Aqueous Solutions Of Metal Salts Research Articles

Synthesis and characterization of novel quinaldic acid based Ni, Fe, and Cr Complexes: A computational and experimental study

Complexes ([Ni(quin-2-c)2(H2O)2]•2H2O, [Fe(quin-2-c)2(H2O)2], [Cr(quin-2-c)2(H2O)2] were synthesized from aqueous solutions of metal salts, quinaldic acid, and semicarbazide. In the crystal structure of the first complex, the nickel atom is chelated by the deprotonated quinaldic acid molecule through the oxygen atom of the carboxyl group, and the heterocyclic nitrogen atom, as well as two water molecules, are coordinated. The other two water molecules are located in the outer sphere. In the structure of the iron and chromium complexes, the metal atoms have a similar complex formation but do not have water molecules in the outer sphere. In all compounds, quinaldic acid acts as a bidentate ligand to form five-membered metallocycles. The electronic structure properties were investigated through theoretical modeling using the B3LYP method at the 6–31 + G(d,p) computational level. Density functional theory (DFT) was employed in quantum chemistry simulations to refine proposed structures and explore the characteristics of frontier orbitals via analysis of frontier molecular orbitals (FMOs). These computations facilitated the identification of specific sites on the surface of molecules by generating molecular electrostatic potential maps and provided insights into the structural and reactive properties. Hirshfeld surface analysis was conducted to examine intermolecular interactions, revealing a prevalence of H⋅⋅⋅H interactions.

Synthesis and Antibacterial Studies of a New Au(III) Complex with 6-Methyl-2-Thioxo-2,3-Dihydropyrimidin-4(1H)-One

This article describes the synthesis of a new metal complex using 6-methyl-2-thioxo-2,3-dihydropyrimidin-4(1H)-one. The compound was analyzed using several methods, including determining its melting point and employing UV-Vis, IR, ATR, 1H NMR, HSQC, and Raman spectroscopy for the free ligand. The metal complex was formed by combining aqueous solutions of metal salts with the ligand dissolved in DMSO and water, along with NaOH in a metal-to-ligand-to-base ratio of 1:4:2. The NMR signals of the ligand were assigned using 1H-1H COSY, DEPT-135, HMBC, and HMQC spectra. Furthermore, the compound’s antimicrobial activity against Gram-positive and Gram-negative bacteria, as well as yeasts, was assessed.

Less efficient skin penetration of the metal allergen Pd2+ compared to Ni2+ and Co2+ from patch test preparations.

Contrary to Ni2+- and Co2+-induced allergic contact dermatitis (ACD), reactions against Pd2+ are rare. However, Pd2+ activates a larger T cell fraction in vitro, suggesting an inefficient skin penetration. This study compares Ni2+, Co2+ and Pd2+ skin penetration from commonly used diagnostic patch test preparations (PTPs) and aqueous metal salt solutions. Using Franz diffusion cell assays, we applied the metals in PTPs (5% NiSO4, 1% CoCl2, 2% PdCl2 and 3% Na2PdCl4) and in solution to pigskin for 48 h, thereby mirroring the time frame of a patch test. The different compartments were analysed individually by inductively coupled plasma mass spectrometry. Metal ions were mainly retained in the upper stratum corneum layers. After application of PTPs, concentrations in the viable skin were lower for Pd2+ (1 and 7 μM) compared to Ni2+ and Co2+ (54 and 17 μM). Ni2+ and Co2+ penetrated the skin more efficiently than Pd2+ and thus may sensitize and elicit ACD more easily. This was observed for ions applied in petrolatum and aqueous solutions. We hypothesize that the differently charged metal complexes are responsible for the varying skin penetration behaviours.

Electrochemical Additive Manufacturing of Binary and Ternary Alloys at the Mircon Scale by Electrohydrodynamic Redox 3D Printing

The need for miniaturisation throughout many different industries brings classical subtractive manufacturing techniques to their limits. Additive manufacturing is able to overcome these limits which has made it a topic of interest in many scientific fields. This additional geometric freedom becomes increasingly important if feature sizes on the micron- or even nano-scale are desired. Multiple different techniques to fabricate device-grade metals at such length-scales have been reported [1]. As one of these techniques, electrohydrodynamic redox printing (EHD-RP) has shown promise to be a versatile fabrication tool [2, 3, 4] depositing dense, pure metallic structures at high deposition rates.In this contribution, we present our work on additively manufactured alloys. First, we introduce a novel EHD-RP approach using aqueous metal salt electrolytes instead of sacrificial anodes as ion sources. The use of metal salts not only expands the range of manufacturable metals, but also enables the fabrication of metal alloys with precise compositional control without the need for additives or a surplus of the less noble metal. We demonstrate this control by fabricating binary and ternary Cu-Ag, Cu-Zn and Cu-Ag-Zn alloys. The composition of the fabricated alloy exactly mirrors the composition of the aqueous metal salt solutions. These systems were chosen as a representative immiscible and miscible system, in order to study different growth mechanisms. Microstructural analysis of Cu-Ag alloys reveals the formation of a metastable mixed phase. Cu-Ag alloys were successively dealloyed to produce nano-porous Ag structures. The compositional control over the Cu-Ag alloy enables precise control of porosity in the dealloyed structures. These nano-porous Ag structures have also been tested as substrates for surface enhanced Raman spectroscopy.(1) L. Hirt, A. Reiser, R. Spolenak & T. Zambelli, Adv. Mater 2017, 29, 1604211(2) A. Reiser, M. Lindén, P. Rohner, A. Marchand, H. Galinski, A. S. Sologubenko, J. M. Wheeler, R. Zenobi, D. Poulikakos & R. Spolenak, Nat. Comm. 2019, 10, 1853(3) M. Nydegger, A. Pruška, H. Galinski, R. Zenobi, A. Reiser & R. Spolenak, Nanoscale 2022, 14, 17418(4) M. Menétrey, L. Koch, A. Sologubenko, S. Gerstl, R. Spolenak & A. Reiser, Small 2022, 18, 2205302

Electrohydrodynamic Redox Printing: A Swiss Army Knife of Metals Microfabrication?

The dissolution and deposition of metals in solvents is widely known and used in a large range of applications, from electroplating to electro-machining. More recently, it has also been used for additive manufacturing (AM) at the sub-micron scale, since electroplated metals offer as-deposited high-quality metals (in terms of porosity and contamination) compared to other small scale AM techniques [1,2]. These intricate, high-quality metal structures have a range of applications in microelectromechanical systems, photonics or micro-robotics. However, the nature of the deposition process requires a conductive substrate to provide the electrons necessary for the localized reduction of metal ions. This requirement renders the direct fabrication of microelectronic devices using electrochemical small scale AM a challenge, as often deposition on electrically insulating substrates is required.Here, we present our work on electrohydrodynamic redox printing (EHD-RP), an electrochemical small scale AM technique, and our efforts towards deposition on various substrates. We’ll first introduce EHD-RP with a focus on our recent work on the deposition from aqueous metal salt solutions onto conductive substrates. We’ll then discuss strategies to expand the concept of EHD-RP towards deposition on non-conductive substrates and how electrically floating structures can be fabricated. These strategies render EHD-RP a versatile technique for metals microfabrication.[1] M. Nydegger, A. Pruška, H. Galinski, R. Zenobi, A. Reiser and R. Spolenak. Additive Manufacturing of Zn with Submicron Resolution and its Conversion into Zn/ZnO core-shell structures. Nanoscale, 2022[2] L. Hirt, A. Reiser, R. Spolenak and T. Zambelli. Additive Manufacturing of Metal Structures at the Micrometer Scale. Adv. Mater., 29(17), 2017

Unraveling ultrasonic assisted aqueous-phase one-step synthesis of porous PtPdCu nanodendrites for methanol oxidation with a CO-poisoning tolerance

The tailored design of tri-metallic Pt-based porous nanodendrites (PNDs) is crucial for green energy production technologies, ascribed to their fancy features, great surface areas, accessible active sites, and stability against aggregation. However, their aqueous-phase one-step synthesis at room temperature remains a daunting challenge. Herein, we present a facile, green, and template-free approach for the one-step synthesis of PtPdCu PNDs by ultrasonication of an aqueous solution of metal salts and Pluronic F127 at 25 ℃, based on natural isolation among nucleation and growth step driven by the disparate reduction kinetics of the metals and acoustic cavitation mechanism of ultrasonic waves. The resultant PtPdCu PNDs formed in a spatial nanodendritic shape with a dense array of branches, open corners, interconnected pores, high surface area (46.9 m2/g), and high Cu content (21 %). The methanol oxidation reaction (MOR) mass activity of PtPdCu PNDs (3.66 mA/µgPt) is 1.45, 2.73, and 2.83 times higher than those of PtPd PNDs, PtCu PNDs, and commercial Pt/C, respectively based on equivalent Pt mass, which is superior to previous PtPdCu catalysts reported elsewhere, besides a superior durability and CO-poisoning tolerance. This study may pave the way for the controlled fabrication of ternary Pt-based PNDs for various electrocatalytic applications.

30 Reference Materials for the Measurement of Metals in Workplace Air

Abstract For the production of filters coated with metal oxides an aqueous metal salt solution is injected into a hydrogen/oxygen flame of a particle generator leading to the pyrolysis of the metal salts into nano-scaled metal oxide dust. The particles are introduced into a large sampling chamber (20 m³) via a dust tunnel (20 m). So far, the system was tested for Zn, Cu, Pb, Co, Ni, Mn and In but it should be suitable with all metals obtainable as soluble metal salts. For sample generation an eight-fold sampling system was developed for the GSP sampler. The constancy of the flow rate is assured by critical orifices. Up to fourteen of these systems can be operated to produce 112 samples in parallel. Nevertheless, for the production of a reference material a significantly higher number of samples will be needed. To achieve this aim the environmental conditions of the dust generation have to be stabilized for consecutive runs. The major problem was the temperature rise of the dust channel during the particle generation due to the heat of the flame. An additional heater was installed to work at a constant temperature of 30 °C. Three consecutive filter series were manufactured. The achieved temperature constancy of 30± 0.5 °C makes it possible to combine the successive filter series. The loadings of the combined series were Cobalt: 3.25±0.058 µg/filter, Nickel: 13.78±0.23 µg/filter, Lead: 109.5±3.0, Copper: 9.65 ±0.18 µg/filter and Zinc: 32.66±0.72 µg/filter.

ДИЗАЙН НАНОЧАСТИЦ ОКСИДОВ ПЕРЕХОДНЫХ МЕТАЛЛОВ С КОНТРОЛИРУЕМОЙ РАЗМЕРНОСТЬЮ

The paper presents generalized experimental data on the influence of synthesis conditions on the structural features of MeO transition metal oxide nanoparticles in a polymer matrix synthesized by chemical condensation. The synthesis process includes the interaction of aqueous solutions of metal salts of varying concentrations with alkalis in the presence of an aqueous solution of the natural polysaccharide arabinogalactan. Controlled growth of oxide nanoparticles was achieved by encapsulation of emerging NPs in a polysaccharide matrix. The structural properties of the obtained samples were analyzed using X-ray diffraction, IR and UV spectroscopy, and TEM and SEM electron microscopy.

Oxygenated Triazine-Heptazine Heterostructure Creates an Enormous Ascension to the Visible Light Photocatalytic Hydrogen Evolution Performance of Porous C3 N4 Nanosheets.

A highly efficient g-C3 N4 photocatalyst is developed by a novel one-pot thermal polymerization method under a salt fog environment generated by heating the aqueous solution of urea and mixed metal salts of NaCl/KCl, namely SF-CN. Thanks to the synergistic effect of the oxygenation and chemical etching of the salt fog, the obtained SF-CN is an oxygenated ultrathin porous carbon nitride with an intermolecular triazine-heptazine heterostructure, meanwhile, shows enlarged specific surface area, greatly enhanced absorption of visible light, narrowed band gap with a lower conduction band, and an increased photocurrent response due to the effective separation of photogenerated holes and electrons, comparing to those of pristine g-C3 N4 . The theoretical simulations further reveal that the triazine-heptazine heterostructure possesses better photocatalytic hydrogen evolution (PHE) capability than pure triazine and heptazine carbon nitrides. In turn, SF-CN demonstrates an excellent visible light PHE rate of 18.13mmolh-1 g-1 , up to 259.00 times of that of pristine g-C3 N4 .

Supercritical Hydrothermal Reactions for Material Synthesis

Abstract Since the early 1990s, Adschiri and his colleagues have performed research on the use of supercritical water in diverse applications, including heavy oil reforming, waste polymer decomposition and chemical raw materials recovery, cellulose hydrolysis and sugar recovery, lignin decomposition and chemical raw materials recovery, and nanoparticle synthesis. Regarding inorganic materials synthesis, they invented supercritical hydrothermal synthesis for the continuous flow synthesis of metal oxide nanoparticles, which has already found worldwide industrial applications. They proposed a two-fluid mixing flow system where an aqueous metal salt solution is mixed with supercritical water to heat the solution to the supercritical state within a very short time, that is not attainable by conventional reactor systems. Organic-inorganic hybrid nanoparticles synthesis was demonstrated in the supercritical state, realizing homogeneous phase formation of organic molecules at high loadings. By optimizing the reaction conditions, small facet-controlled nanoparticles with narrow particle size distribution can be obtained. Organic modification of nanoparticles is shown to be effective for fabricating highly concentrated nanohybrid polymers or nano inks. Furthermore, these synthesized facet-controlled nanoparticles show high catalytic activities. Indeed, it is demonstrated that steam reforming of heavy oils or biomass wastes (black liquor) can occur in water even at low temperatures.

One-Step Synthesis of Functional Sulfonated Polynaphthoylenebenzimidazoles for Biosensing Applications

Polynaphthoylenebenzimidazoles containing functional sulfo groups were synthesized by a one-step method in a sulfuric acid medium with oleum. A polymer-analogous transformation of these polymers with aqueous solutions of metal salts (K, Ca, and Cr) was carried out. Their chemical structure was characterized by FTIR, NMR, and elemental analysis. Polymer salt coatings were deposited on QCM sensor surfaces by electron beam-induced vacuum deposition. The morphology of the coatings was characterized by AFM. It was shown that the coatings formed from a series of polymer salts have different adsorption activity in acetaminophen–water solution compared to distilled water. The QCM results indicate that sensor signal correlates with polymer coating thickness, morphology, and its chemical composition.

Separation of chitin from shrimp shells enabled by transition metal salt aqueous solution and ionic liquid

Chitin is a widely used important industrial polymer mainly from shrimp shells, but its commercial preparation is under the great challenge of serious pollution due to the requirement of HCl and NaOH. Herein, we demonstrated that high purity chitin can be obtained from waste shrimp shells (WSSs) by cascade separation with transition metal salt aqueous solution and ionic liquid (IL). Firstly, calcium carbonate of WSSs was effectively removed in the metal salt aqueous solution driven by the ion exchange interaction. Subsequently, 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) had bifunctional abilities to remove residual protein and introduced metal salts simultaneously by hydrogen bonding and coordination interactions. The key experimental factors affecting the separation process were systematically studied, including the type of metal salts, temperature, and [Bmim]Cl loading. After sequential treatment with a 20 %(mass) NiSO 4 aqueous solution at 130 °C and [Bmim]Cl at 150 °C, the purity of α-chitin can be up to 96.5 %(mass) that meets commercial requirements. The use of metal salts with higher coordination ability makes the preparation of chitin no longer depend on the commonly acid-base reaction, which is conducive to the preservation of chitin structure.

Continuous Flow Synthesis of Cd1-x Znx S and CdS/ZnS Core/Shell Semiconductor Nanoparticles by MicroJet Reactor Technology.

From aqueous precursor solutions of metal salts and sodium sulfide using MicroJet Reactor (MJR) technology Cd1-x Znx S and CdS/ZnS core/shell semiconductor nanoparticles were synthesized. The MJR approach represents an automated, continuous, flexible and scalable route for nanoparticle synthesis, providing a tight control over process parameters and thus simple size, shape and composition control. Since particle sizes below the excitonic Bohr radius were obtained by MJR, the nanoparticulate materials exhibit quantum confinement effects. By varying the precursor ratio the band gap of Cd1-x Znx S Quantum Dots (QDs) could be targeted from 3.1 to 3.6 eV. CdS/ZnS core/shell QDs were prepared by enclosing CdS particles from MJR with ZnS produced by thermal decomposition of a Zn-MPA complex. Adjustment of the shell thickness increased the photoluminescence intensity by 43 %. Synthesis of ternary sulfides in the form of core/shell particles broadens the spectrum of materials accessible by MJR and demonstrates the extraordinary flexibility of the technology.

In-situ enhanced laser absorption in aqueous transition metal salt solution enables high-quality backside wet etching of optical glass by near-infrared lasers

A laser-induced backside wet etching technique using near-infrared laser sources (N-LIBWE) has been proposed for high-quality micromachining of optical glass. Compared with conventional LIBWE using organic dye solutions with high absorption coefficients (∼104–105 cm−1) as the liquid absorbent, the transition metal salt solution used in N-LIBWE shows the absorption coefficient of only 10-1-101 cm−1. Moreover, as we proved in this study, the etching rate of N-LIBWE is independent of the absorptivity of the liquid absorbent. How the etching occurs during N-LIBWE is still controversial. Herein, interface images with a temporal resolution of 4 ns after the start of laser irradiation are captured by a stroboscopic shadowgraphy system. Afterward, the density, pressure, and temperature distribution in the solution are calculated by a physics-based two-dimensional hydrodynamic model to explain the observed interface images. We prove that the localized laser absorption is enhanced with laser irradiation because of the in-situ formation of solid substances. It is the properties of the formed solid products instead of the normal absorption coefficient of the solution that determines the final interface status. We further prove that the formed solid substances in aqueous CuSO4 solutions are primarily amorphous nanoclusters, which benefit the enhancement of laser absorption and tend to attach to the transparent substrates, resulting in the incubation effect in N-LIBWE. Our results provide systematic mechanisms explaining the N-LIBWE process, which also benefit the deep understanding of other liquid-assisted laser materials processing technologies.

In Situ Diagnostics and Role of Light‐Induced Forces in Metal Laser Nanoprinting

AbstractCompared to 3D laser nanoprinting of polymers, the mechanisms in laser nanoprinting of metals are rather poorly understood. For the example of platinum investigated here, the printing process starts with the formation of metal nanoparticles by photo‐reduction of metal salts in aqueous solution in a diffraction‐limited laser focus. To investigate the printing process in situ, a weak continuous‐wave probe laser is co‐focused in addition to the focused femtosecond printing laser. The light of the probe laser is backscattered off the emerging metal structures, and recorded with a temporal resolution of 1 µs. It is found that the formed metal nanoparticles are quickly ejected from the focus on a timescale of some 10 µs. Once a nanoparticle randomly adheres to the substrate surface, it serves as a seed from which structures can be built‐up. The following nanoparticles are sintered onto that seed to form a metallic voxel on a timescale of some 10 ms. By polarization‐dependent experiments and full‐wave optical simulations, it is shown that light‐induced forces onto the nanoparticles play a significant role. The improved understanding of the microscopic processes in metal nanoprinting is a prerequisite for further process optimizations and applications, for example in terms of printed optoelectronics.

Antioxidant Capacity Assessment of Plant Extracts for Green Synthesis of Nanoparticles.

In this work, water extracts from different bio-based products of plant origin were studied to evaluate their antioxidant capacity and their potential to form metal nanoparticles from aqueous solutions. Two traditional tests, the Folin–Ciocalteu assay and the DPPH radical scavenging capacity method were compared with a more recent one, SNPAC, based on the formation of silver nanoparticles. The silver nanoparticle antioxidant capacity method (SNPAC) was optimized for its application in the characterization of the extracts selected in this work; kinetic studies and extract concentration were also evaluated. The extracts were obtained from leaves of oak, eucalyptus, green tea, white and common thyme, white cedar, mint, rosemary, bay, lemon, and the seaweed Sargassum muticum. The results demonstrate that any of these three methods can be used as a quick test to identify an extract to be employed for nanoparticle formation. Additionally, we studied the synthesis of Cu, Fe, Pb, Ni, and Ag nanoparticles using eucalyptus extracts demonstrating the efficiency of this plant extract to form metallic nanoparticles from aqueous metal salt solutions. Metal nanoparticles were characterized by transmission electron microscopy and dynamic light scattering techniques.

Boosting Electrochemical Performance of Hematite Nanorods via Quenching-Induced Alkaline Earth Metal Ion Doping

Ion doping in transition metal oxides is always considered to be one of the most effective methods to obtain high-performance electrochemical supercapacitors because of the introduction of defective surfaces as well as the enhancement of electrical conductivity. Inspired by the smelting process, an ancient method, quenching is introduced for doping metal ions into transition metal oxides with intriguing physicochemical properties. Herein, as a proof of concept, α-Fe2O3 nanorods grown on carbon cloths (α-Fe2O3@CC) heated at 400 °C are rapidly put into different aqueous solutions of alkaline earth metal salts at 4 °C to obtain electrodes doped with different alkaline earth metal ions (M-Fe2O3@CC). Among them, Sr-Fe2O3@CC shows the best electrochemical capacitance, reaching 77.81 mF cm−2 at the current of 0.5 mA cm−2, which is 2.5 times that of α-Fe2O3@CC. The results demonstrate that quenching is a feasible new idea for improving the electrochemical performances of nanostructured materials.

Bioremoval of hazardous cobalt, nickel, chromium, copper and cadmium compounds from contaminated soil by Nicotiana tabacum plants and associated microbiome

Contamination of soils with heavy metals leads to reduction of soil fertility, destruction of natural ecosystems and detrimental effects on the health of society by increasing content of metals in the food chains from microorganisms to plants, animals and humans. Bioremediation is one of the most promising and cost-effective methods of cleaning soils polluted with toxic metals. According to current researchers, microorganisms and plants have the genetic potential to remove toxic metals from contaminated sites. The method of thermodynamic prediction was used to theoretically substantiate the mechanisms of interaction of soil microorganisms and plants with heavy metals. According to the our prediction, exometabolite chelators of anaerobic microorganisms may increase the mobility of metals and thereby contribute to the active transport of metals and their accumulation in plants. Plants of Nicotiana tabacum L. of Djubek cultivar were used as plant material for the current investigation. The examined toxicants were heavy metals, namely cobalt (II), nickel (II), chromium (VI), copper (II) and cadmium (II). The aqueous solutions of metal salts were added to the boxes after two months of plants growing to the final super-high concentration – 500 mg/kg of absolutely dry weight of soil. Quantitative assessments of copper and chromium-resistant microorganisms were made by cultivation on agar nutrient medium NA with a gradient of Cu(II) and Cr(VI). The concentration of metals in soil and plant material (leaves, stems and roots) was determined by atomic absorption method. The study revealed that heavy metals inhibited the growth of the examined tobacco plants. This was expressed by the necrosis of plant tissues and, ultimately, their complete death. Despite this, all investigated heavy metals were accumulated in plant tissues during 3–7 days before death of plants. The uptake of metals was observed in all parts of plants – leaves, stems and roots. The highest concentrations of Co(II), Ni(II), Cd(II), Cr(VI) were found in the leaves, Cu(II) – in the roots. The results show that the bioremoval efficiency of the investigated metals ranged 0.60–3.65%. Given the super-high initial concentration of each of the metals (500 mg/kg), the determined removal efficiency was also high. Cadmium was the most toxic to plants. Thus, the basic points of the thermodynamic prognosis of the possibility of accumulation of heavy metals by phytomicrobial consortium were experimentally confirmed on the example of N. tabacum plants and metal-resistant microorganisms. The study demonstrated that despite the high initial metals concentration, rate of damage and death of plants, metals are accumulated inplant tissues in extremely hight concentrations. Soil microorganisms were observed to have high adaptation potencial to Cu(II) and Cr(VI). In anaerobic conditions, microorganisms presumably mobilize heavy metals, which later are absorbed by plants. The obtained results are the basis for the development of environmental biotechnologies for cleaning contaminated soils from heavy metal compounds.

Single-Step Flame Aerosol Synthesis of Active and Stable Nanocatalysts for the Dry Reforming of Methane.

We introduce a flame-based aerosol process for producing supported non-noble metal nanocatalysts from inexpensive aqueous metal salt solutions, using catalysts for the dry reforming of methane (DRM) as a prototype. A flame-synthesized nickel-doped magnesia (MgO) nanocatalyst (NiMgO-F) was fully physicochemically characterized and tested in a flow reactor system, where it showed stable DRM activity from 500 to 800 °C. A kinetic study was conducted, and apparent activation energies were extracted for the temperature range of 500-650 °C. It was then compared with a Ni-decorated MgO nanopowder prepared by wet impregnation of (1) flame-synthesized MgO (NiMgO-FI) and (2) a commercial MgO nanopowder (NiMgO-CI) and with (3) a NiMgO catalyst prepared by co-precipitation (NiMgO-CP). NiMgO-F showed the highest catalytic activity per mass and per metallic surface area and was stable for continuous H2 production at 700 °C for 50 h. Incorporation of potential promoters and co-catalysts was also demonstrated, but none showed significant performance improvement. More broadly, nanomaterials produced by this approach could be used as binary or multicomponent catalysts for numerous catalytic processes.

Robust Conversion-Type Li/Garnet interphases from metal salt solutions

Garnet-type Li7La3Zr2O12 (LLZO) electrolytes show considerable potentials in solid-state Li metal batteries, yet the serious interfacial problem has hindered its practical application. Herein, we propose a facile strategy to construct conversion-type metal oxides (eg. PbO, ZnO or Co3O4) as lithiophilic layers on garnet surface from metal salt aqueous solutions. Robust garnet/Li interface and greatly reduced interfacial resistance to as small as ~ 10 Ω cm2 can be obtained. Combined with experimental analysis and theoretical calculation (ΔG), the mechanism of lithiophilicity of different metal oxides was explained. The mixed ionic and electronic conductive interlayer which can lead to uniform Li-ion flow is superior to the electronic conductive metal interlayer with poor ionic conductivity causing gradual failure of the interface. As expected, the Li|PbO/LLZTO/PbO|Li cells show the improved critical current density of 1.1 mA cm−2 and excellent cycling stability for 1000 h at 0.3 mA cm−2. With PbO modified garnet, LiNi0.5Co0.2Mn0.3O2|garnet|Li cells operate well at room temperature and all-solid-state LiFePO4/PEO|garnet|Li cells run stably at 0.3 mA cm−2 for at least 100 cycles at 60 ℃.