Transmission Electron Microscopy Measurements Research Articles

Synthesis and characterization of titanium oxynitride catalyst via direct ammonia nitridation of titanium polyacrylate for oxygen reduction reaction

A titanium oxynitride catalyst for the oxygen reduction reaction (ORR) in polymer electrolyte fuel cells was synthesized through the direct ammonia nitridation of titanium complexes. Titanium polyacrylate was employed as the catalyst precursor, and the effect of the calcination temperature between 600 and 1000 °C on the catalyst structure was studied. The catalysts were characterized via X-ray diffraction, X-ray absorption spectroscopy, transmission electron microscopy, cyclic voltammetry, and powder electrical resistivity measurements. The formation of titanium oxynitride particles and deposited carbon was observed for all the samples; however, significant variations in the catalyst structure and catalytic activity were also observed. With an increase in the calcination temperature, nitridation of titanium oxynitride progressed, and the conductivity of the catalyst powder increased. The highest rest potential and ORR current density were achieved with calcination at 800 °C. Importantly, the results suggest that maintaining an optimal nitrogen doping level within the catalyst particles, along with ensuring the formation of electroconductive deposited carbon, is essential for achieving a high ORR current. This work introduces the direct ammonia nitridation of metal complexes as a promising process for designing metal oxynitride catalysts.

Adding More Shape to Nanoscale Reference Materials─LiYF4:Yb,Tm Bipyramids as Standards for Sizing Methods and Particle Number Concentration.

The increasing industrial use of nanomaterials calls for the reliable characterization of their physicochemical key properties like size, size distribution, shape, and surface chemistry, and test and reference materials (RMs) with sizes and shapes, closely matching real-world nonspheric nano-objects. An efficient strategy to minimize efforts in producing nanoscale RMs (nanoRMs) for establishing, validating, and standardizing methods for characterizing nanomaterials are multimethod nanoRMs. Ideal candidates are lanthanide-based, multicolor luminescent, and chemically inert nanoparticles (NPs) like upconversion nanoparticles (UCNPs), which can be prepared in different sizes, shapes, and chemical composition with various surface coatings. This makes UCNPs interesting candidates as standards not only for sizing methods, but also for element-analytical methods like laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS), quantitative bioimaging methods like X-ray fluorescence computed tomography (XFCT), and luminescence methods and correlative measurements. Here, we explore the potential of two monodisperse LiYF4:Yb,Tm bipyramids with peak-to-peak distances of (43 ± 2) nm and (29 ± 2) nm as size standards for small-angle X-ray scattering (SAXS) and tools for establishing and validating the sophisticated simulations required for the analysis of SAXS data derived from dispersions of nonspheric nano-objects. These SAXS studies are supplemented by two-dimensional (2D)-transmission electron microscopy measurements of the UCNP bipyramids. Additionally, the particle number concentration of cyclohexane dispersions of these UCNP bipyramids is determined by absolute SAXS measurements, complemented by gravimetry, thermogravimetric analysis (TGA), and inductively coupled plasma optical emission spectrometry (ICP-OES). This approach enables traceable particle number concentration measurements of ligand-capped nonspheric particles with unknown chemical composition.

Influence of an ultrathin Mn ‘spy layer’ on the static and dynamic magnetic coupling within FePt/NiFe bilayers

Abstract We explore whether insertion of an ultrathin Mn ‘spy layer’ within a magnetic hard/soft bilayer can enable depth-sensitive element-specific measurements of the static and dynamic magnetization, while avoiding significant disruption of the original magnetic state. MgO(110)/FePt(100 Å)/NiFe(200 Å)/Mn(t Mn Å)/NiFe(200 Å) samples with Mn thicknesses of t Mn = 0, 5, and 10 Å were fabricated by magnetron sputtering and studied by element-selective x-ray magnetic circular dichroism (XMCD), vector network analyzer ferromagnetic resonance (VNA-FMR), and x-ray detected ferromagnetic resonance (XFMR). For t Mn = 5 Å, the magnetic reversal properties remain broadly similar to t Mn = 0 Å. For t Mn = 10 Å, the two NiFe layers decouple with XMCD hysteresis loops at the Mn edge showing two switching events that suggest the presence of two distinct Mn-containing regions. While the Mn moments within each region have ferromagnetic order, their relative alignment is antiparallel at high field. Analysis of the magnetic data and additional scanning transmission electron microscopy measurements point to the presence of a Mn layer at the lower NiFe/Mn interface, and the formation of a NiFeMn alloy at the upper Mn/NiFe interface. The Mn moments of the former region lie antiparallel to those of the underlying NiFe layer. The VNA-FMR data suggests that for t Mn = 5 and 10 Å, the interfacial exchange coupling at the FePt/NiFe is suppressed and the in-plane uniaxial magnetic anisotropy of the NiFe is increased, perhaps due to migration of Mn towards the buried interface. The above findings show that Mn is a problematic magnetic spy, and that a Mn thickness of less than 5 Å would be required.

Evaluation of Different Blending Methods to Obtain Copper Composites with Graphene Oxide

This study evaluated mixing methods for producing graphene oxide-reinforced copper matrix composites aiming for a better dispersion of graphene oxide in the composite, using powder metallurgy techniques. The compacted specimens were prepared by four different mixing processes that employed either a mechanical stirrer, rotary evaporator, tip ultrasound, or ultrasound process followed by mechanical stirring. Characterizations were performed using optical microscopy, scanning electron microscopy, X-ray diffraction, Raman spectroscopy, transmission electron microscopy, compression tests, Vickers microhardness, and electrical conductivity measurements. The results indicate that the combined method yields a more homogeneous microstructure and superior mechanical properties, while electrical conductivity was maintained at a level higher than that achieved by the other methods.

Superconductivity at Pd/Bi2Se3 Interfaces Due to Self-Formed PdBiSe Interlayers.

Understanding the physical and chemical processes at the interfaces of metals and topological insulators is crucial for the development of the next generation of topological quantum devices. Here, we report the discovery of robust superconductivity in Pd/Bi2Se3 bilayers fabricated by sputtering Pd on the surface of Bi2Se3. Through transmission electron microscopy measurements, we identify that the observed interfacial superconductivity originates from the diffusion of Pd into Bi2Se3. In the diffusion region, Pd chemically reacts with Bi2Se3 and forms a layer of PdBiSe, a known superconductor with a bulk transition temperature of 1.5 K. Our work provides a method for the introduction of superconductivity into Bi2Se3, laying the foundation for the development of sophisticated Bi2Se3-based topological devices.

Solubility and magnetic properties of Ag−Co−Si alloy synthesized by mechanical alloying and annealing

AbstractThis present work concerns the effect of ternary addition of non‐metallic and diamagnetic silicon on the metastable solubility of the immiscible silver‐cobalt system during the course of ball milling, annealing of the ball milled samples and the corresponding magnetic properties. It should be noted that silicon has a smaller goldsmidt radius (111 pm) than silver (144 pm) and silicon+4 has more valence electrons than silver+1. Keeping the objectives of the current study in mind, silicon may thus be considered as an option for ternary addition, in contrast to metallic components. An attempt has been made to examine the phase changes that occurred in the 50 silver‐40 cobalt‐10 silicon (atom percent) system during ball milling and the subsequent isothermal annealing of the ball milled product. Phase evolution during mechanical alloying and isothermal annealing is identified by means of x‐ray diffraction, differential thermal analysis, high resolution transmission electron microscopy and magnetic measurements. The addition of silicon facilitates cobalt‘s formation of a metastable alloy with copper after 50 hours of ball milling. Annealing significantly improves the magnetic characteristics of materials that have been ball milled; the optimal combination of magnetic properties was obtained after an hour of annealing at 550 °C.

Engineering of Impact Ionization Characteristics in GaAs/GaAsBi Multiple Quantum Well Avalanche Photodiodes.

The presence of large bismuth (Bi) atoms has been shown to increase the spin-orbit splitting energy in bulk GaAsBi, reducing the hole ionization coefficient (β) and thereby reducing the excess noise seen in avalanche photodiodes. In this study, we show that even very thin layers of GaAsBi introduced as quantum wells (QWs) in a GaAs matrix exhibit a significant reduction of β while leaving the electron ionization coefficient, α, largely unchanged. The optical and avalanche multiplication properties of a series of GaAsBi/GaAs multiple quantum well (MQW) p-i-n structures with nominally 5 nm thick, 4.4% Bi GaAsBi QWs, varying from 5 to 63 periods and corresponding barrier widths of 101 to 4 nm were investigated. From photoluminescence, ω-2θ X-ray diffraction, and cross section transmission electron microscopy measurements, the material was found to be of high quality despite the strain introduced by the Bi in all except the samples with 54 and 63 QW periods. Photomultiplication measurements undertaken with different wavelengths showed that α in these MQW structures did not change appreciably with the number of QWs; however, β decreased significantly, especially at lower values, the noise factor, F, is reduced by 58% to 3.5 at a multiplication of 10, compared to a similar thickness bulk GaAs structure without any Bi. This result suggests that Bi-containing QWs could be introduced into the avalanching regions of APDs as a way of reducing their excess noise.

Layer-by-Layer Deposition of Hollow TiO2 Spheres with Enhanced Photoelectric Conversion Efficiency for Dye-Sensitized Solar Cell Applications.

Fabricating photoanodes with a strong light-scattering effect can improve the photoconversion efficiency of dye-sensitized solar cells (DSSCs). In this work, a facile microwave hydrothermal process was developed to prepare Au@TiO2 core-shell nanostructures, and then the Au core was removed by etching, resulting in hollow TiO2. Morphological characterizations such as field emission scanning and transmission electron microscopy measurements have been used for the successful formation of core-shell and hollow TiO2 nanostructures. Next, we attempted to deposit the different-sized hollow TiO2-based microspheres simultaneously on the surface of small-sized TiO2 nanoparticles-based compact film as light-scattering layers via electrophoretic deposition. The deposited hollow TiO2 microspheres constitute bi- and tri-layers that not only improve the light-harvesting properties but also speed up the photogenerated charge transfer. Compared to commercial TiO2 compact film (4.75%), the resulting bi-layer and tri-layered films-based DSSCs displayed power conversion efficiencies of 6.33% and 8.08%, respectively. It is revealed that the deposited bi- and tri-layered films can enhance the light absorption ability via multiple photon reflection. This work validates a novel and controllable strategy to develop light-scattering layers with increased light-harvesting properties for highly efficient dye-sensitized solar cells.

Heterogeneous Integration of High Endurance Ferroelectric and Piezoelectric Epitaxial BaTiO3 Devices on Si

AbstractIntegrating epitaxial BaTiO3 (BTO) with Si is essential for leveraging its ferroelectric, piezoelectric, and nonlinear optical properties in microelectronics. Recently, heterogeneous integration approaches that involve growth of BTO on ideal substrates followed by transfer to a desired substrate show promise of achieving excellent device‐quality films. However, beyond simple demonstrations of the existence of ferroelectricity, robust devices with high endurance are not yet demonstrated on Si using the latter approach. Here, using a novel two‐step approach to synthesize epitaxial BTO using pulsed laser deposition on water‐soluble Sr3Al2O6 (on SrTiO3 substrates), successful integration of high‐quality BTO capacitors on Si is demonstrated, with remanent polarisation Pr = 7 µC cm−2, coercive field Ec = 150 kV cm−1, ferroelectric and electromechanical endurance of > 106 cycles. The study further addresses the challenge of cracking and disintegration of thicker films by first transferring a large area (5 mm x 5 mm) of the templated layer of BTO (≈30 nm thick) on the desired substrate, followed by the growth of high‐quality BTO on this substrate, as revealed by high‐resolution X‐ray diffraction (HRXRD) and high‐resolution scanning transmission electron microscopy (HRSTEM) measurements. These templated Si substrates offer a versatile platform for integrating any epitaxial complex oxides with diverse functionalities onto any inorganic substrate.

Rapid Size Determination of Quasispherical Gold Nanoparticles by Electrocatalysis Efficiency-Regulated Electrochemiluminescence.

The size of gold nanoparticles (AuNPs) largely decides their properties and applications, making the rapid screening of AuNP size important. Despite the fact that AuNP-amplified electrochemiluminescence (ECL) is widely used in various ECL sensing applications, the mechanism of ECL enhancement remains elusive, especially the quantitative relationship between the enhanced ECL intensity and the size of AuNPs. In this work, taking quasispherical and citrate-stabilized AuNPs as model nanoparticles, we have reported that the ECL intensity of the S2O82--O2 system enhanced significantly with the increasing AuNP size. AuNPs acted as bielectrocatalysts for reducing the S2O82- and O2. The further study of enhancement mechanism demonstrates that AuNPs with increasing size facilitate the electron transfer and promote the generation of radicals required for the ECL emission, which produces more emitters-singlet oxygen. Meanwhile, the high surface density of citrate on small AuNPs suppresses the ECL signal by forming an electrostatic barrier. On the basis of the above phenomena, an ECL-based rapid AuNP size screening approach has been established. The accuracy of this platform is verified by the consistent results in comparison to transmission electron microscopy (TEM) measurements. This work not only provides deep insight into the correlation between the AuNP size and the ECL enhancement but also contributes an alternative to the TEM technique for the rapid AuNP size screening. Additionally, this study also extends the exploration of ECL-based structure analysis techniques toward nanomaterials through clarifying the structure-electrocatalytic activity correlation.

Interface Dependent Coexistence of Two‐Dimensional Electron and Hole Gases in Mn‐doped InAs/GaSb

AbstractThe interface of common III‐V semiconductors InAs and GaSb can be utilized to realize a two‐dimensional (2D) topological insulator state. The 2D electronic gas at this interface can yield Hall quantization from coexisting electrons and holes. This anomaly is a determining factor in the fundamental origin of the topological state in InAs/GaSb. Here, the coexistence of electrons and holes in InAs/GaSb is tied to the chemical sharpness of the interface. Magnetotransport, in samples of Mn‐doped InAs/GaSb cleaved from wafers grown at a spatially inhomogeneous substrate temperature, is studied. It is reported that the observation of quantum oscillations and a quantized Hall effect whose behavior, exhibiting coexisting electrons and holes, is tuned by this spatial nonuniformity. Through transmission electron microscopy measurements, it is additionally found that samples that host this co‐existence exhibit a chemical intermixing between group III and group V atoms that extends over a larger thickness about the interface. The issue of intermixing at the interface is systematically overlooked in electronic transport studies of topological InAs/GaSb. These findings address this gap in knowledge and shed important light on the origin of the anomalous behavior of quantum oscillations seen in this 2D topological insulator.

Antimicrobial Activity of Amino-Modified Cellulose Nanofibrils Decorated with Silver Nanoparticles.

Silver nanoparticles (Ag NPs) conjugated with amino-functionalized cellulose nanofibrils (NH2-CNFs) were in situ-prepared by reducing silver ions with free amino groups from NH2-CNFs. The spectroscopy and transmission electron microscopy measurements confirmed the presence of non-agglomerated nanometer-in-size Ag NPs within micrometer-large NH2-CNFs of high (20 wt.-%) content. Although the consumption of amino groups during the formation of Ag NPs lowers the ζ-potential and surface charge of prepared inorganic-organic hybrids (from +31.3 to +19.9 mV and from 2.4 to 1.0 mmol/g at pH 7, respectively), their values are sufficiently positive to ensure electrostatic interaction with negatively charged cell walls of pathogens in acidic and slightly (up to pH ~8.5) alkaline solutions. The antimicrobial activity of hybrid microparticles against various pathogens (Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, and Candida albicans) is comparable with pristine NH2-CNFs. However, a long-timescale use of hybrids ensures the slow and controlled release of Ag+ ions to surrounding media (less than 1.0 wt.-% for one month).

The role of SiO2 buffer layer in the molecular beam epitaxy growth of CsPbBr3 perovskite on Si(111)

Here we present the growth of molecular beam epitaxy (MBE) CsPbBr3 perovskite films in the orthorhombic crystal structure, with unique structural and morphological properties. CsPbBr3 MBE perovskite films, with thickness ranging from a few nm to 300 nm, were grown in ultra-high vacuum on a Si(111)7 × 7 reconstructed surface, and after the formation of about 2 nm of SiO2, obtained exposing the clean reconstructed Si surface to molecular oxygen that serves to decouple the film from substrate. X-ray diffraction, and electron microscopies, such as scanning electron microscopy and high-angle annular dark-field scanning transmission electron microscopy measurements showed remarkable structural, as well as morphological features, indicating extremely high crystallinity over a large area and across the bulk of the perovskite film. Through the X-ray diffraction patterns we found very narrow (002) and (110) reflections of CsPbBr3 in pure orthorhombic phase, exhibiting a full width at half maximum of only 0.035°, value similar to a bulk Si single crystals, and a surface morphology composed of flat areas up to micrometres in lateral size. Our results shed new light both on preparation of high crystal quality perovskite films, and on the intrinsic properties of this striking fully-inorganic materials, which are exploitable for potential applications in electronic/optoelectronic devices and next generation photovoltaic solar cells.

Ultrahigh Energy Storage in (Ag,Sm)(Nb,Ta)O3 Ceramics with a Stable Antiferroelectric Phase, Low Domain-Switching Barriers, and a High Breakdown Strength.

AgNbO3 (AN) antiferroelectrics (AFEs) are regarded as a promising candidate for high-property dielectric capacitors on account of their high maximum polarization, double polarization-electric field (P-E) loop characteristics, and environmental friendliness. However, high remnant polarization (Pr) and large polarization hysteresis loss from room-temperature ferrielectric behavior of AN and low breakdown strength (Eb) cause small recoverable energy density (Wrec) and efficiency (η). To solve these issues, herein, we have designed Sm3+ and Ta5+ co-doped AgNbO3. The addition of Sm3+ and Ta5+ reduces the tolerance factor, polarizability of B-site cations, and domain-switching barriers, enhancing AFE phase stability and decreasing hysteresis loss. Meanwhile, adding Sm3+ and Ta5+ leads to decreased grain sizes, increased band gap, and reduced leakage current, all contributing to increased Eb. As a benefit from the above synergistic effects, a high Wrec of 7.24 J/cm3, η of 72.55%, power density of 173.73 MW/cm3, and quick discharge rate of 18.4 ns, surpassing those of many lead-free ceramics, are obtained in the (Ag0.91Sm0.03)(Nb0.85Ta0.15)O3 ceramic. Finite element simulations for the breakdown path and transmission electron microscopy measurements of domains verify the rationality of the design strategy.

Enhanced properties of hard metal WC-Ni processed from nanostructured powders

In this study, we investigated the effects of nanostructured composite powders (WC-Ni), nickel binder content, and sintering techniques on the morphology and mechanical properties of tungsten carbide. An alternative low-temperature gas-solid reaction route with a short reaction time was employed to produce nanostructured composite powders with 5 and 15 wt% Ni. The powders were consolidated using spark plasma sintering (SPS) and conventional vacuum furnace sintering at temperatures of 1350 °C and 1450 °C. The composite powders were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and particle size measurements. The expansion/contraction of the compacted nanocomposite powders was studied through dilatometric analysis. The composite powders exhibited a uniform distribution of Ni, in both compositions. For the WC-5 wt% Ni nanocomposite powders, the average crystallite sizes for WC and Ni were 41.6 nm and 46.2 nm, respectively. While, for the WC-15 wt% Ni nanocomposite, the crystallite sizes for WC and Ni were 45.6 and 38.4 nm. The sintered composites were evaluated through XRD, SEM, measurements of density and Vickers hardness. The enhanced sinterability of the nanostructured powders enabled their consolidation into (WC-Ni) hard metal with densities approaching the theoretical relative density of 96.07 %, even with low binder content (5 wt% Ni). This is attributed to the uniform distribution of Ni and an extensive Ni-WC interface present prior to sintering. The SPS process at 1350 °C produced sintered bodies (WC-5 wt% Ni and WC-15 wt% Ni) with higher Vickers hardness (2322 HV and 1512 HV, respectively) and superior microstructural quality compared to samples produced by conventional vacuum furnace techniques. These results demonstrated that the mechanical properties of the system WC-Ni processed by SPS are superior to those obtained by vacuum furnace. Therefore, WC-Ni hard metals processed by this approach is a promising alternative to conventional hard metals (WC-Co) for a wide range of applications.

NiCo2O4-Nanoparticle-Catalyzed Microwave-Assisted Dehydrogenative Direct Oxidation of Primary Alcohols to Carboxylic Acids under Oxidant-Free Conditions

AbstractHere, we report the NiCo2O4-nanoparticle-catalyzed dehydrogenative direct oxidation of primary alcohols to carboxylic acid in the presence of KOH under microwave irradiation in the absence of any oxidant in good to excellent yields (75–99%) within a short reaction time (5–10 min). The polycrystalline cubic spinel phase of NiCo2O4 nanoparticles (NPs) with an average size of 25 nm were synthesized by the co-precipitation method and analyzed properly by using powder X-ray diffraction, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, and transmission electron microscopy measurements. The NiCo2O4 NPs were stable under the reaction conditions and reused for up to eight cycles without appreciable loss in the yield of benzoic acid. According to mechanistic insight, the KOH acts as a second oxygen source and is essential for the synthesis of carboxylic acid from alcohols. The hydrogen gas was found to be the only byproduct of this method detected by chemical reactions.

Recycling of reduced graphene oxide from graphite rods in disposable zinc battery applicable to optical sensing

We report a low cost, simple method to fabricate reduced graphene oxide (rGO) optical sensors from recycled batteries. The rGO nanosheets were exfoliated by electrochemical method under the assistant of electric arc using 5 % KOH or NaOH electrolytes. The rGO nanosheets show interlayer distances ranging from 3.98 to 6.22 Å, and thicknesses from 0.62 to 6.00 nm, corresponding from 1 to 10 layers, respectively, determined from X-ray diffraction (XRD), atomic force microscopy (AFM), and transmission electron microscopy (TEM) measurements. Selected area electron diffraction (SAED) measurement indicates that rGO nanosheets content Miller-Bravais indices of (1–210) and (0–110) planes, and the hexagonal diffraction pattern of (0–110) plane of graphene sheets with d-spacing of 2.13 Å. Low defect densities in exfoliated rGO nanosheets were confirmed by ID/IG ratios ∼0.16 to 0.18 via Raman. The rGO nanosheets exfoliated in NaOH electrolyte have 19.35 % lower oxygen content compared to those exfoliated in KOH electrolyte inspected from XPS spectra. The performance of the rGO optical sensors is controlled by defects created from oxygen functional groups formed during exfoliation process. The responsivity and response (rise) time of NaOH-exfoliated rGO sensor are 0.46 A/W and 2.3 s, respectively. These values are 21 % (for responsivity) larger and 35 % (for rise time) smaller than those of KOH-exfoliated rGO sensor. The best-in-class of high gain were demonstrated in this study for the rGO optical sensors prepared from disposed graphite rods. The results demonstrate how disposed batteries can be recycled to produce photodetectors and other optoelectronic devices using cheap and relatively nontoxic methods.

Synthesis and color-tunable emission of ZnGaOx with different cation ratios by a polyacrylamide gel method

ZnGaOx nanoparticles with varied ratios of Zn2+ to Ga3+ were synthesized by a polyacrylamide gel route. The phase purity and structure are confirmed by X-ray diffraction (XRD), Fourier transform infrared spectrometer (FTIR) and X-ray photoelectron spectrometer (XPS). High crystal quality and elemental distribution are determined by transmission electron microscopy (TEM) measurements. The band gaps of the samples ranging from 3.22 to 4.47 eV are estimated by ultraviolet–visible (UV–Vis) diffuse refectance spectroscopy (DRS). Under the excitation of 325 nm laser light, ZnGaOx nanoparticles with the Zn2+/Ga3+ molar ratios of 0.8:2 and 0.7:2 show two emission peaks at 415 and 510 nm. A marked emission band at 695 nm is observed from the samples with Zn2+/Ga3+ molar ratios of 0.6:2, 0.5:2 and 0.4:2. The luminescence mechanism is discussed based on the experimental results. The luminescence color of as-synthesized samples gradually shifts from blue-green to green-yellow region with decreasing Zn2+/Ga3+ ratio. Interestingly, the sample with Zn2+/Ga3+ ratio of 0.7:2 has the CIE chromaticity coordinates of (x = 0.26, y = 0.33) close to the coordinates (x = 0.33, y = 0.33) of pure white light. Together, ZnGaOx phosphors with different emission colors without doping with rare earths have considerable potential applications in tunable light emitting diodes (LEDs) and color display.

Investigating Co and Fe Single-Atom (SA) Decorated NS-Doped Reduced Graphene Oxide (Co SA/NS-rGO, Fe SA/NS-rGO) Catalysts for NOx - to NH3 Pulsed Electroreduction

Electrochemical NH3 production has attracted much attention due to its potential to compensate for and supplement the Haber-Bosch process that produces hundreds of billions of kg of NH3 annually.1 One of the proposed electrochemical pathways to produce NH3 is the N2 reduction reaction. However, this reaction suffers from a high bond dissociation energy of 945 kJ mol−1, low NH3 Faradaic efficiency (F.E.) at high overpotentials, and NH3 quantification problems, limiting the extent of its applications.2,3 On the other hand, other N-containing species, NO3 - and NO2 -, that are commonly found in sewages and agricultural water, hold great potential for electrochemical NH3 production owing to their high NH3 yield rate and F.E. as well as building a self-sustaining NH3 production cycle working tandem with denitrification processes.1,4 In this study, we investigated Co and Fe single-atom (SA) decorated NS-doped reduced graphene oxide (Co SA/NS-rGO and Fe SA/NS-rGO) catalysts for nitrate reduction reaction (NO3RR) and nitrite reduction reaction (NO2RR). Both materials have defect-rich properties owing to preserving the nature of doped graphene materials even after the metal incorporation. The presence of the layered structure of graphene and homogenous distribution of Fe and Co SAs in the doped graphene basal plane is shown through High-Resolution Scanning Transmission Electron Microscopy (HR-STEM) measurements. In addition to the Co and Fe SAs on the NS-rGO planes, SEM and X-ray Photoelectron Spectroscopy (XPS) investigations demonstrated that CoS and FeS could be simultaneously formed.We performed NO3RR and NO2RR experiments in 0.1 M KOH + 0.1 M KNO3 and 0.1 M KOH + 0.1 M KNO2 electrolytes with constant Ar purging in a glass H-Cell with a Nafion proton exchange membrane. We obtained NH3 with 65% F.E. at -0.4 V and a maximum of 2 mol s-1 molM -1 yield rate using Co SA/NS-rGO catalyst while with 60% F.E. at -0.5 V and 2.3 mol s-1 molM -1 yield rate using Fe SA/NS-rGO catalyst for NO3RR. Furthermore, the ∼10% NO2 - F.E. that is obtained for NO3RR experiments at -0.3 V and a significant increase in NH3 F.E. after -0.3 V for NO2RR indicates that NO3 - to NO2 - reduction takes place at this potential and our catalysts follow a two-step electron transfer mechanism. Moreover, linear sweep voltammetry (LSV) measurements indicated an onset potential of -0.4 V and -0.5 V for Co SA/NS-rGO and Fe SA/NS-rGO, respectively, for the NO3RR which are in excellent agreement with NO3RR F.E. results. We demonstrate that after prereduction at high negative potentials and with optimizations in experimental conditions, one can obtain >80% NH3 F.E. for NO3RR.To further increase the NH3 yield, three different pulsed electroreduction studies such as applying a potential at (1) the open circuit potential (OCP), (2) NO2 - reduction potential, (3) Co2+ or Fe2+ red-ox potentials and NH3 reduction potentials for 1-5 s intervals were performed. On Co SA/NS-rGO, an increased NH3 F.E. of ∼100% at -0.4 V was obtained under pulsed conditions. Also, by modulating NO3 - to NO2 - conversion to more negative potentials by pulsed electroreduction, significantly higher NH3 F.E. values were obtained for both catalysts. The higher NH3 F.E. and lower overpotential of Co SA/NS-rGO compared to Fe SA/NS-rGO could be attributed to the CoS formation that is more stable than FeS.

Synthesis of an Ultra-high Hardness Nanostructured AlSi10Mg Alloy via A Hybrid Laser Powder Bed Fusion/High-Pressure Torsion Approach

The hybrid combination of laser powder bed fusion (L-PBF) and high-pressure torsion, respectively an additive manufacturing (AM) and severe plastic deformation (SPD) has recently emerged as an important field of study due to the ability to produce novel nanostructured metals/alloys with simultaneous enhancements in mechanical (hardness, yield and tensile strengths) and functional (corrosion and wear) performances. Pioneering studies on the hybrid L-PBF/HPT approach was focused on 316L stainless steel (316L SS) and AlCuMg alloys due to their widespread engineering applications. AlSi10Mg, an alloy widely used in the automotive industry is expected to benefit from this hybrid combination but has not been investigated before. Thus, this study aims to investigate the microstructural features and hardness of the nanostructured AlSi10Mg attained by the hybrid L-PBF/HPT technique via transmission electron microscopy (TEM) and Vickers microhardness (HV) measurements, respectively. The results showed novel microstructures, including nano-scale grain sizes (< 200 nm), nano-sized Mg2Si precipitates (~200 nm), and dense dislocation networks. The average hardness value was determined as 230 ± 20 HV, homogeneously distributed throughout the disk surface as indicated by the low deviation (error bar). The microstructures of L-PBF/HPT-synthesised AlSi10Mg are different and significantly refined than conventionally cast AlSi10Mg, which contributed to the two- to four-fold hardness (typical HV values of as-cast AlSi10Mg ranges from 60 – 68 HV) increase via grain boundary and dislocation strengthening mechanisms.