electrochemically active sites for the catalytic conversion of polysulfide. The optimized S/Cu1.8Se cathode efficiently promotes and stabilizes the sulfur electrochemistry, thus improving significantly the LSB performance, including an outstanding cyclability over 1000 cycles at 3 C with a capacity fading rate of just 0.029% per cycle, a superb rate capability up to 5 C, and a high areal capacity of 6.07 mAh cm-2 under high sulfur loading. Overall, the present work proposes a crystal phase and defect engineering strategy toward fast and durable sulfur electrochemistry, demonstrating great potential in developing practical LSBs.

A High Conductivity 1D π-d Conjugated Metal-Organic Framework with Efficient Polysulfide Trapping-Diffusion-Catalysis in Lithium-Sulfur Batteries.

The shuttling behavior and sluggish conversion kinetics of the intermediate lithium polysulfides (LiPS) represent the main obstructions to the practical application of lithium-sulfur batteries (LSBs). Herein, a 1D π-d conjugated metal-organic framework (MOF), Ni-MOF-1D, is presented as an efficient sulfur host to overcome these limitations. Experimental results and density functional theory calculations demonstrate that Ni-MOF-1D is characterized by a remarkable binding strength for trapping soluble LiPS species. Ni-MOF-1D also acts as an effective catalyst for S reduction during the discharge process and Li2 S oxidation during the charging process. In addition, the delocalization of electrons in the π-d system of Ni-MOF-1D provides a superior electrical conductivity to improve electron transfer. Thus, cathodes based on Ni-MOF-1D enable LSBs with excellent performance, for example, impressive cycling stability with over 82% capacity retention over 1000 cycles at 3 C, superior rate performance of 575 mAh g-1 at 8 C, and a high areal capacity of 6.63 mAh cm-2 under raised sulfur loading of 6.7 mg cm-2 . The strategies and advantages here demonstrated can be extended to a broader range of π-d conjugated MOFs materials, which the authors believe have a high potential as sulfur hosts in LSBs.

In(Ga)As quantum dot formation on group-III assisted catalyst-free InGaAs nanowires.

Growth of GaAs and In(x)Ga(1-x)As nanowires by the group-III assisted molecular beam epitaxy growth method on (001)GaAs/SiO(2) substrates is studied in dependence on growth temperature, with the objective of maximizing the indium incorporation. Nanowire growth was achieved for growth temperatures as low as 550 °C. The incorporation of indium was studied by low temperature micro-photoluminescence spectroscopy, Raman spectroscopy and electron energy loss spectroscopy. The results show that the incorporation of indium achieved by lowering the growth temperature does not have the effect of increasing the indium concentration in the bulk of the nanowire, which is limited to 3-5%. For growth temperatures below 575 °C, indium rich regions form at the surface of the nanowires as a consequence of the radial growth. This results in the formation of quantum dots, which exhibit spectrally narrow luminescence.

Characterization of individual barium titanate nanorods and their assessment as building blocks of new circuit architectures.

In this work, we report on the integration of individual BaTiO(3) nanorods into simple circuit architectures. Polycrystalline BaTiO(3) nanorods were synthesized by electrophoretic deposition (EPD) of barium titanate sol into aluminium oxide (AAO) templates and subsequent annealing. Transmission electron microscopy (TEM) observations revealed the presence of slabs of hexagonal polymorphs intergrown within cubic grains, resulting from the local reducing atmosphere during the thermal treatment. Electrical measurements performed on individual BaTiO(3) nanorods revealed resistivity values between 10 and 100 Ω cm, which is in good agreement with typical values reported in the past for oxygen-deficient barium titanate films. Consequently the presence of oxygen vacancies in their structure was indirectly validated. Some of these nanorods were tested as proof-of-concept humidity sensors. They showed reproducible responses towards different moisture concentrations, demonstrating that individual BaTiO(3) nanorods may be integrated in complex circuit architectures with functional capacities.

Effectiveness of nitrogen incorporation to enhance the photoelectrochemical activity of nanostructured TiO2:NH3 versus H2-N2 annealing.

Highly ordered TiO(2) nanohole layers were synthesized by anodic oxidation of titanium foils using ethylene glycol and ammonium fluoride as the electrolyte. The effectiveness of different methods, namely annealing at 500 °C in NH(3) and in H(2) diluted in N(2), to incorporate nitrogen into TiO(2) and thus extend its photoelectrochemical (PEC) activity to the visible range was studied. The intra-gap levels introduced by both processes were identified by means of XPS and PL measurements. Water splitting experiments demonstrated that annealing in H(2) improved the photocatalytic activity of pure TiO(2), while annealing in ammonia led to a decrease in the PEC performance.

Contact resistance stability and cation mixing in a Vulcan-based LiNi1/3Co1/3Mn1/3O2 slurry for semi-solid flow batteries.

The Semi-Solid Flow Battery (SSFB) is an interesting energy storage system (ESS) for stationary applications but, in spite of the significant work presented on this technology so far, understanding the chemical and physical factors limiting its electrochemical performance is still blurred by measurements under static conditions rather than under real operando conditions. In this study, we have used Vulcan carbon as a conductive additive to formulate LiNi1/3Co1/3Mn1/3O2 (NCM) based slurries as the catholyte to characterize electrical and electrochemical performances using a 3-electrode flow cell by electrochemical impedance spectroscopy (EIS) and galvanostatic charge/discharge (GCD), respectively. The results are correlated with post-mortem analyses of recovered slurries using Scanning Electron Microscopy (SEM), Raman spectroscopy and Rietveld refinement of the NCM crystal structure. Due to the improved electrochemical cycling stability of the Vulcan-based NCM slurry and cell configuration used for measurements, we have been able to characterize the system in terms of electrical contributions and correlate them with particle degradation as well as detect antisite defect formation on cycling. The electrical stability of the contact resistance and cation mixing are identified as factors limiting the performance of the semi-solid slurry. The latter is frequently reported in porous electrodes for Li-ion batteries but, to our knowledge, it has not been reported for SSFBs to date.