High-angle Annular Dark-field Scanning Research Articles

Noncovalent Grafting of Molecular Complexes to Solid Supports by Counterion Confinement.

Grafting molecular complexes on solid supports is a facile strategy to synthesize advanced materials. Here, we present a general and simple method for noncovalent grafting on charge-neutral surfaces. Our method is based on the generic principle of counterion confinement in surface micropores. We demonstrate the power of this approach using a set of three platinum complexes: Pt1 (Pt1L4(BF4)2, L = p-picoline), Pt2 (Pt2L4(BF4)4, L = 2,6-bis(pyridine-3-ylethynyl)pyridine), and Pt12 (Pt12L24(BF4)24, L = 4,4'-(5-methoxy-1,3-phenylene)dipyridine). These complexes share the same counterion (BF4-) but differ vastly in their size, charge, and structure. Imaging of the grafted materials by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC-HAADF-STEM) and energy-dispersive X-ray (EDX) showed that our method results in a homogeneous distribution of both complexes and counterions. Nitrogen sorption studies indicated a decrease in the available surface area and micropore volume, providing evidence for counterion confinement in the surface micropores. Following the adsorption of the complexes over time showed that this is a two-step process: fast surface adsorption by van der Waals forces was followed by migration over the surface and surface binding by counterion confinement. Regarding the binding of the complexes to the support, we found that the surface-adsorbate binding constant (KS) increases quadratically with the number of anions per complex up to KS = 1.6 × 106 M-1 equaling ΔG°ads = -35 kJ mol-1 for the surface binding of Pt12. Overall, our method has two important advantages: first, it is general, as you can anchor different complexes (with different charges, counterions, and/or sizes); second, it promotes the distribution of the complexes on the support surface, creating well-distributed sites that can be used in various applications across several areas of chemistry.

Hydroxyl-Bonded Ru on Metallic TiN Surface Catalyzing CO2 Reduction with H2O by Infrared Light.

Synchronized conversion of CO2 and H2O into hydrocarbons and oxygen via infrared-ignited photocatalysis remains a challenge. Herein, the hydroxyl-coordinated single-site Ru is anchored precisely on the metallic TiN surface by a NaBH4/NaOH reforming method to construct an infrared-responsive HO-Ru/TiN photocatalyst. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (ac-HAADF-STEM) and X-ray absorption spectroscopy (XAS) confirm the atomic distribution of the Ru species. XAS and density functional theory (DFT) calculations unveil the formation of surface HO-RuN5-Ti Lewis pair sites, which achieves efficient CO2 polarization/activation via dual coordination with the C and O atoms of CO2 on HO-Ru/TiN. Also, implanting the Ru species on the TiN surface powerfully boosts the separation and transfer of photoinduced charges. Under infrared irradiation, the HO-Ru/TiN catalyst shows a superior CO2-to-CO transformation activity coupled with H2O oxidation to release O2, and the CO2 reduction rate can further be promoted by about 3-fold under simulated sunlight. With the key reaction intermediates determined by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and predicted by DFT simulations, a possible photoredox mechanism of the CO2 reduction system is proposed.

Adjustment of a novel β′-type precipitate in a creep-aged Mg−15 wt%Gd alloy

A Mg−15 wt%Gd binary alloy was prepared by hot-extrusion and then creep-aged at 200 °C under a constant stress of 200 MPa in this work. Compared with the traditional aging, creep aging clearly accelerated the age-hardening response, as the aging time for the peak yield strength was shorten from 72h to ∼16h. In the peak-creep-aged sample, a novel precipitation structure, named as β′H herein, was observed as the dominant precipitate. Interestingly, these dense β′H precipitates preferred to distributing along a certain direction which generally deviated from the extrusion direction (ED) by 54–67°. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) characterization revealed that this novel β′H precipitate is composed of distorted Gd-rich hexagonal units, with the chemical formula of Mg7Gd2 and having a monoclinic structure, a = 0.671 nm, b = 1.727 nm, c = 0.521 nm and β = 100.7°. Density functional theory (DFT) calculations suggest that the applied stress during creep aging could provide an effective tensile stress for the motion of the surrounding Mg atoms when forming the β′H structure.

Demetallation and reduction induced ultra-dispersed PtZn alloy confined in zeolite for propane dehydrogenation

Developing efficient bimetallic Pt-based catalyst is highly desired for propane dehydrogenation (PDH) process. Typical co-impregnation method often results in inhomogeneous distributions of metal species on supports. Herein, we reported a facile method to support PtZn bimetal alloy nanoparticles onto Beta zeolite, mainly existing as highly dispersed Pt1Zn1 alloy species. Zn@Beta was first synthesized by hydrothermal method with the aid of ethylenediamine (EDA), leading to the introduction of Zn atoms into zeolite lattice. An impregnation process was subsequently employed to support Pt species. During this process, skeleton Zn atoms migrated out of the framework and were then reduced together with Pt in flowing H2, leading to the formation of PtZn alloy with mainly Pt1Zn1 structures. Cs-corrected high-angle annular dark-field scanning transmission election microscope and X-ray absorption fine structure analyses revealed that this method was more conducive to the formation of PtZn alloy compared with the co-impregnation method. The obtained catalyst of 0.3Pt1Zn@Beta exhibited initial propane conversion of 36.8% and propylene selectivity of 99.3% combined with low deactivation rate (0.004 h–1) over 24 h with propane WHSV of 4.7 h–1 at 550 °C. The catalyst also exhibited good PDH performance in a long-term reaction (180 h) and robustness during regeneration reactions by simply flushing hydrogen.

Design of Ir/Pt dual electrocatalysts loaded on exfoliated acetylene black for Li air battery application

This study introduces a novel type of electrocatalysts, where Pt and Ir nanoparticles were incorporated onto exfoliated acetylene black (FAB) substrate. These electrocatalysts were engineered to exhibit dual activity, simultaneously facilitating both oxygen reduction reaction and oxygen evolution reaction. The successful creation of these dual-function electrocatalysts, namely FAB180-Pt/Ir and FAB60-Pt/Ir, was confirmed through characterization techniques including transmission electron microscopy (TEM), x-ray photoelectron spectroscopy (XPS), energy-dispersive x-ray spectroscopy (EDS), and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). Ultimately, this bimetallic Pt-Ir catalyst, supported on exfoliated acetylene black (FAB), hold potential for application in Li-air batteries.

Statistical 3D morphology characterization of vaterite microspheres produced by engineered Escherichia coli

Hollow vaterite microspheres are important materials for biomedical applications such as drug delivery and regenerative medicine owing to their biocompatibility, high specific surface area, and ability to encapsulate a large number of bioactive molecules and compounds. We demonstrated that hollow vaterite microspheres are produced by an Escherichia coli strain engineered with a urease gene cluster from the ureolytic bacteria Sporosarcina pasteurii in the presence of bovine serum albumin. We characterized the 3D nanoscale morphology of five biogenic hollow vaterite microspheres using 3D high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) tomography. Using automated high-throughput HAADF-STEM imaging across several sample tilt orientations, we show that the microspheres evolved from a smaller more ellipsoidal shape to a larger more spherical shape while the internal hollow core increased in size and remained relatively spherical, indicating that the microspheres produced by this engineered strain likely do not contain the bacteria. The statistical 3D morphology information demonstrates the potential for using biogenic calcium carbonate mineralization to produce hollow vaterite microspheres with controlled morphologies. Statement of significanceThe nanoscale 3D structures of biomaterials determine their physical, chemical, and biological properties, however significant efforts are required to obtain a statistical understanding of the internal 3D morphology of materials without damaging the structures. In this study, we developed a non-destructive, automated technique that allows us to understand the nanoscale 3D morphology of many unique hollow vaterite microspheres beyond the spectroscopy methods that lack local information and microscopy methods that cannot interrogate the full 3D structure. The method allowed us to quantitatively correlate the external diameters and aspect ratios of vaterite microspheres with their hollow internal structures at the nanoscale. This work demonstrates the opportunity to use automated transmission electron microscopy to characterize nanoscale 3D morphologies of many biomaterials and validate the chemical and biological functionality of these materials.

Atomic Structure of Hardening Precipitates in Al-Mg-Si Alloys: Influence of Minor Additions of Cu and Zn.

Shifting toward sustainability and low carbon emission necessitates recycling. Aluminum alloys can be recycled from postconsumer scrap with approximately 5% of the energy needed to produce the same amount of primary alloys. However, the presence of certain alloying elements, such as copper and zinc, as impurities in recycled Al-Mg-Si alloys is difficult to avoid. This work has investigated the influence of tiny concentrations of Cu (0.05 wt %) and Zn (0.06 wt %), individually and in combination, on the precipitate crystal structures in Al-Mg-Si alloys in peak aged and overaged conditions. To assess whether such concentrations can affect the hardening precipitate structures, atomic resolution high-angle annular dark-field scanning transmission electron microscopy and atom probe tomography were adopted. The results indicate that low levels of Cu or Zn have a significant influence. Both elements showed a relatively high tendency to incorporate into precipitate structures, where Cu occupies specific atomic sites, creating its own local atomic configurations. However, Zn exhibited distinct behavior through the formation of extended local areas with 2-fold symmetry and mirror planes, not previously observed in precipitates in Al-Mg-Si alloys. Incorporation of Cu and/or Zn will influence the precipitates' electrochemical potential relative to matrix- and precipitate-free zones and thus the corrosion resistance. Furthermore, the presence of Cu/Zn structures (e.g., β'Cu, Q'/C) enhances the thermal stability of these precipitates and, accordingly, the mechanical properties of the material. The results obtained from this work are highly relevant to the topic of recycling of aluminum alloys, where accumulation of certain alloying elements is almost unavoidable; thus, tight compositional control might be critical to avoid quality degradation.

A precipitation pathway of T1 phase via heterogeneous nucleation on Li-rich particle in Al-Cu-Li alloy

The hexagonal T1 (Al2CuLi) phase is the main strengthening precipitate in Al-Cu-Li alloys and is usually considered to be formed heterogeneously at dislocations during artificial aging. The precipitation scenario in Al-Cu-Li-Mg alloy has been revisited using high-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and in-situ heating inside TEM. Octahedral nano-complexes consisting of T1 precursors (T1p) on {111} facets of early-precipitated δ'(Al3Li) particles form at under-aging stage in the investigated alloy. This nano-complex with an average diameter of 5–10 nm is a transitional structure, which gradually dissolve to facilitate the transformation of a small portion of large precursors toward T1 precipitates. The T1p is determined to be isostructural to orthorhombic Ω phase based on atomic-resolution HAADF-STEM observations. The subsequent inward diffusion of Li is believed to promote the transition from Ω-like T1p to T1. An alternative precipitation path toward the key hardening T1 precipitate is thus proposed and could explain the formation of T1 precipitates apart from those at the dislocations. Our findings suggest complex multiple precipitation pathways for T1 phase should exist in Al-Cu-Li alloys.

Structural analysis of η14 phase and its forming mechanism in Al-Zn-Mg-Cu alloy

The structural characteristic and formation mechanism of a latest reported η14 phase formed in Al-Zn-Mg-Cu alloy were systematically studied by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). By detail structural analysis, the orientation relationship (OR) of the η14 and Al matrix is modified as: (112¯0)η14//(11¯2¯)Al, [1¯103]η14//[1¯11¯]Al and [1¯100]η14//[3¯1¯1¯]Al. Structural analysis demonstrated that the η14 phase displays the C14 Laves stacking structure, however, the Zn1 and Zn2 columns composed the R'-units are only half filled by Zn. This phenomenon is mainly due to the Zn1–2 columns composed the R'-units and Zn3 column composed the R-units formed with different processes, leading to uneven intensity among these columns for the η14 phase. The formation mechanism of the η14 phase does not shows any relevance with the faulted layers reported in previous work. In contrast, The η14 phase is suggested to evolved from a metastable η14’ phase with OR of (0001)η14’//(021¯)Al and [112¯0]η14’//[11¯2¯]Al, formed by regularly replacements of Zn and Mg at the (021¯)Al habit planes The special habit plane of η14’ phase contributes to the unusual OR of η14 phase with Al matrix. Our findings extend the understanding of the precipitates formation and evolution appearing in Al-Zn-Mg-Cu alloys.

Site-occupation and structure relaxation behavior of C14-type stoichiometric and iron-rich Fe2Nb Laves phases with addition of aluminum or chromium

Powder X-ray diffraction Rietveld refinement for Al- or Cr-added stoichiometric and Fe-rich off-stoichiometric C14-type Fe2Nb Laves phases were examined to elucidate the site-occupation behavior of Al and Cr, and the resulting changes in the lattice parameters and the c/a axial ratio in the Fe2Nb Laves phases. In the case of the stoichiometric composition of the Fe2Nb Laves phase, no anti-site atoms were presented at the Fe and Nb both sites Al or Cr addition to the Fe-33.3at%Nb Laves phase by replacing Fe with Al or Cr did not generate anti-site Fe atoms, and Al and Cr preferentially occupied the Fe sites. Al and Cr atoms can replace Fe atoms at both the 6 h and 2a Fe sites in the case of Fe-rich alloy, and they also can occupy the Nb site (4f) by replacing anti-site Fe atoms. However, Al and Cr had no preferential occupation of any of these sites. The accuracy of Rietveld refinement was confirmed by observation through high-angle annular dark-field scanning transmission electron microscopy. The lattice parameters of the a and c axes increased almost linearly with increasing the added Al or Cr concentrations, but the c/a ratio showed different behavior. Therefore, the change in c/a cannot be explained solely in terms of the concentration of the added element; however, it is proposed that the change in c/a is interpreted by using parameters consistent with site-occupancy values.

Study on the Microstructure of Mg-4Zn-4Sn-1Mn-xAl As-Cast Alloys.

In this study, the microstructure of the Mg-4Zn-4Sn-1Mn-xAl (x = 0, 0.3 wt.%, denoted as ZTM441 and ZTM441-0.3Al) as-cast alloys was investigated using scanning electron microscopy (SEM), focused-ion/electron-beam (FIB) micromachining, transmission electron microscopy (TEM), and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). The analysis results revealed that the microstructure of the ZTM441 and ZTM441-0.3Al as-cast alloys both mainly consist of the α-Mg matrix, skeleton-shaped MgZn2 eutectic texture, block-shaped Mg2Sn, and Zn/Sn-rich nanoscale precipitate bands along the grain boundary and the interdendrite. Nanoscale α-Mn dispersoids formed in the grain in the ZTM441 alloy, while no α-Mn formed in the ZTM441-0.3Al alloy instead of nanoscale Al3Mn2 particles. In the ZTM441 as-cast alloy, part of the Zn element is dissolved into the α-Mn phase, and part of the Mn element is dissolved into the MgZn2 phase, but in the ZTM441-0.3Al alloy, there are no such characteristics of mutual solubility. Zn and Mn elements are easy to combine in ZTM441 as-cast alloy, while Al and Mn are easy to combine in ZTM441-0.3Al as-cast alloy. The Mg-Zn phases have not only MgZn2-type crystal structure but also Mg4Zn7- and Mg149Zn-type crystal structure in the ZTM441-0.3Al as-cast alloy. The addition of Al changes the combination of Mn and Zn, promotes the formation of Al3Mn2, and the growth of the grain.

Copper-Bearing Magnetite and Delafossite in Copper Smelter Slags

The cooling paths and kinetics in the system Cu-Fe-O are investigated by the empirical micro- and nanoscale analysis of slags from the flash furnace smelter at Olympic Dam, South Australia. We aim to constrain the exsolution mechanism of delafossite (Cu1+Fe3+O2) from a spinel solid solution (magnetite, Fe3O4) and understand why cuprospinel (CuFe2O4) is never observed, even though, as a species isostructural with magnetite, it might be expected to form. Flash furnace slags produced in the direct-to-blister copper smelter at Olympic Dam contain four Cu-bearing phases: Cu-bearing magnetite, delafossite, metallic copper, and cuprite. Delafossite coexists with magnetite as rims and lamellar exsolutions, as well as bladed aggregates, associated with cuprite within Si-rich glass. The empirical compositions of magnetite and rim delafossite are (Fe2+6.89Cu2+0.86Co0.13Mg0.15Si0.02)8.05 (Fe3+15.52Al0.41Ti0.01Cr0.01)15.95O32, and (Cu1+0.993Co0.002Mg0.002)0.997(Fe3+0.957Al0.027Ti0.005Si0.004)0.993O2, respectively. The measured Cu content of magnetite represents a combination of a solid solution (~6 mol.% cuprospinel endmember) and exsolved delafossite lamellae. Atomic-resolution high-angle annular dark field scanning transmission electron microscope (HAADF STEM) imaging shows epitaxial relationships between delafossite lamellae and host magnetite. Defects promoting the formation of copper nanoparticles towards the lamellae margins suggest rapid kinetics. Dynamic crystallization under locally induced stress in a supercooled system (glass) is recognized from misorientation lamellae in delafossite formed outside magnetite grains. The observations are concordant with crystallization during the cooling of molten slag from 1300 °C to <1080 °C. Melt separation through an immiscibility gap below the solvus in the system Cu-Fe-O is invoked to form the two distinct delafossite associations: (i) melt-1 from which magnetite + delafossite form; and (ii) melt-2 from which delafossite + cuprite form. Such a path also corroborates the published data explaining the lack of cuprospinel as a discrete phase in the slag. Delafossite rims form on magnetite at a peritectic temperature of ~1150 °C via a reaction between the magnetite and copper incorporated in the oxide/Si-rich melt. The confirmation of such a reaction is supported by the observed misfit orientation (~10°) between the rim delafossite and magnetite. HAADF STEM imaging represents a hitherto underutilized tool for understanding pyrometallurgical processes, and offers a direct visualization of phase relationships at the smallest scale that can complement both experimental approaches and theoretical studies based on thermodynamic modelling.

Thermodynamic modelling for the long-period stacking ordered phase in Mg–Y–Al system: Construction and application

An adequate thermodynamic model is required for describing the long-period stacking ordered (LPSO) phase because previously developed models cannot account for the accurate atomic occupancy of the LPSO structure. In this study, atomic structures of the equilibrated 18R and 10H phases in Mg–Y–Al alloys were systematically investigated via atomic-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-TEM) and first-principles calculations. Three structures (α-type, β-type, and γ-type) with different numbers of Mg layers (one, two, and three, respectively) sandwiched between L12 structures were present in the 18R phase. Meanwhile, δ-type (without Mg layers), ε-type (with one Mg layer), and ζ-type (with two Mg layers) structures were detected in the 10H phase. The presence of the interstitial atoms in the L12 structure was confirmed by TEM and theoretical calculations. Based on the obtained results, a new thermodynamic model for the LPSO phase was constructed and successfully applied to establish the thermodynamic description of the Mg–Y–Al system. The CALPHAD-type calculation data obtained using the proposed thermodynamic description were in good agreement with the experimental results. The findings of this study can help elucidate the formation mechanism of LPSO phases and guide Mg–Y–Al alloy design.

CO rich syngas production from catalytic CO2 gasification-reforming of biomass components on Ni/CeO2

The advancement of biomass utilization technology is vital for addressing global climate change and the depletion of fossil resources. CO rich syngas production from the CO2 gasification-reforming of biomass components (cellulose, xylan, lignin, and starch) was investigated by a two-stage fixed bed reactor. The four biomass components were heated from room temperature to 600 °C in a CO2 atmosphere, among which lignin exhibited the highest residue fraction (51.6 wt.%) and the lowest gas yield (5.7 mmol gbiomass−1), whereas cellulose demonstrated the highest gas yield from CO2 gasification-reforming (14.6 mmol gbiomass−1). Nanorod CeO2 supported Ni catalysts were used to enhance volatile (tar) CO2 reforming reactions, and the gas yield increased by 104.3 % for cellulose, 103.3 % for xylan, 149.3 % for lignin, and 128.3 % for starch compared with noncatalytic CO2 gasification-reforming. Furthermore, the structure of fresh and used catalysts were characterized by X-ray diffraction (XRD), N2 adsorption/desorption isotherm, scanning electron microscope (SEM), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), H2-temperature programmed reduction (H2-TPR), and thermogravimetry (TGA). For the CO2 gasification-reforming of cellulose, the optimum CO yield of 27.6 mmol gbiomass−1 was achieved at a gasification/reforming temperature of 600/700 °C and a biomass/catalyst ratio of 6.25 using 2 %Ni/CeO2 catalyst. The stability tests of catalysts showed an approximately linear decrease in CO yield with the increase of the number of cycles, and catalyst deactivation resulted from Ni sintering and coke deposition.

Modulating the Coordination Environment of Carbon-Dot-Supported Fe Single-Atom Nanozymes for Enhanced Tumor Therapy.

Herein, carbon dot (CD)-supported Fe single-atom nanozymes with high content of pyrrolic N and ultrasmall size (ph-CDs-Fe SAzyme) are fabricated by a phenanthroline-mediated ligand-assisted strategy. Compared with phenanthroline-free nanozymes (CDs-Fe SAzyme), ph-CDs-Fe SAzyme exhibit higher peroxidase (POD)-like activity due to their structure similar to that of ferriporphyrin in natural POD. Aberration-corrected high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and X-ray absorption fine structure spectroscopy (XAFS) analyses show that metal Fe is dispersed in ph-CDs-Fe SAzyme as single atoms. Steady-state kinetic studies show that the maximum velocity (Vmax ) and turnover number (kcat ) of H2 O2 homolyticcleavage catalyzed by ph-CDs-Fe SAzyme are 3.0 and 6.2 more than those of the reaction catalyzed by CDs-Fe SAzyme. Density functional theory (DFT) calculations show that the energy barrier of the reaction catalyzed by ph-CDs-Fe SAzyme is lower than that catalyzed by CDs-Fe SAzyme. Antitumor efficacy experiments show that ph-CDs-Fe SAzyme can efficiently inhibit the growth of tumor cells both in vitro and in vivo by synergistic chemodynamic and photothermal effects. Here a new paradigm is provided for the development of efficient antitumor therapeutic approaches based on SAzyme with POD-like activity.

Degraded creep resistance induced by static precipitation strengthening in high-pressure die casting Mg–Al–Sm alloy

Relationship between precipitation strengthening and creep resistance improvement has been an important topic for the widespread applications of magnesium alloys. Generally, static precipitation strengthening through thermal stable precipitates would generate satisfactory creep resistance. However, an opposite example is presented in this work and we propose that the size of precipitates plays a crucial role in controlling the operative creep mechanisms. In addition, the precipitate components along with their crystal structures in the crept Mg–4Al–3Sm–0.4Mn samples with/without pre-aging were thoroughly studied using Cs aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). Previous aging generates a large density of fine precipitates (< ∼5 nm) homogeneously distributing in Mg matrix and exhibiting satisfactory strengthening effect. However, the number density of precipitate strings consisting of several or even dozens of relatively coarse precipitates (∼10 nm) was significantly decreased at the same time. As revealed in this work, the relatively coarse particles in Mg matrix are much more efficient than the fine precipitates in promoting dislocation climb. Therefore, the rate-controlling mechanisms are transferred from dislocation climb to dislocation slip after previous aging, thus leading to degradation of creep resistance. Moreover, there are mainly five types of precipitates/clusters, namely β″-(Al, Mg)3Sm, Al5Sm3, ordered Al–Sm cluster, ordered Al–Mn cluster and ordered/unordered AlMnSm clusters. The crystal structures of the former two precipitates were discussed and the formation mechanisms of the precipitates/clusters were revealed.

Principle on Selecting the Coordination Ligands of Palladium Precursors Encapsulated by Zeolite for an Efficient Purification of Formaldehyde at Ambient Temperature.

High-performance zeolite-supported noble metal catalysts with low loading and high dispersion of active components are the most promising materials for achieving the complete oxidation of formaldehyde (HCHO) at room temperature. In this work, palladium nanoparticles (Pd NPs) with different sizes were successfully encapsulated inside the silicalite-1 (S-1) zeolite framework by using diverse stabling ligands via the one-pot method. Thereafter, the rule on selecting the coordinative ligands for palladium was clarified: more N atoms, a short carbon chain, a smaller branch chain, and bidentate coordination are characteristics of an ideal ligand. Accordingly, the best-performing 0.2Pd@S-1(Ethylenediamine) catalyst exhibited outstanding performance for HCHO oxidation, achieving 100% conversion even at room temperature. High-resolution high-angle annular dark-field scanning transmission electron microscopy (HR HAADF-STEM) and density functional theory (DFT) calculations indicate that the chelate is formed by complexation of Pd2+ ions with ethylenediamine, displaying the smallest spatial site resistance simultaneously with the zeolite synthesis, resulting in Pd located mostly within the 5-membered ring (5-MR) channels of S-1 after calcination, thus limiting the growth of Pd clusters and promoting their dispersion.

Atomic-scale investigation of precipitate phases in QE22 Mg alloy

Precipitation-hardenable commercial Mg alloy QE22 (Mg-2.5Ag-2.0Nd-0.7Zr, wt.%) has excellent mechanical properties, but precipitates in this alloy have not been well understood. In this work, precipitate phases γ'', γ, and δ formed during the isothermal ageing process at 150, 200, 250, and 300 °C have been characterized using atomic-resolution high-angle annular dark-field scanning transmission electron microscopy and atomic-scale energy-dispersive X-ray spectroscopy. The morphology, crystal structure, and orientation relationship of these precipitate phases have been determined. Domain boundaries usually exist in a single γ particle, which can be characterized by a separation vector of [11¯01]α. The δ phase forms in situ from its precursor γ phase, consequently leading to the formation of three different variants within a single δ particle. The nucleation of the δ phase is strongly related to the domain boundaries of the γ phase. The formation of the γ phase may be promoted by its precursor γ'' phase. The similarities in atomic structures of the γ'', γ, and δ phases are described and discussed, indicating that transformations between these precipitate phases can be accomplished through the diffusion of added alloying elements.

Atomically dispersed copper-nickel electrocatalyst for highly selective electroreduction of CO2 at a wide potential range

Designing and synthesising electrocatalysts with low overpotential, high activity, selectivity, and stability for the CO2 reduction reaction (CO2RR) is crucial for addressing environmental challenges and realising the artificial carbon cycle. In this study, we successfully synthesised a nitrogen-doped carbon-supported diatomic electrocatalyst comprising atomically dispersed CuN4 and NiN4 bimetallic centers. This was confirmed through extensive characterisation using high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption spectroscopy techniques. The as-synthesised CBN-CuNi electrocatalyst exhibited exceptional selectivity and stability in CO2RR. Over a wide potential range from − 0.60 to − 1.10 V vs RHE, CBN-CuNi maintained over 90% Faraday efficiency for CO (FECO) production. Notably, at − 0.9 V vs RHE, it achieved a remarkable selectivity with a maximum FECO of 97.9%, surpassing single metal catalysts, including CBN-Ni and CBN-Cu. Furthermore, CBN-CuNi demonstrated outstanding stability, sustaining over 90% FECO production for 40 h of continuous electrolysis, surpassing many existing electrocatalysts. These findings highlight the potential of the as-synthesised bimetallic electrocatalyst CBN-CuNi in the electrochemical reduction of CO2 to CO, contributing to advancing the artificial carbon cycle and addressing environmental concerns.

Single-atom Pd loaded on nitrogen-doped carbon as a bifunctional catalyst for the electrochemical degradation of 2,4-dichlorophenol

A nitrogen-doped carbon-anchored single atom Pd (SA-Pd/NC) electrocatalyst was prepared by pyrolysis of Pd-doped zeolite imidazolite framework (ZIF) precursors. The SA-Pd/NC catalyst was characterized by high-resolution transmission electron microscopy, aberration-corrected high-angle annular dark field scanning transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectrometry and applied in the degradation of 2,4-dichlorophenol (2,4-DCP). We demonstrate that the SA-Pd/NC catalyst has dual functions, with both electrocatalytic hydrodechlorination (ECH) activity and in situ heterogeneous electro-Fenton (hetero-EF) activity even at low current density. The ECH process was the main pathway of 2,4-DCP degradation without oxygen aeration. Under aerobic conditions, hetero-EF coupling with ECH occurred simultaneously on the SA-Pd/NC cathode, i.e., the dechlorination product phenol was oxidatively degraded with the reactive oxygen species produced on the electrode. The degradation rate of 2,4-DCP and TOC removal rate reached 95.1% and 37.6%, respectively, with a current density of 2.5 mA cm−2 and an initial pH of 3.0. This work provides the design of bifunctional single-atom catalysts for 2,4-DCP degradation, including dechlorination and mineralization.