Dark-field Scanning Transmission Electron Microscopy Research Articles

Experimental and theoretical studies on a Mg2InRE-type prismatic precipitate plate in a series of Mg-In-RE ternary alloys

In precipitation-hardening Mg-In-Sm alloy, a category of novel Mg2InSm prismatic plates have been built successfully and its crystal structure and atomic coordination were studied by atomic scale high-angle annular dark-field scanning transmission electron microscopy. The Mg2InSm plate has an orthorhombic structure, whose stability can be verified by first-principles calculations. Similarly, with the substitution of other rare earth (RE) for Sm, a series of Mg2InRE orthorhombic structures are also predicted to be stable. The findings are expected to guide the future design of effective precipitation strengthening phases in Mg–based alloys.

Vacancy-Enhanced Sb-N4 Sites for the Oxygen Reduction Reaction and Zn-Air Battery.

With the advantages of a Fenton-inactive characteristic and unique p electrons that can hybridize with O2 molecules, p-block metal-based single-atom catalysts (SACs) for the oxygen reduction reaction (ORR) have tremendous potential. Nevertheless, their undesirable intrinsic activity caused by the closed d10 electronic configuration remains a major challenge. Herein, an Sb-based SAC featuring carbon vacancy-enhanced Sb-N4 active centers, corroborated by the results of high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure, has been developed for an incredibly effective ORR. The obtained SbSA-N-C demonstrates a positive half-wave potential of 0.905 V and excellent structural stability in alkaline environments. Density functional theory calculations reveal that the carbon vacancies weaken the adsorption between Sb atoms and the OH* intermediate, thus promoting the ORR performance. Practically, the SbSA-N-C-based Zn-air batteries achieve impressive outcomes, such as a high power density of 181 mW cm-2, showing great potential in real-world applications.

Reconstructing the 3D Coordinates of Guest:Host OLED Blends with Single Atom Resolution.

The performance of electronic and semiconductor devices is critically dependent on the distribution of guest molecules or atoms in a host matrix. One prominent example is that of organic light-emitting diode (OLED) displays containing phosphorescent emitters, now ubiquitous in handheld devices and high-end televisions. In such OLEDs the phosphorescent guest [normally an iridium(III)-based complex] is typically blended into a host matrix, and charge injection and transport, exciton formation and decay, and hence overall device performance are governed by the distribution of the emissive guest in the host. Here high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) is used with depth sectioning to reconstruct the 3D distribution of emissive iridium(III) complexes, fac-tris(2-phenylpyridine)iridium(III) [Ir(ppy)3], blended into the amorphous host material, tris(4-carbazoyl-9-ylphenyl)amine (TCTA), by resolving the position of each single iridium(III) ion. It is found that most Ir(ppy)3 complexes are clustered with at least one other, even at low concentrations, and that for films of 20wt.% Ir(ppy)3 essentially all the complexes are interconnected. The results validate the morphology of blend films created using molecular dynamics simulations which mimic the evaporation film-forming process and are also consistent with the experimentally measured charge transport and photophysical properties.

“Invisible” radioactive cesium atoms revealed: Pollucite inclusion in cesium-rich microparticles (CsMPs) from the Fukushima Daiichi Nuclear Power Plant

Understanding radioactive Cs contamination has been a central issue at Fukushima Daiichi and other nuclear legacy sites; however, atomic-scale characterization of radioactive Cs in environmental samples has never been achieved. Here we report, for the first time, the direct imaging of radioactive Cs atoms using high-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). In Cs-rich microparticles collected from Japan, we document inclusions that contain 27 – 36 wt% of Cs (reported as Cs2O) in a zeolite: pollucite. The compositions of three pollucite inclusions are (Cs1.86K0.11Rb0.19Ba0.22)2.4(Fe0.85Zn0.84X0.31)2.0Si4.1O12, (Cs1.19K0.05Rb0.19Ba0.22)1.7(Fe0.66Zn0.32X0.41)1.4Si4.6O12, and (Cs1.27K0.21Rb0.29Ba0.15)1.9(Fe0.60Zn0.32X0.69)1.6Si4.4O12 (X includes other cations). HAADF-STEM imaging of pollucite, viewed along the [111] zone axis, revealed an array of Cs atoms, which is consistent with a simulated image using the multi-slice method. The occurrence of pollucite indicates that locally enriched Cs reacted with siliceous substances during the Fukushima meltdowns, presumably through volatilization and condensation. Beta radiation doses from the incorporated Cs are estimated to reach 106 – 107 Gy, which is more than three orders of magnitude less than typical amorphization dose of zeolite. The atomic-resolution imaging of radioactive Cs is an important advance for better understanding the fate of radioactive Cs inside and outside of nuclear reactors damaged by meltdown events.

Plasmon assisted synthesis of TiN-supported single-atom nickel catalysts

We report the deposition of single atom nickel catalyst on refractory plasmonic titanium nitride (TiN) nanomaterials supports using the wet synthesis method under visible light irradiation. TiN nanoparticles efficiently absorb visible light to generate photoexcited electrons and holes. Photoexcited electrons reduce nickel precursor to deposit Ni atoms on TiN nanoparticles’ surface. The generated hot holes are scavenged by the methanol. We studied the Ni deposition on TiN nanoparticles by varying light intensity, light exposure time, and metal precursor concentration. These studies confirmed the photodeposition method is driven by hot electrons and helped us to find optimum synthesis conditions for single atoms deposition. We characterized the nanocatalysts using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), energy dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS). We used density functional theory (DFT) calculations to predict favorable deposition sites and aggregation energy of Ni atoms on TiN. Surface defect sites of TiN are most favorable for single nickel atoms depositions. Interestingly, the oxygen sites on native surface oxide layer of TiN also exhibit strong binding with the single Ni atoms. Plasmon enhanced synthesis method can facilitate photodeposition of single atom catalysts on a wide class of metallic supports with plasmonic properties.

Transmission electron microscopy reveals clusters of Au–Ag nanoparticles formed in TiO2 thin film, with enhanced plasmonic response

This work reports on the influence of nanoparticle (NP) size distribution and the chemical nature of gold (Au) and/or silver (Ag) NPs in the localized surface plasmon resonance (LSPR) responses. The NPs were produced embedded in a titanium dioxide (TiO2) thin film, deposited by reactive magnetron sputtering technique followed by in-vacuum thermal treatment at 400 °C. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) gave quantitative key information in terms of both the size and distribution of the noble metal NPs. The average Feret diameter was 17 nm (σ = 8) and 55 nm (σ = 28) for Au/TiO2 and Ag/TiO2 films, respectively, while the Au–Ag/TiO2 film showed intermediate values, with an average size of 22 nm (σ = 9). HAAD-STEM, complemented by EDX chemical mapping, revealed an unusual formation of cluster structures containing local distributions of bimetallic (alloyed) Au–Ag NPs. The synergetic characteristics and properties of such bimetallic Au–Ag NPs resulted in an outstanding LSPR sensitivity compared to the monometallic counterparts. Furthermore, the analysis of the average nearest neighbor distances (about one order of magnitude lower than counterparts) suggests the existence of plasmonic hotspots relevant to be explored in sensing and surface-enhanced spectroscopies.

A method to synthesize specific active Cu sites of single-atom catalysts with high stability for acetylene hydration

Single-atom catalysts (SACs) have received much attention in the realm of energy and catalytic conversion due to their maximum atomic efficiency. Herein, we report a cascade anchoring strategy for the preparation of a Cu-S1O2 species of single-atom catalyst attached to a carbon carrier containing P and S (Cu-S1O2 SA/CPS) with a content of 12.4 wt%. Over the Cu-S1O2 SA/CPS catalyst, the conversion of 95.8% and selectivity of 87.2% for acetylene hydration could still be achieved at 70 h (T = 200°C, GHSV(C2H2) = 90 h−1 and VH2O/VC2H2 = 4). X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) tests reveal that the Cu atoms of Cu-S1O2 SA/CPS are predominantly coordinated in a trinary manner (Cu-S1O2). Based on high-resolution aberration-corrected high-angle annular dark-field scanning transmission electron microscope (HAADF-STEM), it is demonstrated that the Cu single-atom sites are highly dispersed in Cu-S1O2 SA/CPS. It is evident from the scanning electron microscopy (SEM) that Cu-S1O2 SA/CPS has a two-dimensional layered structure. The specific structure of the active site Cu is primarily attributed to the coordination of S and O atoms, resulting in its superior stability for acetylene hydration towards the synthesis of acetaldehyde. Density functional theory (DFT) calculations confirm that the formation of the Cu-S1O2 site facilitates the activation of acetylene, which is a pivotal step in the acetylene hydration process and considered as the rate-determining step. This article not only introduces an innovative strategy in the synthesis of Cu SACs but also represents a significant breakthrough in the stability of Cu SACs in acetylene hydration.

Atomic-Scale Imaging of Clay Mineral Nanosheets and Their Supramolecular Complexes through Electron Microscopy: A Supramolecular Chemist's Perspective.

Recent advancements in electron microscopy techniques have revolutionized the ability to directly visualize and understand the intricate world of supramolecular chemistry. This paper provides a concise overview of a study delving into the atomic-scale imaging of monolayer clay mineral nanosheets and their associated supramolecular complexes. The imaging is conducted by harnessing the power of aberration-corrected scanning transmission electron microscopy (STEM). Clay mineral nanosheets, with their anionic charge and ultrathin thickness (of 1 nm), serve as a stable Coulombic host material for cationic guest molecules through electrostatic interactions, facilitating exceptional stability and control during observation. By incorporation of heavy-metal atom markers coordinated within the target molecules, high-angle annular dark field STEM enables a clear visualization of these supramolecular complexes. This approach helps to overcome the limitations of graphene-based systems and expands the possibilities of atomic-scale imaging of nonperiodic molecular assemblies formed by weak supramolecular interactions. The fusion of electron microscopy techniques with the principles of supramolecular and material chemistry offers exciting opportunities for studying the structure, behavior, and properties of complex supramolecular systems. It sheds light on the intricate molecular architectures and design principles governing these systems. This study showcases the immense potential of electron microscopy in supramolecular chemistry and invites researchers from various disciplines to explore the transformative possibilities of atomic-scale imaging in the field.

Impact of varied zeolite materials on nickel catalysts in CO2 methanation

Ni catalysts supported on 4A, 5A, 13X, ZSM-5, and BEA zeolites were prepared using the vacuum-heating method for CO2 methanation. These support materials play a pivotal role in shaping the catalysts' properties and their catalytic performance. High-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and energy-dispersive X-ray spectroscopy (EDS) mappings suggest a significant concentration of Ni nanoparticles situated on the external surfaces of catalysts with low Si/Al ratios zeolites (Ni-4A, Ni-5A, and Ni-13X). These Ni nanoparticles exhibit characteristics of weaker metal-support interaction, lower metal reduction temperatures, and moderate H2 adsorption activity. Moreover, these low Si/Al ratio zeolites demonstrate robust CO2 adsorption activity. These properties endow Ni-5A and Ni-13X catalysts with heightened CO2 conversion (70.4–70.9%) and methane selectivity (92.4–96.4%). In contrast, high Si/Al ratio zeolite-based catalysts (Ni-ZSM-5 and Ni-BEA) exhibit smaller Ni particles, strong metal-support interaction and weaker CO2 adsorption activity, resulting in reduced CO2 methanation activity and decreased methane selectivity (71.2–73.4%). The normalized CO2 conversion rate presents a correlation with the average Ni particle size.

Vertically Stacked Amorphous Ir/Ru/Ir Oxide Nanosheets for Boosted Acidic Water Splitting.

Integrating multiple functional components into vertically stacked heterostructures offers a prospective approach to manipulating the physicochemical properties of materials. The synthesis of vertically stacked heterogeneous noble metal oxides remains a challenge. Herein, we report a surface segregation approach to create vertically stacked amorphous Ir/Ru/Ir oxide nanosheets (NSs). Cross-sectional high-angle annular darkfield scanning transmission electron microscopy images demonstrate a three-layer heterostructure in the amorphous Ir/Ru/Ir oxide NSs, with IrOx layers located on the upper and lower surfaces, and a layer of RuOx sandwiched between the two IrOx layers. The vertically stacked heterostructure is a result of the diffusion of Ir atoms from the amorphous IrRuOx solid solution to the surface. The obtained A-Ir/Ru/Ir oxide NSs display an ultralow overpotential of 191 mV at 10 mA cm-2 toward acid oxygen evolution reaction and demonstrate excellent performance in a proton exchange membrane water electrolyzer, which requires only 1.63 V to achieve 1 A cm-2 at 60 °C, with virtually no activity decay observed after a 1300 h test.

Electrochemically structured tantalum surfaces via anodization for core-shell nanostructures: Optimization and characterization of Zn-ZnO nanoparticle deposition using magnetron sputtering

This study explores the electrochemical anodization of tantalum surfaces to create nanostructured substrates for the deposition of Zn-ZnO nanoparticles (NPs) through magnetron sputtering. The anodization process, conducted at different potentials (25 V and 50 V), resulted in tantalum surfaces with distinct dimple structures. The formation of these nano-level dimples is attributed to the dynamic equilibrium between the continuous formation and dissolution of the anodic TaOx layer. The dimple diameter is observed to increase with applied potential, correlating with the dissolution rate of the anodic oxide. The NP deposition parameters were studied in two steps. First, the effect of the deposition conditions on the nanoparticle size and distribution was evaluated and optimized on silicon substrates. Second, the conditions that resulted in the optimum size and distribution of the nanoparticles were utilized in tantalum substrates and evaluated to which extent these conditions were reproduced onto the anodized Ta substrate. Comparisons of Zn-ZnO nanoparticle depositions on silicon and tantalum substrates reveal similar island growth trends, with differences in nanoparticle size and distribution attributed to substrate properties. Further investigation involves anodized tantalum substrates with varying dimple sizes, and deposition conditions are adjusted with bias voltage, pressure, and deposition time to control nanoparticle characteristics. Characterization of the Zn-ZnO nanoparticles deposited on anodized tantalum surfaces is performed using scanning electron microscopy, high-angle annular dark-field scanning transmission electron microscopy, and energy-dispersive x-ray spectroscopy. The resulting core-shell structures are confirmed through structural analysis, revealing a core of hexagonal close-packed Zn and a shell of ZnO. The study demonstrates the influence of substrate properties and deposition conditions on the morphology and composition of Zn-ZnO nanoparticles, providing insights for applications in nanoelectronics and catalysis.

Quantifying the thickness of WTe2 using atomic-resolution STEM simulations and supervised machine learning.

For two-dimensional (2D) materials, the exact thickness of the material often dictates its physical and chemical properties. The 2D quantum material WTe2 possesses properties that vary significantly from a single layer to multiple layers, yet it has a complicated crystal structure that makes it difficult to differentiate thicknesses in atomic-resolution images. Furthermore, its air sensitivity and susceptibility to electron beam-induced damage heighten the need for direct ways to determine the thickness and atomic structure without acquiring multiple measurements or transferring samples in ambient atmosphere. Here, we demonstrate a new method to identify the thickness up to ten van der Waals layers in Td-WTe2 using atomic-resolution high-angle annular dark-field scanning transmission electron microscopy image simulation. Our approach is based on analyzing the intensity line profiles of overlapping atomic columns and building a standard neural network model from the line profile features. We observe that it is possible to clearly distinguish between even and odd thicknesses (up to seven layers), without using machine learning, by comparing the deconvoluted peak intensity ratios or the area ratios. The standard neural network model trained on the line profile features allows thicknesses to be distinguished up to ten layers and exhibits an accuracy of up to 94% in the presence of Gaussian and Poisson noise. This method efficiently quantifies thicknesses in Td-WTe2, can be extended to related 2D materials, and provides a pathway to characterize precise atomic structures, including local thickness variations and atomic defects, for few-layer 2D materials with overlapping atomic column positions.

Atomically thin Co-doped nickel oxide/hydroxide superstructure toward high-energy supercapacitors

Atomically thin nanosheets can expose almost all electroactive sites, which deliver outstanding electrochemical performances. However, the direct fabrication of atomically thin nanosheets array on conductive substrates as binder-free electrodes remains a challenge. Herein, atomically thin (ca. 1.4 nm) Co-doped nickel oxide/hydroxide (CoNiOHx) nanosheets superstructure is grown on Ni foam via an alanine-induced in-situ synthesis strategy. High-angle annular dark-field scanning transmission electron microscope (HAADF-STEM) verifies the formation of Co8Ni16O32 mesophase between Co-doped Ni(OH)2 and NiO in the optimized sample. Density functional theory (DFT) calculations demonstrate an improved electrical conductivity and low deprotonation energy in Co8Ni16O32, contributing to elevated electrochemical performances. As expected, the electrode delivers a super-high specific capacity of 2244 mC cm−2 (ca. 1268 C g−1) at 2 mA cm−2 and prominent long-life span with no capacity decay after 5000 cycles. Moreover, the asymmetric supercapacitor constructed by coupling the above cathode and activated carbon (AC) anode displays a high energy density of 73.3 Wh kg−1 at the power density of 2250 W kg−1, as well as meritorious cycling stability. This work provides a new strategy for the construction of atomically thin superstructure on conductive metal substrate with high energy storage capability.

Laser additive remanufacturing Ni-based multilayers reinforced with dual-scale tungsten carbides via a novel integrated strategy

This study entailed the development of a novel integrated strategy that incorporates hot-wire-feed laser deposition and remelting for repairing stainless steel having WC-Ni composite multilayers reinforced with homogeneously distributed dual-scale tungsten carbide particles. The microstructural characteristics, phase compositions, and microstructural evolution of the composites obtained under three representative combinations of operating parameters were thoroughly investigated. On the basis of the partial dissolution of WC/W2C particles and the temperature variation of the molten pool between laser deposition and remelting, microsized WC particles were successfully synthesized in situ around the large retained WC/W2C in the repaired zone when the optimal energy input during the repair process was employed. Combined atomic-scale high-angle annular dark-field scanning transmission electron microscopy, high-resolution transmission electron microscopy, and ab initio analysis based on density functional theory calculations were employed to reveal the crystallographic orientation relationship between in situ WC and the matrix. The growth mechanism and morphology evolution were clarified. Compared to the substrate, the surface wear resistance of the obtained multilayers was significantly improved owing to the duplex-strengthening effect of the evenly distributed reinforcements in terms of the retained WC/W2C and in situ WC particles. This study affords new insights into the tailoring of reinforcements in composites with excellent wear performance for repairing metallic components.

Growth mechanism of star-shaped Au–Ag nanoparticles synthesized by ascorbic acid reduction and underpotential deposition

The growth mechanism of star-shaped Au–Ag nanoparticles, which is important for improving the absorption efficiency of nanoparticles in the near-infrared region, remains to be clarified. In this study, the growth mechanism by stabilizing certain facets of Au in spines by underpotential deposition of Ag was investigated. The nanoparticles were analyzed primarily by scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy. Analysis of spines on nanoparticles synthesized with an Au/Ag ratio of 18/4 revealed that approximately 1 nm of Ag was deposited on the topmost surface of Au, and the growth direction of spines was <200>. Underpotential deposition of Ag nanolayers on specific facets of the spines on nanoparticles was observed for the first time by elemental mapping and high-angle annular dark-field STEM tomography. These findings are expected to contribute to the morphology control of plasmonic nanoparticles.

Enhanced N2O decomposition on Rh/ZrO2 catalysts through the promotional effect of palladium

Supported rhodium oxide (RhOx) catalysts have emerged as highly promising for effectively catalytic decomposition of N2O, hence contributing to the mitigation of greenhouse gas emission and combating global warming. Supported RhOx catalysts outperform catalysts employing zeolites and composite metal oxides even under challenging conditions involving O2, H2O, and CO2. This study explores the augmentation of Rh/ZrO2 (RhOx supported on monoclinic ZrO2) catalyst efficiency through the addition of palladium (Pd) to yield RhPd/ZrO2. The augmented catalyst demonstrates notable improvements in N2O decomposition under both N2O-only and more realistic conditions (N2O + O2 + H2O + CO2). Various techniques, including high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption spectroscopy, were employed to investigate the structural characteristics of Rh and Pd species on ZrO2. Kinetic studies further delved into the promotional effect, revealing that the introduction of Pd enhanced the catalytic activity of RhOx catalysts by augmenting their thermal reduction capability. This enhancement proved beneficial in facilitating the efficient progression of the rate-determining step for N2O catalytic decomposition, namely the thermal reduction of the catalyst to produce gaseous O2, particularly at low temperatures. These results highlight the potential of Pd-mediated improvements in Rh/ZrO2 catalysts for sustainable and efficient N2O decomposition.

Single-atom iridium doped ultrathin MoS2 layers as a highly efficient catalyst for the hydrodeoxygenation of 5-hydroxymethylfurfural

The catalytic transformation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) is of great importance within the context of biomass valorization, but remains a major challenge due to the complicated reaction networks. Herein, single-atom Ir doped ultrathin MoS2 layers were synthesized and used as catalyst for the hydrodeoxygenation of HMF, yielding 96.5% of DMF. The single atomic structure of Ir was determined by X-ray diffraction (XRD), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray absorption fine structure analysis (XAFS), and X-ray photoelectron spectroscopy (XPS). Furthermore, the Ir doped MoS2 catalyst showed excellent stability and did not deactivate after five reaction cycles. This work expands the applications of single-atom catalysts and introduces a new and highly efficient catalyst for the sustainable production of DMF.

Spontaneous Deposition of Single Platinum Atoms on Anatase TiO2 for Photocatalytic H2 Evolution.

Single-atom (SA) decoration has emerged as a frontier in catalysis due to its unique characteristics. Recently, decorated Pt single atoms on titania have shown promise in photocatalytic hydrogen evolution. In this work, we demonstrate that Pt SAs can spontaneously deposit on the surface, driven by electrostatic forces; the key is to determine the golden pH and surface potential. We conducted a comprehensive investigation into the influence of the pH of the deposition precursor on the spontaneous adsorption of Pt SAs onto TiO2 nanosheets (TiNSs). We introduced a straightforward pH-dependent and charge-dependent strategy for the solid electrostatic anchoring of Pt SAs on TiO2. Furthermore, we established that the level of Pt loading can be controlled by adjusting the precursor pH. X-ray photoelectron spectroscopy (XPS) and high-angle annular dark-field imaging scanning transmission electron microscopy (HAADF-STEM) were used to evaluate the Pt SA-decorated samples. Photocatalytic hydrogen production activity was assessed under ultraviolet (UV) (365 nm) irradiation. Notably, we found that at a pH of 8, slightly below the measured point of zero charge (PZC), a unique mixture of Pt clusters and single atoms was deposited on the surface of TiNSs. This unique composition significantly improved hydrogen production, resulting in ∼3.7 mL of hydrogen generated after 8 h of UV exposure by only 10 mg of the Pt-decorated TiNS (with Pt loadings of 0.12 at. %), which is ∼300 times higher than the undecorated TiNS.

Dynamically Reconstructed Triple-Copper-Vacancy Associates Confined in Cu Nanowires Enabling High-Rate and Selective CO2 Electroreduction to C2+ Products.

Electrochemically reconstructed Cu-based catalysts always exhibit enhanced CO2 electroreduction performance; however, it still remains ambiguous whether the reconstructed Cu vacancies have a substantial impact on CO2 -to-C2+ reactivity. Herein, Cu vacancies are first constructed through electrochemical reduction of Cu-based nanowires, in which high-angle annular dark-field scanning transmission electron microscopy image manifests the formation of triple-copper-vacancy associates with different concentrations, confirmed by positron annihilation lifetime spectroscopy. In situ attenuated total reflection-surface enhanced infrared absorption spectroscopy discloses the triple-copper-vacancy associates favor *CO adsorption and fast *CO dimerization. Moreover, density-functional-theory calculations unravel the triple-copper-vacancy associates endow the nearby Cu sites with enriched and disparate local charge density, which enhances the *CO adsorption and reduces the CO-CO coupling barrier, affirmed by the decreased *CO dimerization energy barrier by 0.4eV. As a result, the triple-copper-vacancy associates confined in Cu nanowires achieve a high Faradaic efficiency of over 80% for C2+ products in a wide current density range of 400-800mA cm-2 , outperforming most reported Cu-based electrocatalysts.

Electrocatalysis of ammonia on NiCu nanoclusters with higher activity and stability synthesized by a simplified polyol technique

This work focuses on a simplified polyol process by which to synthesize five different NiCu/C nanoclusters (NCs) electrocatalysts with the variation of mass and atomic ratio. NCs are characterized by X-ray diffractometry (XRD), X-ray photoelectron spectroscopy, transmission electron spectroscopy (TEM), and scanning electron microscopy with energy-dispersive spectroscopy (EDS) for their crystallite and electronic structures, morphological studies, and elemental composition. The high-angle annular dark-field scanning TEM coupled with EDS elemental mapping has confirmed that nanoparticles (NPs) are formed with Ni and Cu, and NPs are subsequently noted to conform into NCs in such a fashion that NiCu NPs are interconnected to each other rather than overlapping considered a unique distribution of NiCu NCs on the carbon support observed in STEM. NPs arrangement in the conformation of NCs has largely increased in the coverage of NiCu-oxyhydroxides working as active sites for ammonia electrocatalysis evidenced in cyclic voltammograms and XPS investigation. NCs were employed for the oxidation of NH4OH, NH4Cl, NH4NO3, and (NH4)2SO4 of which NiCu/C-2 has shown the highest performance over other NiCu/C samples and their individuals. NiCu/C-2 is also found to have higher stability than other mono/bi-metallic electrocatalysts on the stability test preformed in an electrochemical environment. In addition, the sharp drops of the current in the chronoamperometric curves have been investigated during the stability test.