Single-atom catalysts with anionic metal centers: Promising electrocatalysts for the oxygen reduction reaction and beyond

Ongoing efforts to develop single-atom catalysts(SACs) for the oxygen reduction reaction(ORR) typically focus on SACs with cationic metal centers,while SACs with anionic metal centers(anionic SACs) have been generally neglected.However,anionic SACs may offer excellent active sites for ORR,since anionic metal centers could facilitate the activation of O_(2) by back donating electrons to the antibonding orbitals of O_(2).In this work,we propose a simple guideline for designing anionic SACs:the metal centers should have larger electronegativity than the surrounding atoms in the substrate on which the metal atoms are supported.By means of density functional theory(DFT) simulations,we identified 13 anionic metal centers(Co,Ni,Cu,Ru,Rh,Pd,Ag,Re,Os,Ir,Pt,Au,and Hg) dispersed on pristine or defective antimonene substrates as new anionic SACs,among which anionic Au and Co metal centers exhibit limiting potentials comparable to,or even better than,conventional Pt-based catalysts towards ORR.We also found that anionic Os and Re metal centers on the defective antimonene can electrochemically catalyze the nitrogen reduction reaction(NRR) with a limiting potential close to that of stepped Ru(0001).Overall,our work shows promise towards the rational design of anionic SACs and their utility for applications as electrocatalysts for ORR and other important electrochemical reactions.

Amorphous Iridium Oxide-Integrated Anode Electrodes with Ultrahigh Material Utilization for Hydrogen Production at Industrial Current Densities

Herein,ionomer-free amorphous iridium oxide(IrO_(x))thin electrodes are first developed as highly active anodes for proton exchange membrane electrolyzer cells(PEMECs)via low-cost,environmentally friendly,and easily scalable electrodeposition at room temperature.Combined with a Nafion 117 membrane,the IrO_(x)-integrated electrode with an ultralow loading of 0.075 mg cm^(-2)delivers a high cell efficiency of about 90%,achieving more than 96%catalyst savings and 42-fold higher catalyst utilization compared to commercial catalyst-coated membrane(2 mg cm^(-2)).Additionally,the IrO_(x)electrode demonstrates superior performance,higher catalyst utilization and significantly simplified fabrication with easy scalability compared with the most previously reported anodes.Notably,the remarkable performance could be mainly due to the amorphous phase property,sufficient Ir^(3+)content,and rich surface hydroxide groups in catalysts.Overall,due to the high activity,high cell efficiency,an economical,greatly simplified and easily scalable fabrication process,and ultrahigh material utilization,the IrO_(x)electrode shows great potential to be applied in industry and accelerates the commercialization of PEMECs and renewable energy evolution.

Multiphase cooperation for multilevel strain accommodation in a single-crystalline BiFeO_(3) thin film

The functionalities and diverse metastable phases of multiferroic BiFeO_(3)(BFO)thin films depend on the misfit strain.Although mixed phase-induced strain relaxation in multiphase BFO thin films is well known,it is unclear whether a singlecrystalline BFO thin film can accommodate misfit strain without the involvement of its polymorphs.Thus,understanding the strain relaxation behavior is key to elucidating the lattice strain–property relationship.In this study,a correlative strain analysis based on dark-field inline electron holography(DIH)and quantitative scanning transmission electron microscopy(STEM)was performed to reveal the structural mechanism for strain accommodation of a single-crystalline BFO thin film.The nanoscale DIH strain analysis results indicated a random combination of multiple strain states that acted as a primary strain relief,forming irregularly strained nanodomains.The STEM-based bond length measurement of the corresponding strained nanodomains revealed a unique strain accommodation behavior achieved by a statistical combination of multiple modes of distorted structures on the unit-cell scale.The globally integrated strain for each nanodomain was estimated to be close to1.5%,irrespective of the nanoscale strain states,which was consistent with the fully strained BFO film on the SrTiO_(3) substrate.Density functional theory calculations suggested that strain accommodation by the combination of metastable phases was energetically favored compared to single-phase-mediated relaxation.This discovery allows a comprehensive understanding of strain accommodation behavior in ferroelectric oxide films,such as BFO,with various low-symmetry polymorphs.

Electrochemically Grown Ultrathin Platinum Nanosheet Electrodes with Ultralow Loadings for Energy-Saving and Industrial-Level Hydrogen Evolution

Nanostructured catalyst-integrated electrodes with remarkably reduced catalyst loadings,high catalyst utilization and facile fabrication are urgently needed to enable cost-effective,green hydrogen production via proton exchange membrane electrolyzer cells(PEMECs).Herein,benefitting from a thin seeding layer,bottom-up grown ultrathin Pt nanosheets(Pt-NSs)were first deposited on thin Ti substrates for PEMECs via a fast,template-and surfactant-free electrochemical growth process at room temperature,showing highly uniform Pt surface coverage with ultralow loadings and vertically well-aligned nanosheet morphologies.Combined with an anode-only Nafion 117 catalyst-coated membrane(CCM),the Pt-NS electrode with an ultralow loading of 0.015 mgPt cm−2 demonstrates superior cell performance to the commercial CCM(3.0 mgPt cm^(−2)),achieving 99.5%catalyst savings and more than 237-fold higher catalyst utilization.The remarkable performance with high catalyst utilization is mainly due to the vertically well-aligned ultrathin nanosheets with good surface coverage exposing abundant active sites for the electrochemical reaction.Overall,this study not only paves a new way for optimizing the catalyst uniformity and surface coverage with ultralow loadings but also provides new insights into nanostructured electrode design and facile fabrication for highly efficient and low-cost PEMECs and other energy storage/conversion devices.

Chelation-mediated in-situ formation of ultrathin cobalt(oxy)hydroxides on hematite photoanode towards enhanced photoelectrochemical water oxidation

In this work,a facile chelation-mediated route was developed to fabricate ultrathin cobalt(oxy)hydroxides(CoOOH)nanosheets on hematite photoanode(Fe_(2)O_(3)).The route contains two steps of the adsorption of[Co-EDTA]^(2-)species on Fe_(2)O_(3) nanorod array followed by the hydrolysis in alkaline solution.The resulting CoOOH/Fe_(2)O_(3) exhibits a remarkably improved photocurrent density of 2.10 mA cm^(-2) at 1.23 V vs.RHE,which is ca.2.8 times that of bare Fe_(2)O_(3).In addition,a negative shift of onset potential ca.200 mV is achieved.The structural characterizations reveal the chelate EDTA plays important roles that enhance the adsorption of Co species and the formation of contact between CoOOH and Fe_(2)O_(3).(Photo)electrochemical analysis suggests,besides providing active sites for water oxidation,CoOOH at large extent promotes the charge separation and the charge transfer via passivating surface states and suppressing charge recombination.It also found CoOOH possesses some oxygen vacancies,which could act as trapping centers for photogenerated holes and facilitate the charge separation.Intensity modulated photocurrent spectroscopy(IMPS)shows that,under low applied potential the water oxidation mainly occurs on CoOOH,while under high applied potential the water oxidation could occur on both CoOOH and Fe_(2)O_(3).The findings not only provide an efficient strategy for designing ultrathin(oxy)hydroxides on semiconductors for PEC applications but also put forward a new insight on the role of CoOOH during water oxidation.

Ni_xWO_(2.72) nanorods as an efficient electrocatalyst for oxygen evolution reaction

Ni_xWO_(2.72) nanorods(NRs) are synthesized by a one-pot reaction of Ni(acac)_2 and WCl_4. In the rod structure, Ni(Ⅱ) intercalates in the defective perovskite-type WO_(2.72) and is stabilized. The Ni_xWO_(2.72) NRs show the x-dependent electrocatalysis for the oxygen evolution reaction(OER) in 0.1 M KOH with Ni_(0.78)WO_(2.72) being the most efficient, even outperforming the commercial Ir-catalyst. The synthesis is not limited to Ni_xWO_(2.72) but can be extended to M_xWO_(2.72)(M = Co, Fe) as well,providing a new class of oxide-based catalysts for efficient OER and other energy conversion reactions.

Multidimensional images and aberrations in STEM

Recent advances in scanning transmission electron microscopy(STEM)have led to increased development of multidimensional STEM imaging modalities and novel image reconstruction methods.This interest arises because the main electron lens in a modern transmission electron microscope usually has a diffraction-space information limit that is significantly better than the real-space resolution of the same lens.This state-of-affairs is sometimes shared by other scattering methods in modern physics and contributes to a broader excitement surrounding multidimensional techniques that scan a probe while recording diffraction-space images,such as ptychography and scanning nano-beam diffraction.However,the contrasting resolution in the two spaces raises the question as to what is limiting their effective performance.Here,we examine this paradox by considering the effects of aberrations in both image and diffraction planes,and likewise separate the contributions of pre-and post-sample aberrations.This consideration provides insight into aberration-measurement techniques and might also indicate improvements for super-resolution techniques.

Functionally graded structure of a nitride-strengthened Mg_(2)Si-based hybrid composite

The ex-situ incorporation of the secondary SiC reinforcement,along with the in-situ incorporation of the tertiary and quaternary Mg_(3)N_(2) and Si_(3)N_(4) phases,in the primary matrix of Mg_(2)Si is employed in order to provide ultimate wear resistance based on the laser-irradiation-induced inclusion of N_(2) gas during laser powder bed fusion.This is substantialized based on both the thermal diffusion-and chemical reactionbased metallurgy of the Mg_(2)Si–SiC/nitride hybrid composite.This study also proposes a functional platform for systematically modulating a functionally graded structure and modeling build-direction-dependent architectonics during additive manufacturing.This strategy enables the development of a compositional gradient from the center to the edge of each melt pool of the Mg_(2)Si–SiC/nitride hybrid composite.Consequently,the coefficient of friction of the hybrid composite exhibits a 309.3%decrease to–1.67 compared to–0.54 for the conventional nonreinforced Mg_(2)Si structure,while the tensile strength exhibits a 171.3%increase to 831.5 MPa compared to 485.3 MPa for the conventional structure.This outstanding mechanical behavior is due to the(1)the complementary and synergistic reinforcement effects of the SiC and nitride compounds,each of which possesses an intrinsically high hardness,and(2)the strong adhesion of these compounds to the Mg_(2)Si matrix despite their small sizes and low concentrations.

Revolutionizing Material Boundaries: High-Performance Diamond-Coated Steel via Long-Term MPCVD

This research explores Microwave Plasma Chemical Vapor Deposition (MPCVD) for depositing diamond films on steel alloys (316L, 4140, and 1018) with a vanadium carbide interlayer to enhance adhesion and compatibility. The study reveals that a soft vanadium carbide interlayer and the FCC lattice match lead to a Ta-C film. The results of the graphite inhibition and diamond deposition varied with the steel alloy underlayer composition. In the 316L steel alloy, we successfully formed a thick, compressive strain-induced, sp3-bonded tetrahedral amorphous carbon layer without graphite. The findings have wide-ranging applications in environments demanding high durability and thermal conductivity.

Benchmarking graph neural networks for materials chemistry

Graph neural networks(GNNs)have received intense interest as a rapidly expanding class of machine learning models remarkably well-suited for materials applications.To date,a number of successful GNNs have been proposed and demonstrated for systems ranging from crystal stability to electronic property prediction and to surface chemistry and heterogeneous catalysis.However,a consistent benchmark of these models remains lacking,hindering the development and consistent evaluation of new models in the materials field.Here,we present a workflow and testing platform,MatDeepLearn,for quickly and reproducibly assessing and comparing GNNs and other machine learning models.We use this platform to optimize and evaluate a selection of top performing GNNs on several representative datasets in computational materials chemistry.From our investigations we note the importance of hyperparameter selection and find roughly similar performances for the top models once optimized.We identify several strengths in GNNs over conventional models in cases with compositionally diverse datasets and in its overall flexibility with respect to inputs,due to learned rather than defined representations.Meanwhile several weaknesses of GNNs are also observed including high data requirements,and suggestions for further improvement for applications in materials chemistry are discussed.

The joint automated repository for various integrated simulations (JARVIS) for data-driven materials design

The Joint Automated Repository for Various Integrated Simulations(JARVIS)is an integrated infrastructure to accelerate materials discovery and design using density functional theory(DFT),classical force-fields(FF),and machine learning(ML)techniques.JARVIS is motivated by the Materials Genome Initiative(MGI)principles of developing open-access databases and tools to reduce the cost and development time of materials discovery,optimization,and deployment.

Synthesis of RE(OH)_2Cl and REOCl (RE=Eu, Tb) nanostructures

Anisotropic structures, nanoneedles, and nanospindles of rare earth hydroxychloride （RE（OH）2Cl） and oxychloride （REOCl） （rare earth=Eu and Tb） were synthesized. The rare earth hydroxychloride nanostructures were formed via a thermally assisted hydrolysis of the rare-earth sesquioxide nanocrystals. The morphological evolution of the nanostructures was studied using high-resolution transmission electron microscopy and scanning electron microscopy, while the structural evolution was investigated using X-ray diffraction techniques. The thermal stability of the rare earth hydroxychlorides was investigated using thermogravimetric analysis. The rare earth oxychloride nanospindles were synthesized via a simple heat-treatment of rare earth hydroxychloride nanospindles.

A review of the interactions between ceria and H2 and the applications to selective hydrogenation of alkynes

Cerium oxide(ceria) has found a wide variety of applications in catalysis including as a catalyst, a modifier, or a support, largely thanks to its robust redox properties and versatile acid-base function. While it is often utilized for oxidation reactions, ceria has recently attracted intense research interest for its unusual ability to selectively hydrogenate alkynes to alkenes. The intriguing hydrogenation ability of ceria has sparked renewed research efforts to understand how pure ceria works as a hydrogenation catalyst. In this review, recent advances in both experimental and computational studies of ceria are summarized, focusing on the interaction of ceria with H2 and in hydrogenation reactions. Significant insights from various studies including in situ spectroscopy/microscopy and theoretic modeling of ceria in hydrogen-involved reactions are discussed, which shed light on the origin of the hydrogenation ability of ceria and the reaction mechanisms involved in ceria-catalyzed alkyne hydrogenation. Ways to further improve both the mechanistic understanding and catalytic performance of ceria-based materials for hydrogenation reactions are proposed at the end in the summary and outlook section.

A bridge for accelerating materials by design

Recent technical advances in the area of nanoscale imaging,spectroscopy and scattering/diffraction have led to unprecedented capabilities for investigating materials structural,dynamical and functional characteristics.In addition,recent advances in computational algorithms and computer capacities that are orders of magnitude larger/faster have enabled large-scale simulations of materials properties starting with nothing but the identity of the atomic species and the basic principles of quantum and statistical mechanics and thermodynamics.Along with these advances,an explosion of high-resolution data has emerged.This confluence of capabilities and rise of big data offer grand opportunities for advancing materials sciences but also introduce several challenges.In this perspective,we identify challenges impeding progress towards advancing materials by design(e.g.,the design/discovery of materials with improved properties/performance),possible solutions and provide examples of scientific issues that can be addressed using a tightly integrated approach where theory and experiments are linked through big-deep data.

Preface to Special Issue on Advances in Ceria Catalysis

Ceria,which acts as a“star”among the metal-oxides,has established to be one of the most promising materials for chemical transformations and energy applications owing to its redox and acid–base properties.Ceria has become a key component in three-way catalytic converters,water-gas shift reaction,CO oxidation,methane combustion,and complex organic reactions.More importantly,introducing of other metals to ceria,tailoring the shape of the ceria,and reducing structure size of ceria,usually decrease the formation energy of oxygen vacancy(V?)and lead to unique catalytic performances.

Optimizing carbon/carbon supercapacitors in aqueous alkali sulfates electrolytes

Neutral aqueous alkali sulfate has shown great interests for developing environmentally friendly high voltage and high energy supercapacitors. This work focuses on systematically investigating the properties of symmetric carbon/carbon supercapacitors in neutral aqueous alkali sulfates. At room temperature, the largest power and energy density were obtained with K2SO4 electrolyte due to the smallest cation dimensions and highest electrical conductivity. At low temperature, aqueous Li2SO4 electrolyte presents the best performance due to the largest solubility, allowing a long-term stability at temperatures ranging between 20℃ and –10℃ at a maximum voltage of 1.8 V. The excellent stability has been confirmed that capacitance retention achieves as high as 92% after 10,000 cycles. The capacitance variations with temperatures could essentially result from kinetic diffusion barrier, ion dimension changes and fewer pseudo-capacitance contributions under different temperatures. This work highlights the selected virtues of different alkali sulfate electrolytes for enhanced supercapacitors.

Structure and Mechanical Properties of Waterborne Polyurethane-based Composites Filled with Self-assembled Supramolecular Nanoplatelets

New composites of waterborne polyurethane （WPU） as a matrix were prepared by incorporating rigid supramolecular nanoplatelets （SNs） as filler, which were self-assembled by the selective inclusion of β-cyclodextrin （β-CD） onto poly（propylene oxide） （PPO） segment in the poly（ethylene oxide）- block-PPO-block-poly（ethylene oxide） （PEO-b-PPO-b-PEO）. It is worth noting that, when the loading level of SN is lower than 3wt%, the SNs with moderate PEO length result in the simultaneous increase in strength, elongation and Young＇s modulus in contrast with neat WPU. If there is no stretching free PEO chain, both strength and elongation decrease in spite of an increase in Young＇s modulus. However, too long PEO chains result in the decrease of mechanical performances while the relatively higher loading-level of SNs also inhibits the enhancement of strength and elongation.

Activation and surface reactions of CO and H2 on ZnO powders and nanoplates under CO hydrogenation reaction conditions

Activation and surface reactions of CO and H2 on ZnO powders and nanoplates under CO hydrogenation reaction conditions were(quasi) in situ studied using temperature programmed surface reaction spectra, diffuse reflectance Fourier transform infrared spectroscopy, inelastic neutron scattering spectroscopy and electron paramagnetic resonance. CO undergoes disproportion reaction to produce gaseous CO2 and surface carbon adatoms, and adsorbs to form surface formate species. H2 adsorption forms dominant irreversibly-adsorbed surface hydroxyl groups and interstitial H species and very minor surface Zn-H species. Surface formate species and hydroxyl groups react to produce CO2 and H2, while surface carbon adatoms are hydrogenated by surface Zn-H species sequentially to produce CH(a), CH2(a), CH3(a)and eventually gaseous CH4. The ZnO nanoplates, exposing a higher fraction of Zn-ZnO(0001) and OZnO(000–1) polar facets, are more active than the ZnO powders to catalyze CO hydrogenation to CH4.These results provide fundamental understanding of the reaction mechanisms and structural effects of CO hydrogenation reaction catalyzed by ZnO-based catalysts.

Exploring the Spatial Control of Topotactic Phase Transitions Using Vertically Oriented Epitaxial Interfaces

Engineering oxygen vacancy formation and distribution is a powerful route for controlling the oxygen sublattice evolution that affects diverse functional behavior.The controlling of the oxygen vacancy formation process is particularly important for inducing topotactic phase transitions that occur by transformation of the oxygen sublattice.Here we demonstrate an epitaxial nanocomposite approach for exploring the spatial control of topotactic phase transition from a pristine perovskite phase to an oxygen vacancy-ordered brownmillerite(BM)phase in a model oxide La_(0.7)Sr_(0.3)MnO_(3)(LSMO).Incorporating a minority phase NiO in LSMO films creates ultrahigh density of vertically aligned epitaxial interfaces that strongly influence the oxygen vacancy formation and distribution in LSMO.Combined structural characterizations reveal strong interactions between NiO and LSMO across the epitaxial interfaces leading to a topotactic phase transition in LSMO accompanied by significant morphology evolution in NiO.Using the NiO nominal ratio as a single control parameter,we obtain intermediate topotactic nanostructures with distinct distribution of the transformed LSMO-BM phase,which enables systematic tuning of magnetic and electrical transport properties.The use of self-assembled heterostructure interfaces by the epitaxial nanocomposite platform enables more versatile design of topotactic phase structures and correlated functionalities that are sensitive to oxygen vacancies.

Probing the Wave Nature of Light-Matter Interaction

The wave-particle duality of light is a controversial topic in modern physics. In this context, this work highlights the ability of the wave-nature of light on its own to account for the conservation of energy in light-matter interaction. Two simple fundamental properties of light as wave are involved: its period and its power P. The power P depends only on the amplitude of the wave’s electric and magnetic fields (Poynting’s vector), and can easily be measured with a power sensor for visible and infrared lasers. The advantage of such a wave-based approach is that it unveils unexpected effects of light’s power P capable of explaining numerous results published in current scientific literature, of correlating phenomena otherwise considered as disjointed, and of making predictions on ways to employ the electromagnetic (EM) waves which so far are unexplored. In this framework, this work focuses on determining the magnitude of the time interval that, coupled with light’s power P, establishes the energy conserved in the exchange of energy between light and matter. To reach this goal, capacitors were excited with visible and IR lasers at variable average power P. As the result of combining experimental measurements and simulations based on the law of conservation of energy, it was found that the product of the period of the light by its power P fixes the magnitude of the energy conserved in light’s interaction with the capacitors. This finding highlights that the energy exchanged is defined in the time interval equal to the period of the light’s wave. The validity of the finding is shown to hold in light’s interaction with matter in general, e.g. in the photoelectric effect with x-rays, in the transfer of electrons between energy levels in semiconducting interfaces of field effect transistors, in the activation of photosynthetic reactions, and in the generation of action potentials in retinal ganglion cells to enable vision in vertebrates. Finally, the validity of the finding is investigated in the low frequency spectrum of the EM waves by exploring possible consequences in microwave technology, and in harvesting through capacitors the radio waves dispersed in the environment after being used in telecommunications as a source of usable electricity.