Cathodic Deposition-Assisted Synthesis of Thin Glass MOF Films for High-Performance Gas Separations.

Glass metal-organic framework (MOF) films can be fabricated from their crystalline counterparts through a melt-quenching process and are prospective candidates for gas separation because of the elimination of the grain boundaries in crystalline MOF films. However, current techniques are limited to producing glass MOF films with a thickness of tens of micrometers, which leads to ultralow gas permeances. Here, we report a novel cathodic deposition-assisted synthesis of glass ZIF-62 films with a thickness as low as ~1 µm. Electrochemical analyses and deposition experiments suggest that the cathodic deposition can lead to pure crystalline ZIF-62 films with a controllable thickness of ~2 µm to ~15 µm. Accordingly, glass ZIF-62 films with a thickness of ~1 µm to ~10 µm can be obtained after a thermal treatment. The fabricated defect-free glass ZIF-62 film measuring 2 µm in thickness shows a remarkable CO2/N2 and CO2/CH4 selectivity of 31.4 and 33.4, respectively, with a CO2 permeance which is over 30 times higher than the best-performing glass ZIF-62 films in literature.

Scalable Electrodeposition of Liquid Metal from an Acetonitrile-Based Electrolyte for Highly Integrated Stretchable Electronics.

The advancement of highly integrated stretchable electronics requires the development of scalable sub-micrometer conductor patterning. Eutectic gallium indium (EGaIn) is an attractive conductor for stretchable electronics, as its liquid metallic character grants it high electrical conductivity upon deformation. However, its high surface tension makes its patterning with sub-micrometer resolution challenging. In this work, this limitation is overcome by way of the electrodeposition of EGaIn. A non-aqueous acetonitrile-based electrolyte that exhibits high electrochemical stability and chemical orthogonality is used. The electrodeposited material leads to low-resistance lines that remain stable upon (repeated) stretching to a 100% strain. Because electrodeposition benefits from the resolution of mature nanofabrication methods used to pattern the base metal, the proposed "bottom-up" approach achieves a record-high density integration of EGaIn regular lines of 300 nm half-pitch on an elastomer substrate by plating on a gold seed layer prepatterned by nanoimprinting. Moreover, vertical integration is enabled by filling high-aspect-ratio vias. This capability is conceptualized by the fabrication of an omnidirectionally stretchable 3D electronic circuit, and demonstrates a soft-electronic analog of the stablished damascene process used to fabricate microchip interconnects. Overall, this work proposes a simple route to address the challenge of metallization in highly integrated (3D) stretchable electronics.

Exploring Pt-Pd Alloy Nanoparticle Cluster Formation through Conventional Sizing Techniques and Single-Particle Inductively Coupled Plasma-Sector Field Mass Spectrometry.

Accurate characterization of Pt-Pd alloy nanoparticle clusters (NCs) is crucial for understanding their synthesis using Gas-Diffusion Electrocrystallization (GDEx). In this study, we propose a comprehensive approach that integrates conventional sizing techniques-scanning electron microscopy (SEM) and dynamic light scattering (DLS)-with innovative single-particle inductively coupled plasma-sector field mass spectrometry (spICP-SFMS) to investigate Pt-Pd alloy NC formation. SEM and DLS provide insights into morphology and hydrodynamic sizes, while spICP-SFMS elucidates the particle size and distribution of Pt-Pd alloy NCs, offering rapid and orthogonal characterization. The spICP-SFMS approach presented enables detailed characterization of Pt-Pd alloy NCs, which was previously challenging due to the absence of multi-element capabilities in conventional spICP-MS systems. This innovative approach not only enhances our understanding of bimetallic nanoparticle synthesis, but also paves the way for tailoring these materials for specific applications, marking a significant advancement in the field of nanomaterial science.

Fluorine-free organic electrolytes for the stable electrodeposition of neodymium metal.

Electrowinning is regarded as a clean process to recover neodymium metal from secondary sources such as spent Nd-Fe-B permanent magnets, but the current methods are severely limited by a high energy consumption (molten salts), or by the high costs and environmental impact of the electrolyte components (ionic liquids). Therefore, there is a demand for more sustainable electrowinning methods for the recovery of neodymium metal. Inspired by our own previous work and the work of others, we developed new fluorine-free organic electrolytes that enable the electrodeposition of neodymium metal at room temperature. The electrolytes consist of solvated neodymium borohydride, Nd(BH4)3, dissolved in the ether solvents tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-MeTHF), 1,2-dimethoxyethane (DME) and diethylene glycol dimethyl ether (diglyme, G2), and these complexes can be prepared entirely from non-fluorinated precursors such as neodymium(III) chloride (NdCl3) and sodium borohydride (NaBH4). In contrast to our previous bis(trifluoromethylsulfonyl)imide-containing electrolytes, electrodeposition of neodymium proceeds over time without significant loss of current density, indicating a higher stability against unwanted side-reactions that lead to passivation of the deposit on the electrode. Characterization of the deposits by scanning electron microscopy (SEM), energy-dispersive X-ray fluorescence (EDX), and X-ray photoelectron spectroscopy (XPS) unambiguously indicated the presence of neodymium metal.

Sideways propelled bimetallic rods at the water/oil interface.

The motion of self-propelling microswimmers is significantly affected by confinement, which can enhance or reduce their mobility and also steer the direction of their propulsion. While their interactions with solid boundaries have already received considerable attention, many aspects of the influence of liquid-liquid interfaces (LLI) on active particle propulsion still remain unexplored. In this work, we studied the adsorption and motion of bimetallic Janus sideways propelled rods dispersed at the interface between an aqueous solution of hydrogen peroxide and oil. The wetting properties of the bimetallic rods result in a wide distribution of their velocities at the LLI. While a fraction of rods remain immotile, we note a significant enhancement of motility for the rest of the particles with velocities of up to 8 times higher in comparison to those observed near a solid wall. Liquid-liquid interfaces, therefore, can provide a new way to regulate the propulsion of bimetallic particles.

Electrosynthesis of Metal-Organic Framework Films with Well-Defined Facets.

The deposition of metal-organic framework (MOF) films with defined exposed facets is important to enhance the performance of these films for, for example, catalysis or separations. In this work, MOF films with specific exposed facets are electrodeposited anodically on various substrates (e. g. on copper-sputtered Si wafers, copper meshes, copper foams, and polypropylene membranes). The influence of the deposition parameters, including the pH of the solution, current density, concentration of linker, and solvent, on the exposed facets of the deposited MOFs was investigated. The results suggest that precise control over the supersaturation during anodic deposition is a possible strategy for synthesizing MOF crystals with well-defined exposed facets. This approach provides a powerful toolbox for various applications requiring crystal facet control of MOF films.

Designing Oxide Catalysts for Oxygen Electrocatalysis: Insights from Mechanism to Application.

The electrochemical oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are fundamental processes in a range of energy conversion devices such as fuel cells and metal-air batteries. ORR and OER both have significant activation barriers, which severely limit the overall performance of energy conversion devices that utilize ORR/OER. Meanwhile, ORR is another very important electrochemical reaction involving oxygen that has been widely investigated. ORR occurs in aqueous solutions via two pathways: the direct 4-electron reduction or 2-electron reduction pathways from O2 to water (H2O) or from O2 to hydrogen peroxide (H2O2). Noble metal electrocatalysts are often used to catalyze OER and ORR, despite the fact that noble metal electrocatalysts have certain intrinsic limitations, such as low storage. Thus, it is urgent to develop more active and stable low-cost electrocatalysts, especially for severe environments (e.g., acidic media). Theoretically, an ideal oxygen electrocatalyst should provide adequate binding to oxygen species. Transition metals not belonging to the platinum group metal-based oxides are a low-cost substance that could give a d orbital for oxygen species binding. As a result, transition metal oxides are regarded as a substitute for typical precious metal oxygen electrocatalysts. However, the development of oxide catalysts for oxygen reduction and oxygen evolution reactions still faces significant challenges, e.g., catalytic activity, stability, cost, and reaction mechanism. We discuss the fundamental principles underlying the design of oxide catalysts, including the influence of crystal structure, and electronic structure on their performance. We also discuss the challenges associated with developing oxide catalysts and the potential strategies to overcome these challenges.

Boosting Lean Electrolyte Lithium-Sulfur Battery Performance with Transition Metals: A Comprehensive Review.

Lithium-sulfur (Li-S) batteries have received widespread attention, and lean electrolyte Li-S batteries have attracted additional interest because of their higher energy densities. This review systematically analyzes the effect of the electrolyte-to-sulfur (E/S) ratios on battery energy density and the challenges for sulfur reduction reactions (SRR) under lean electrolyte conditions. Accordingly, we review the use of various polar transition metal sulfur hosts as corresponding solutions to facilitate SRR kinetics at low E/S ratios (< 10 µL mg-1), and the strengths and limitations of different transition metal compounds are presented and discussed from a fundamental perspective. Subsequently, three promising strategies for sulfur hosts that act as anchors and catalysts are proposed to boost lean electrolyte Li-S battery performance. Finally, an outlook is provided to guide future research on high energy density Li-S batteries.

Cathodic deposition of MOF films: mechanism and applications.

Metal-organic framework (MOF) thin films could be used for ion/molecular sieving, sensing, catalysis, and energy storage, but thus far no large-scale applications are known. One of the reasons is the lack of convenient and controllable fabrication methods. This work reviews the cathodic deposition of MOF films, which has advantages (e.g., simple operations, mild conditions, and controllable MOF film thickness/morphology) over other reported techniques. Accordingly, we discuss the mechanism of the cathodic deposition of MOF films which consists of the electrochemically triggered deprotonation of organic linkers and the formation of inorganic building blocks. Thereafter, the main applications of cathodically deposited MOF films are introduced with the aim of showing this technique's wide-ranging applications. Finally, we give the remaining issues and outlooks of the cathodic deposition of MOF films to drive its future development.

Realizing High-Performance Cathodes with Cationic and Anionic Redox Reactions in High-Sodium-Content P2-Type Oxides for Sodium-Ion Batteries.

P2-type layered transition-metal oxides with anionic redox reactions are promising cathodes for sodium-ion batteries. In this work, a high-sodium-content P2-type Na7/9Li1/9Mg1/9Cu1/9Mn2/3O2 (NLMC) cathode material is prepared by substituting Li/Mg/Cu for Mn sites in Na2/3MnO2. The Li/Mg ions trigger the anionic redox reaction, while the Cu ions enhance the structure stability during electrochemical cycling. As a result, the oxide has a high reversible capacity of 225 mAh g-1 originating from both cationic and anionic redox activities with a capacity retention of 77% after 100 cycles. The migration energy barrier and Na ion diffusion kinetics are studied using density functional theory (DFT) calculations and the galvanostatic intermittent titration technique. Furthermore, X-ray diffraction, DFT, scanning electron microscopy, and transmission electron microscopy are applied to reveal the structural evolution and charge compensation of NLMC, providing a thorough understanding of the structural and morphology evolution of Na-deficient oxides during cycling. The results are inspiring for the design of a high-Na content P2-type layered oxide cathode for sodium-ion batteries.

Critical Role of Phosphorus in Hollow Structures Cobalt-Based Phosphides as Bifunctional Catalysts for Water Splitting.

Cobalt phosphides electrocatalysts have great potential for water splitting, but the unclear active sides hinder the further development of cobalt phosphides. Wherein, three different cobalt phosphides with the same hollow structure morphology (CoP-HS, CoP2 -HS, CoP3 -HS) based on the same sacrificial template of ZIF-67 are prepared. Surprisingly, these cobalt phosphides exhibit similar OER performances but quite different HER performances. The identical OER performance of these CoPx -HS in alkaline solution is attributed to the similar surface reconstruction to CoOOH. CoP-HS exhibits the best catalytic activity for HER among these CoPx -HS in both acidic and alkaline media, originating from the adjusted electronic density of phosphorus to affect absorption-desorption process on H. Moreover, the calculated ΔGH* based on P-sites of CoP-HS follows a quite similar trend with the normalized overpotential and Tafel slope, indicating the important role of P-sites for the HER process. Moreover, CoP-HS displays good performance (cell voltage of 1.67 V at a current density of 50 mA cm-2 ) and high stability in 1 M KOH. For the first time, this work detailly presents the critical role of phosphorus in cobalt-based phosphides for water splitting, which provides the guidance for future investigations on transition metal phosphides from material design to mechanism understanding.

Cathodic Electrodeposition of MOF Films Using Hydrogen Peroxide.

Metal-organic framework (MOF) films can be made by cathodic electrodeposition, where a Brønsted base is formed electrochemically which deprotonates the MOF linkers that are present in solution as undissociated/partially dissociated weak acids. However, the co-deposition of metal and the narrow range of possible metal nodes limit the scope of this method. In this work, we propose the use of hydrogen peroxide (hydrogen peroxide assisted cathodic deposition or HPACD), to overcome these limitations. Electrochemical measurements indicate that in DMF, hydrogen peroxide is reduced to superoxide anions that deprotonate the carboxylic ligands. This single-electron reduction happens at much higher potentials than all previous reported methods. This prevents the co-deposition of metal and extends the range of possible metal nodes. Various pure MOF films (HKUST-1, MIL-53(Fe) and MOF-5) were prepared via this approach. HPACD was also used for the preparation of patterned MOF films and of flexible Cu-BTC coated paper membranes which reject 99.1 % of Rose Bengal from water with a permeance of 8.4 L m-2 h-1 bar-1 .

Carbon Nanotube Fibers Decorated with MnO2 for Wire-Shaped Supercapacitor.

Fibers made from CNTs (CNT fibers) have the potential to form high-strength, lightweight materials with superior electrical conductivity. CNT fibers have attracted great attention in relation to various applications, in particular as conductive electrodes in energy applications, such as capacitors, lithium-ion batteries, and solar cells. Among these, wire-shaped supercapacitors demonstrate various advantages for use in lightweight and wearable electronics. However, making electrodes with uniform structures and desirable electrochemical performances still remains a challenge. In this study, dry-spun CNT fibers from CNT carpets were homogeneously loaded with MnO2 nanoflakes through the treatment of KMnO4. These functionalized fibers were systematically characterized in terms of their morphology, surface and mechanical properties, and electrochemical performance. The resulting MnO2-CNT fiber electrode showed high specific capacitance (231.3 F/g) in a Na2SO4 electrolyte, 23 times higher than the specific capacitance of the bare CNT fibers. The symmetric wire-shaped supercapacitor composed of CNT-MnO2 fiber electrodes and a PVA/H3PO4 electrolyte possesses an energy density of 86 nWh/cm and good cycling performance. Combined with its light weight and high flexibility, this CNT-based wire-shaped supercapacitor shows promise for applications in flexible and wearable energy storage devices.

Electrochemical behavior and electrodeposition of gallium in 1,2-dimethoxyethane-based electrolytes.

The electrochemical behavior and electrodeposition of gallium was studied in a non-aqueous electrolyte comprising of gallium(iii) chloride and 1,2-dimethoxyethane (DME). Electrochemical quartz crystal microbalance (EQCM) and rotating ring disk electrode (RRDE) measurements indicate that reduction of gallium(iii) is a two-step process: first from gallium(iii) to gallium(i), and then from gallium(i) to gallium(0). The morphology and elemental composition of the electrodeposited layer were examined using scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). Metallic gallium was deposited as spheres with diameters of several hundred nanometers that were stacked on top of each other. X-ray photoelectron spectroscopy (XPS) revealed that each gallium sphere was covered by a thin gallium oxide shell. Electrochemical experiments indicated that these oxide layers are electrically conductive, as gallium can be electrodeposited and partially stripped on or from the layer of spheres below. This was further evidenced by simultaneous electrodeposition of gallium and indium, using indium as a tracer. Electrodeposition of gallium from an O2-containing electrolyte resulted in spheres with smaller diameters. This was due to the formation thicker oxide shells, through which diffusion of gallium atoms that were electrodeposited on the surface, was slower. The concentration of gallium adatoms on top of the gallium spheres to form a new sphere therefore reaches the critical concentration for nucleating a new gallium sphere sooner, leading to smaller spheres.

Electrodeposition of neodymium and dysprosium from organic electrolytes.

A new class of organic electrolytes has been developed for the electrodeposition of rare-earth metals at room temperature. These electrolytes consist of a rare-earth bis(trifluoromethylsulfonyl)imide or chloride salt and a borohydride salt, dissolved in the ether solvents 1,2-dimethoxyethane or 2-methyltetrahydrofuran. In these electrolytes, a soluble lanthanide(iii) borohydride complex [Ln(BH4)4]- is formed, which allows for the electrodeposition of neodymium- or dysprosium-containing layers. The electrochemistry of these electrolytes was characterized by cyclic voltammetry. The deposits were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray fluorescence (EDX) and X-ray photoelectron spectroscopy (XPS), and the results suggest the presence of metallic neodymium and dysprosium.

'Sweeping rods': cargo transport by self-propelled bimetallic microrods moving perpendicular to their long axis.

A possible application of self-propelling particles is the transport of microscopic cargo. Maximizing the collection and transport efficiency of particulate matter requires the area swept by the moving particle to be as large as possible. One such particle geometry are rods propelled perpendicular to their long axis, that act as "sweepers" for collecting particles. Here we report on the required Janus coating to achieve such motion, and on the dynamics of the collection and transport of microscopic cargo by sideways propelled Janus rods.

Indium electrodeposition from indium(iii) methanesulfonate in DMSO.

The electrochemical behavior and electrodeposition of indium was investigated at 26 °C and 160 °C from a solution composed of indium(iii) methanesulfonate and dimethylsulfoxide (DMSO). Indium(iii) methanesulfonate was synthesized from indium(iii) oxide and methanesulfonic acid (MSA). Cyclic voltammetry, quartz crystal microbalance measurements and rotating ring disk electrode experiments indicated that reduction of indium(iii) to both indium(i) and indium(0) occurs. Yet, reduction to metallic indium was found to be the predominant process. Deposited indium could be stripped to indium(i). This unstable species disproportionated to indium(iii) and indium(0), leading to the formation of micron-sized metallic indium particles in the electrolyte. At 26 °C, indium deposited on glassy carbon as smooth, flat films whereas at 160 °C, it deposits as droplets.

The Decay Mechanism Related to Structural and Morphological Evolution in Lithium-Rich Cathode Materials for Lithium-Ion Batteries.

Li-rich oxides have garnered intense interest recently for their excellent capacity in rechargeable lithium-ion batteries (LIBs). However, poor cycling stability and capacity degradation during the cycling process impede their practical application. Herein, two ball-shaped cobalt-free oxide materials, Li1.1 Mg0.05 Ni0.3 Mn0.55 O2 and Li1.1 Zn0.05 Ni0.3 Mn0.55 O2 , which exhibit excellent cycling performance at a high current between 2 V and 4.8 V, are demonstrated. The two Li-rich materials are prepared from hydrothermally synthesized carbonated precursors. Both oxides exhibit high reversible capacities of 237 and 231 mAh g-1 at 20 mA g-1 , respectively, originating from the redox of Ni2+ /Ni4+ and O2- /(O2 )n- . Li1.1 Mg0.05 Ni0.3 Mn0.55 O2 presents excellent cycling stability after 200 cycles with 90 % capacity retention. Studies of the structural evolution upon electrochemical cycling implies the cathodes undergo a volume expansion, which results in continuous expanding, cracking, and crushing of the spherical particles, which further induces capacity fading in the cathodes.

Spin transition nanoparticles made electrochemically.

Materials displaying novel magnetic ground states signify the most exciting prospects for nanoscopic devices for nanoelectronics and spintronics. Spin transition materials, e.g., spin liquids and spin glasses, are at the forefront of this pursuit; but the few synthesis routes available do not produce them at the nanoscale. Thus, it remains an open question if and how their spin transition nature persists at such small dimensions. Here we demonstrate a new route to synthesize nanoparticles of spin transition materials, gas-diffusion electrocrystallization (GDEx), wherein the reactive precipitation of soluble metal ions with the products of the oxygen reduction reaction (ORR), i.e., in situ produced H2O2, OH-, drives their formation at the electrochemical interface. Using mixtures of Cu2+ and Zn2+ as the metal precursors, we form spin transition materials of the herbertsmithite family-heralded as the first experimental material known to exhibit the properties of a quantum spin liquid (QSL). Single-crystal nanoparticles of ∼10-16 nm were produced by GDEx, with variable Cu/Zn stoichiometry at the interlayer sites of ZnxCu4-x(OH)6Cl2. For x = 1 (herbertsmithite) the GDEx nanoparticles demonstrated a quasi-QSL behavior, whereas for x = 0.3 (0.3 < x < 1 for paratacamite) and x = 0 (clinoatacamite) a spin-glass behavior was evidenced. Finally, our discovery not only confirms redox reactions as the driving force to produce spin transition nanoparticles, but also proves a simple way to switch between these magnetic ground states within an electrochemical system, paving the way to further explore its reversibility and overarching implications.

Enhancing the solubility of 1,4-diaminoanthraquinones in electrolytes for organic redox flow batteries through molecular modification.

1,4-Diaminoanthraquinones (DAAQs) are a promising class of redox-active molecules for use in nonaqueous redox flow batteries (RFBs) because they can have up to five electrochemically accessible and reversible oxidation states. However, most of the commercially available DAAQs have a low solubility in the polar organic solvents that are typically used in RFBs, in particular when supporting electrolyte salts are present. This significantly limits the energy densities that can be achieved. We have functionalized the amino groups in the DAAQ structure with three types of chains, namely alkyl chains, cationic alkyl chains and oligoethylene glycol ether chains, and measured the solubility of these derivatives in various organic solvents by quantitative UV-Vis absorption spectroscopy. The DAAQ derivatives with higher polarity exhibit a significantly higher solubility in commonly used organic electrolytes in comparison to apolar derivatives. Cyclic voltammetry was used to assess the viability of the DAAQs as redox-active species for RFBs. Although the cationic DAAQ derivatives have an enhanced solubility in the electrolytes, the cathodic redox reactions have a poor reversibility, most likely due to an internal decomposition reaction of their reduced forms. The oligoethylene-glycol-ether-functionalized DAAQs are the most promising compounds for use in organic RFB electrolytes because they have the optimal combination of high solubility and a high reversibility of the redox couples.