Nanoporous graphene-based thin-film microelectrodes for in vivo high-resolution neural recording and stimulation.

One of the critical factors determining the performance of neural interfaces is the electrode material used to establish electrical communication with the neural tissue, which needs to meet strict electrical, electrochemical, mechanical, biological and microfabrication compatibility requirements. This work presents a nanoporous graphene-based thin-film technology and its engineering to form flexible neural interfaces. The developed technology allows the fabrication of small microelectrodes (25 µm diameter) while achieving low impedance (∼25 kΩ) and high charge injection (3-5 mC cm-2). In vivo brain recording performance assessed in rodents reveals high-fidelity recordings (signal-to-noise ratio >10 dB for local field potentials), while stimulation performance assessed with an intrafascicular implant demonstrates low current thresholds (<100 µA) and high selectivity (>0.8) for activating subsets of axons within the rat sciatic nerve innervating tibialis anterior and plantar interosseous muscles. Furthermore, the tissue biocompatibility of the devices was validated by chronic epicortical (12 week) and intraneural (8 week) implantation. This work describes a graphene-based thin-film microelectrode technology and demonstrates its potential for high-precision and high-resolution neural interfacing.

Unraveling Exchange Coupling in Ferrites Nano-Heterostructures.

The magnetic coupling of a set of SrFe12 O19 /CoFe2 O4 nanocomposites is investigated. Advanced electron microscopy evidences the structural coherence and texture at the interfaces of the nanostructures. The fraction of the lower anisotropy phase (CoFe2 O4 ) is tuned to assess the limits that define magnetically exchange-coupled interfaces by performing magnetic remanence, first-order reversal curves (FORCs), and relaxation measurements. By combining these magnetometry techniques and the structural and morphological information from X-ray diffraction, electron microscopy, and Mössbauer spectrometry, the exchange intergranular interaction is evidenced, and the critical thickness within which coupled interfaces have a uniform reversal unraveled.

Tunable particle-agglomeration and magnetic coupling in bi-magnetic nanocomposites.

A set of non-stoichiometric Zn-Co-ferrite nanoparticles (NPs) was prepared by thermal decomposition of metallic complexes, in the presence of oleic acid, and, after a ligand-exchange process, was coated by a hydrophilic surfactant: these NPs were used as seeds in a sol-gel self-combustion synthesis to prepare nanocomposites (NCs) with a fixed weight ratio. Our focus here is the development of an efficient synthetic approach to control the magnetic coupling between a hard-magnetic matrix (Sr-ferrite) and NPs. The physico-chemical synthetic conditions (temperature, pH, colloidal stability) were optimized in order to tune their effect on the final particles' agglomeration in the matrix. We demonstrate that our synthetic approach is a novel way to produce strongly magnetically coupled NCs, where the final extrinsic properties could be tuned by controlling (i) the agglomeration of seeds in the matrix and (ii) their elemental doping.

Low-Cost, High-Yield Zinc Oxide-Based Nanostars for Alkaline Overall Water Splitting.

The investigation of high-efficiency and sustainable electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline media is critical for renewable energy technologies. Here, we report a low-cost and high-yield method to obtain ZnOHF-ZnO-based 2D nanostars (NSs) by means of chemical bath deposition (CBD). The obtained NSs, cast onto graphene paper substrates, were used as active materials for the development of a full water splitting cell. For the HER, NSs were decorated with an ultralow amount of Pt nanoparticles (11.2 µg cm-2), demonstrating an overpotential of 181 mV at a current density of 10 mA cm-2. The intrinsic activity of Pt was optimized, thanks to the ZnO supporting nanostructures, as outlined by the mass activity of Pt (0.9 mA mgPt-1) and its turnover frequency (0.27 s-1 for a Pt loading of 11.2 µg cm-2). For the OER, bare NSs showed a remarkable result of 355 mV at 10 mA cm-2 in alkaline media. Pt-decorated and bare NSs were used as the cathode and anode, respectively, for alkaline electrochemical water splitting, assessing a stable overpotential of 1.7 V at a current density of 10 mA cm-2. The reported data pave the way toward large-scale production of low-cost electrocatalysts for green hydrogen production.

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.

Highly Durable Nanoporous Cu2-xS Films for Efficient Hydrogen Evolution Electrocatalysis under Mild pH Conditions.

Copper-based hydrogen evolution electrocatalysts are promising materials to scale-up hydrogen production due to their reported high current densities; however, electrode durability remains a challenge. Here, we report a facile, cost-effective, and scalable synthetic route to produce Cu2-xS electrocatalysts, exhibiting hydrogen evolution rates that increase for ∼1 month of operation. Our Cu2-xS electrodes reach a state-of-the-art performance of ∼400 mA cm-2 at -1 V vs RHE under mild conditions (pH 8.6), with almost 100% Faradaic efficiency for hydrogen evolution. The rise in current density was found to scale with the electrode electrochemically active surface area. The increased performance of our Cu2-xS electrodes correlates with a decrease in the Tafel slope, while analyses by X-ray photoemission spectroscopy, operando X-ray diffraction, and in situ spectroelectrochemistry cooperatively revealed the Cu-centered nature of the catalytically active species. These results allowed us to increase fundamental understanding of heterogeneous electrocatalyst transformation and consequent structure-activity relationship. This facile synthesis of highly durable and efficient Cu2-xS electrocatalysts enables the development of competitive electrodes for hydrogen evolution under mild pH conditions.

Brookite TiO2 Nanorods as Promising Electrochromic and Energy Storage Materials for Smart Windows.

Electrochromic smart windows (ESWs) offer an attractive option for regulating indoor lighting conditions. Electrochromic materials based on ion insertion/desertion mechanisms also present the possibility for energy storage, thereby increasing overall energy efficiency and adding value to the system. However, current electrochromic electrodes suffer from performance degradation, long response time, and low coloration efficiency. This work aims to produce defect-engineered brookite titanium dioxide (TiO2 ) nanorods (NRs) with different lengths and investigate their electrochromic performance as potential energy storage materials. The controllable synthesis of TiO2 NRs with inherent defects, along with smaller impedance and higher carrier concentrations, significantly enhances their electrochromic performance, including improved resistance to degradation, shorter response times, and enhanced coloration efficiency. The electrochromic performance of TiO2 NRs, particularly longer ones, is characterized by fast switching speeds (20 s for coloration and 12 s for bleaching), high coloration efficiency (84.96 cm2  C-1 at a 600 nm wavelength), and good stability, highlighting their potential for advanced electrochromic smart window applications based on Li+ ion intercalation.

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.

Stoichiometry modulates the optoelectronic functionality of zinc phosphide (Zn3-xP2+x).

Predictive synthesis-structure-property relationships are at the core of materials design for novel applications. In this regard, correlations between the compositional stoichiometry variations and functional properties are essential for enhancing the performance of devices based on these materials. In this work, we investigate the effect of stoichiometry variations and defects on the structural and optoelectronic properties of monocrystalline zinc phosphide (Zn3P2), a promising compound for photovoltaic applications. We use experimental methods, such as electron and X-ray diffraction and Raman spectroscopy, along with density functional theory calculations, to showcase the favorable creation of P interstitial defects over Zn vacancies in P-rich and Zn-poor compositional regions. Photoluminescence and absorption measurements show that these defects create additional energy levels at about 180 meV above the valence band. Furthermore, they lead to the narrowing of the bandgap, due to the creation of band tails in the region of around 10-20 meV above the valence and below the conduction band. The ability of zinc phosphide to form off-stoichiometric compounds provides a new promising opportunity for tunable functionality that benefits applications. In that regard, this study is crucial for the further development of zinc phosphide and its application in optoelectronic and photovoltaic devices, and should pave the way for defect engineering in this kind of material.

Electrochemical Conversion of Alcohols into Acidic Commodities on Nickel Sulfide Nanoparticles.

The electrocatalytic oxidation of alcohols is a potentially cost-effective strategy for the synthesis of valuable chemicals at the anode while simultaneously generating hydrogen at the cathode. For this approach to become commercially viable, high-activity, low-cost, and stable catalysts need to be developed. Herein, we demonstrate an electrocatalyst based on earth-abundant nickel and sulfur elements. Experimental investigations reveal the produced NiS displays excellent electrocatalytic performance associated with a higher electrochemical surface area (ECSA) and the presence of sulfate ions on the formed NiOOH surface in basic media. The current densities reached for the oxidation of ethanol and methanol at 1.6 V vs reversible hydrogen electrode (RHE) are up to 175.5 and 145.1 mA cm-2, respectively. At these high current densities, the Faradaic efficiency of methanol to formate conversion is 98% and that of ethanol to acetate is 81%. Density functional theory calculations demonstrate the presence of the generated sulfate groups to modify the electronic properties of the NiOOH surface, improving electroconductivity and electron transfer. Besides, calculations are used to determine the reaction energy barriers, revealing the dehydrogenation of ethoxy groups to be more favorable than that of methoxy on the catalyst surface, which explains the highest current densities obtained for ethanol oxidation.

Sub-nanometer mapping of strain-induced band structure variations in planar nanowire core-shell heterostructures.

Strain relaxation mechanisms during epitaxial growth of core-shell nanostructures play a key role in determining their morphologies, crystal structure and properties. To unveil those mechanisms, we perform atomic-scale aberration-corrected scanning transmission electron microscopy studies on planar core-shell ZnSe@ZnTe nanowires on α-Al2O3 substrates. The core morphology affects the shell structure involving plane bending and the formation of low-angle polar boundaries. The origin of this phenomenon and its consequences on the electronic band structure are discussed. We further use monochromated valence electron energy-loss spectroscopy to obtain spatially resolved band-gap maps of the heterostructure with sub-nanometer spatial resolution. A decrease in band-gap energy at highly strained core-shell interfacial regions is found, along with a switch from direct to indirect band-gap. These findings represent an advance in the sub-nanometer-scale understanding of the interplay between structure and electronic properties associated with highly mismatched semiconductor heterostructures, especially with those related to the planar growth of heterostructured nanowire networks.

Sustainable oxygen evolution electrocatalysis in aqueous 1 M H2SO4 with earth abundant nanostructured Co3O4.

Earth-abundant electrocatalysts for the oxygen evolution reaction (OER) able to work in acidic working conditions are elusive. While many first-row transition metal oxides are competitive in alkaline media, most of them just dissolve or become inactive at high proton concentrations where hydrogen evolution is preferred. Only noble-metal catalysts, such as IrO2, are fast and stable enough in acidic media. Herein, we report the excellent activity and long-term stability of Co3O4-based anodes in 1 M H2SO4 (pH 0.1) when processed in a partially hydrophobic carbon-based protecting matrix. These Co3O4@C composites reliably drive O2 evolution a 10 mA cm-2 current density for >40 h without appearance of performance fatigue, successfully passing benchmarking protocols without incorporating noble metals. Our strategy opens an alternative venue towards fast, energy efficient acid-media water oxidation electrodes.

Defect Engineering in Solution-Processed Polycrystalline SnSe Leads to High Thermoelectric Performance.

SnSe has emerged as one of the most promising materials for thermoelectric energy conversion due to its extraordinary performance in its single-crystal form and its low-cost constituent elements. However, to achieve an economic impact, the polycrystalline counterpart needs to replicate the performance of the single crystal. Herein, we optimize the thermoelectric performance of polycrystalline SnSe produced by consolidating solution-processed and surface-engineered SnSe particles. In particular, the SnSe particles are coated with CdSe molecular complexes that crystallize during the sintering process, forming CdSe nanoparticles. The presence of CdSe nanoparticles inhibits SnSe grain growth during the consolidation step due to Zener pinning, yielding a material with a high density of grain boundaries. Moreover, the resulting SnSe-CdSe nanocomposites present a large number of defects at different length scales, which significantly reduce the thermal conductivity. The produced SnSe-CdSe nanocomposites exhibit thermoelectric figures of merit up to 2.2 at 786 K, which is among the highest reported for solution-processed SnSe.

Rotated domains in selective area epitaxy grown Zn3P2: formation mechanism and functionality.

Zinc phosphide (Zn3P2) is an ideal absorber candidate for solar cells thanks to its direct bandgap, earth-abundance, and optoelectronic characteristics, albeit it has been insufficiently investigated due to limitations in the fabrication of high-quality material. It is possible to overcome these factors by obtaining the material as nanostructures, e.g. via the selective area epitaxy approach, enabling additional strain relaxation mechanisms and minimizing the interface area. We demonstrate that Zn3P2 nanowires grow mostly defect-free when growth is oriented along the [100] and [110] of the crystal, which is obtained in nanoscale openings along the [110] and [010] on InP(100). We detect the presence of two stable rotated crystal domains that coexist in the structure. They are due to a change in the growth facet, which originates either from the island formation and merging in the initial stages of growth or lateral overgrowth. These domains have been visualized through 3D atomic models and confirmed with image simulations of the atomic scale electron micrographs. Density functional theory simulations describe the rotated domains' formation mechanism and demonstrate their lattice-matched epitaxial relation. In addition, the energies of the shallow states predicted closely agree with transition energies observed by experimental studies and offer a potential origin for these defect transitions. Our study represents an important step forward in the understanding of Zn3P2 and thus for the realisation of solar cells to respond to the present call for sustainable photovoltaic technology.

Photodehydrogenation of Ethanol over Cu2O/TiO2 Heterostructures.

The photodehydrogenation of ethanol is a sustainable and potentially cost-effective strategy to produce hydrogen and acetaldehyde from renewable resources. The optimization of this process requires the use of highly active, stable and selective photocatalytic materials based on abundant elements and the proper adjustment of the reaction conditions, including temperature. In this work, Cu2O-TiO2 type-II heterojunctions with different Cu2O amounts are obtained by a one-pot hydrothermal method. The structural and chemical properties of the produced materials and their activity toward ethanol photodehydrogenation under UV and visible light illumination are evaluated. The Cu2O-TiO2 photocatalysts exhibit a high selectivity toward acetaldehyde production and up to tenfold higher hydrogen evolution rates compared to bare TiO2. We further discern here the influence of temperature and visible light absorption on the photocatalytic performance. Our results point toward the combination of energy sources in thermo-photocatalytic reactors as an efficient strategy for solar energy conversion.

Nickel Iron Diselenide for Highly Efficient and Selective Electrocatalytic Conversion of Methanol to Formate.

The electro-oxidation of methanol to formate is an interesting example of the potential use of renewable energies to add value to a biosourced chemical commodity. Additionally, methanol electro-oxidation can replace the sluggish oxygen evolution reaction when coupled to hydrogen evolution or to the electroreduction of other biomass-derived intermediates. But the cost-effective realization of these reaction schemes requires the development of efficient and low-cost electrocatalysts. Here, a noble metal-free catalyst, Ni1- x Fex Se2 nanorods, with a high potential for an efficient and selective methanol conversion to formate is demonstrated. At its optimum composition, Ni0.75 Fe0.25 Se2 , this diselenide is able to produce 0.47 mmol cm-2  h-1 of formate at 50 mA cm-2 with a Faradaic conversion efficiency of 99%. Additionally, this noble-metal-free catalyst is able to continuously work for over 50 000 s with a minimal loss of efficiency, delivering initial current densities above 50 mA cm-2 and 2.2 A mg-1 in a 1.0 m KOH electrolyte with 1.0 m methanol at 1.5 V versus reversible hydrogen electrode. This work demonstrates the highly efficient and selective methanol-to-formate conversion on Ni-based noble-metal-free catalysts, and more importantly it shows a very promising example to exploit the electrocatalytic conversion of biomass-derived chemicals.

Electrocatalytic Behavior of PtCu Clusters Produced by Nanoparticle Beam Deposition.

State-of-the-art electrocatalysts for electrolyzer and fuel cell applications currently rely on platinum group metals, which are costly and subject to supply risks. In recent years, a vast collection of research has explored the possibility of reducing the Pt content in such catalysts by alloying with earth-abundant and cheap metals, enabling co-optimization of cost and activity. Here, using nanoparticle beam deposition, we explore the electrocatalytic performance of PtCu alloy clusters in the hydrogen evolution reaction (HER). Elemental compositions of the produced bimetallic clusters were shown by X-ray photoelectron spectroscopy (XPS) to range from 2 at. % to 38 at. % Pt, while high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) combined with energy dispersive X-ray (EDX) spectroscopy indicated that the predominant cluster morphologies could be characterized as either a fully mixed alloy or as a mixed core with a Cu-rich shell. In contrast with previous studies, a monotonic decrease in HER activity with increasing Cu content was observed over the composition range studied, with the current density measured at -0.3 V (vs reversible hydrogen electrode) scaling approximately linearly with Pt at. %. This trend opens up the possibility that PtCu could be used as a reference system for comparing the composition-dependent activity of other bimetallic catalysts.

Optical and electronic properties of silver nanoparticles embedded in cerium oxide.

Wide bandgap oxides can be sensitized to visible light by coupling them with plasmonic nanoparticles (NPs). We investigate the optical and electronic properties of composite materials made of Ag NPs embedded within cerium oxide layers of different thickness. The electronic properties of the materials are investigated by x-ray and ultraviolet photoemission spectroscopy, which demonstrates the occurrence of static charge transfers between the metal and the oxide and its dependence on the NP size. Ultraviolet-visible spectrophotometry measurements show that the materials have a strong absorption in the visible range induced by the excitation of localized surface plasmon resonances. The plasmonic absorption band can be modified in shape and intensity by changing the NP aspect ratio and density and the thickness of the cerium oxide film.

Coordination Polymer to Atomically Thin, Holey, Metal-Oxide Nanosheets for Tuning Band Alignment.

Holey 2D metal oxides have shown great promise as functional materials for energy storage and catalysts. Despite impressive performance, their processing is challenged by the requirement of templates plus capping agents or high temperatures; these materials also exhibit excessive thicknesses and low yields. The present work reports a metal-based coordination polymer (MCP) strategy to synthesize polycrystalline, holey, metal oxide (MO) nanosheets with thicknesses as low as two-unit cells. The process involves rapid exfoliation of bulk-layered, MCPs (Ce-, Ti-, Zr-based) into atomically thin MCPs at room temperature, followed by transformation into holey 2D MOs upon the removal of organic linkers in aqueous solution. Further, this work represents an extra step for decorating the holey nanosheets using precursors of transition metals to engineer their band alignments, establishing a route to optimize their photocatalysis. The work introduces a simple, high-yield, room-temperature, and template-free approach to synthesize ultrathin holey nanosheets with high-level functionalities.