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We examined the electrical and local structural properties of a VO2 film at different electric fields using electrical resistance and x-ray absorption fine structure (XAFS) measurements at the V K edge in the temperature range of 30–100 °C. The Tc value of the metal-to-insulator transition (MIT) during both heating and cooling decreases with electric field. When the electric field exceeds a certain value, the MIT becomes sharper due to Joule heating. The MIT, the structural phase transition (SPT), and the pre-edge peak transition of the VO2 do not congruently occur at a uniform temperature. A metallic VO2 is observed in only the rutile (or M2) symmetry. An electric field induces a substantial amount of conduction electrons in insulating VO2. Simultaneously measured resistance and XAFS reveal that Joule heating caused by an external electric field significantly affects the MIT and SPT of VO2.

Anomalous x-ray scattering (AXS) and extended x-ray absorption fine structure (EXAFS) were used to determine the local structure of Mo in CrFeCoNiMox (x = 0.11, 0.18, and 0.23), a high-entropy alloy with a face-centered cubic (FCC) lattice. No superlattice peaks were observed down to the 10–4 intensity level. This observation along with the nearly constant decrease of the FCC diffraction peaks above the Mo K absorption edge suggests that Mo atoms have no preferred site occupancy in the FCC lattice. Modeling of the EXAFS data suggests a local chemical order in CrFeCoNiMox, where in Mo-rich samples (e.g., x = 0.23), Mo atoms are preferably surrounded by lighter atoms, such as Cr.

A single-atom Pt1 /CeO2 catalyst formed by atom trapping (AT, 800 °C in air) shows excellent thermal stability but is inactive for CO oxidation at low temperatures owing to over-stabilization of Pt2+ in a highly symmetric square-planar Pt1 O4 coordination environment. Reductive activation to form Pt nanoparticles (NPs) results in enhanced activity; however, the NPs are easily oxidized, leading to drastic activity loss. Herein we show that tailoring the local environment of isolated Pt2+ by thermal-shock (TS) synthesis leads to a highly active and thermally stable Pt1 /CeO2 catalyst. Ultrafast shockwaves (>1200 °C) in an inert atmosphere induced surface reconstruction of CeO2 to generate Pt single atoms in an asymmetric Pt1 O4 configuration. Owing to this unique coordination, Pt1 δ+ in a partially reduced state dynamically evolves during CO oxidation, resulting in exceptional low-temperature performance. CO oxidation reactivity on the Pt1 /CeO2 _TS catalyst was retained under oxidizing conditions.

Oxygen redox plays a prominent role in enhancing the energy density of Mn-based layered cathodes. However, understanding the factors affecting the reversibility of oxygen redox is nontrivial due to the complicated concurrent structural and chemical transformations. Herein, we show that local Mn‒O symmetry induced structural and chemical evolutions majorly dictate the reversibility of oxygen redox of NaxLiyMn1-yO2 in Na cells. We find that NaxLi­yMn1-yO2 with Jahn-Teller distorted MnO6 octahedra undergoes severe Mn dissolution during cycling, which destabilizes the transition metal layer resulting in poor Li retention and irreversible oxygen redox. Jahn-Teller distortion of MnO6 octahedra can be suppressed by modulating the local charge of Mn and Mn‒O distance through Mg/Ti dual doping. This leads to reduced Mn dissolution resulting in more reversible oxygen redox. Such stabilization significantly improves the electrochemical performance of Mg/Ti dual doped NaxLiyMn1-yO2. Through this work, we show that promoting reversible oxygen redox can benefit from structural stabilization at local length scale, and that modifying the chemical environment through doping chemistry is an efficient strategy to promote local structural stability and thus, oxygen redox.

ConspectusThe redox reaction pathway is crucial to the sustainable production of the fuels and chemicals required for a carbon-neutral society. Our society is becoming increasingly dependent on devices using batteries and electrolyzers, all of which rely on a series of redox reactions. The overall properties of oxide materials make them very well suited for such electrochemical and catalytic applications due to their associated cationic redox properties and the static site-adsorbate interactions. As these technologies have matured, it has become apparent that defect-driven redox reactions, defect-coupled diffusion, and structural transformations that are both time- and rate-dependent are also critical materials processes. This change in focus, considering not only redox properties but also more complex, dynamic behaviors, represents a new research frontier in the molecular sciences as they are strongly linked to device operation and degradation and lie at the heart of various phenomena that take place at electrochemical interfaces. Fundamental studies of the structural, electronic, and chemical transformation mechanisms are key to the advancement of materials and technological innovations that could be implemented in various electrochemical systems.In this Account, we focus on recent studies and advances in characterizing and understanding the dynamic redox evolution and structural transformations that take place in model perovskites and layered oxides under reactive conditions and correlate them with degradation mechanisms and operations in electrolyzers and batteries. We show that the dynamic evolution of oxygen vacancies and cationic migration in the surface or bulk occurs at the solid-liquid interface, using a combination of different synchrotron-based X-ray spectroscopies and scattering probes. Detailed redox-structure-reactivity correlation studies show how defects and diffusion processes can be tailored to drive various physical and chemical transformations in electrolyzers and batteries. We also highlight a strong correlation between oxygen redox reactivity and structural reorganization in both model thin films and particles, helping to bridge the gap between fundamental studies of the reaction mechanism and device applications. On the basis of these findings, we discuss strategies to probe and tune the redox reactivity and structural stability of the redox-active oxide interphase toward devising efficient pathways for energy and chemical harvesting.

Multiferroic oxide heterostructures consisting of ferromagnetic and ferroelectric components hold the promise for nonvolatile magnetic control via ferroelectric polarization, advantageous for the low-dissipation spintronics. Modern understanding of the magnetoelectric coupling in these systems involves structural, orbital, and magnetic reconstructions at interfaces. Previous works have long proposed polarization-dependent interfacial magnetic structures; however, direct evidence is still missing, which requires advanced characterization tools with near-atomic-scale spatial resolutions. Here, extensive polarized neutron reflectometry (PNR) studies have determined the magnetic depth profiles of PbZr0.2Ti0.8O3/La0.67Sr0.33MnO3 (PZT/LSMO) bilayers with opposite self-polarizations. When the LSMO is 2-3 nm thick, the bilayers show two magnetic transitions on cooling. However, temperature-dependent magnetization is different below the lower-temperature transition for opposite polarizations. PNR finds that the LSMO splits into two magnetic sublayers, but the inter-sublayer magnetic couplings are of opposite signs for the two polarizations. Near-edge X-ray absorption spectroscopy further shows contrasts in both the Mn valences and the Mn-O bond anisotropy between the two polarizations. This work completes the puzzle for the magnetoelectric coupling model at the PZT/LSMO interface, showing a synergic interplay among multiple degrees of freedom toward emergent functionalities at complex oxide interfaces.

P2-structured Na0.67Ni0.33Mn0.67O2 (PNNMO) is a promising Na-ion battery cathode material, but its rapid capacity decay during cycling remains a hurdle. Li doping in layered transition-metal oxide (TMO) cathode materials is known to enhance their electrochemical properties. Nevertheless, the influence of Li at different locations in the structure has not been investigated. Here, the crystallographic role and electrochemical impact of lithium on different sites in PNNMO is investigated in Li x Na0.67-y Ni0.33Mn0.67O2+δ (0.00 ≤ x ≤ 0.2, y = 0, 0.1). Lithium occupancy on prismatic Na sites is promoted in Na-deficient (Na < 0.67) PNNMO, evidenced by ex situ and operando synchrotron X-ray diffraction, X-ray absorption spectroscopy, and 7Li solid-state nuclear magnetic resonance. Partial substitution of Na with Li leads to enhanced stability and slightly increased specific capacity compared to PNNMO. In contrast, when lithium is located primarily on octahedral TM sites, capacity is increased but at the cost of stability.

Fe-N-C with atomically dispersed Fe single atoms is the most promising candidate to replace platinum for the oxygen reduction reaction (ORR) in fuel cells. However, the conventional synthesis procedures require quantities solvents and metal precursors, sluggish adsorption process, and tedious washing, resulting in limited metal doping and uneconomical for large-scale production. For the first time, Fe2O3 is adopted as the Fe precursor to derive abundant single Fe atoms dispersed on carbon surfaces. The Fe-N-C catalyst synthesized by this simple method shows an excellent ORR activity with half-wave potentials of 0.82 and 0.90 V in acidic and alkaline solutions, respectively. A single fuel cell with an optimized Fe-N-C cathode shows a high peak power density of 0.84 W cm-2. The solid-state transformation synthesis method developed in this study may shed light on mass production of single-atom-based catalysts.

With the increasing application of steel–concrete-steel (SCS) composite structures in engineering constructions, the mechanical behaviors of steel plates and concrete in SCS structures are becoming increasingly important. This study aimed to evaluate the individual smeared behaviors of the steel plate and concrete from some tested SCS panels and analyze the main characteristics of the plates and concrete. An incremental step analysis method was used to analyze prior experimental research, in which seven SCS panels were subjected to proportional biaxial tension–compression loading. This method is based on Navier’s three principles (stress equilibrium, strain compatibility, and the constitutive laws of materials). Using this method, the smeared behaviors of the steel plates and concrete were evaluated. Through analysis, it was found that these smeared behaviors exhibit the following characteristics: When plastic flow occurs, the smeared stress state of steel plates flows on the yield surface after yielding, which results in an increasing principal tensile stress and a decreasing principal compressive stress. For the concrete in the principal compressive direction of the SCS panels, confinement and softening effects may coexist. The concrete in the principal tensile direction of the SCS panels exhibits two different behaviors, and an unexpected compressive stress may be generated. These findings will provide a clearer understanding of the mechanical behaviors of concrete and steel plates in SCS panels in future research.

By increasing the charging voltage, a cell specific energy of >400 W h kg−1 is achievable with LiNi0.8Mn0.1Co0.1O2 in Li metal batteries. However, stable cycling of high-nickel cathodes at ultra-high voltages is extremely challenging. Here we report that a rationally designed sulfonamide-based electrolyte enables stable cycling of commercial LiNi0.8Co0.1Mn0.1O2 with a cut-off voltage up to 4.7 V in Li metal batteries. In contrast to commercial carbonate electrolytes, the electrolyte not only suppresses side reactions, stress-corrosion cracking, transition-metal dissolution and impedance growth on the cathode side, but also enables highly reversible Li metal stripping and plating leading to a compact morphology and low pulverization. Our lithium-metal battery delivers a specific capacity >230 mA h g−1 and an average Coulombic efficiency >99.65% over 100 cycles. Even under harsh testing conditions, the 4.7 V lithium-metal battery can retain >88% capacity for 90 cycles, advancing practical lithium-metal batteries. Charging at high voltages in principle makes batteries energy dense, but this is often achieved at the cost of the cycling stability. Here the authors design a sulfonamide-based electrolyte to enable a Li metal battery with a state-of-the-art cathode at an ultra-high voltage of 4.7 V while maintaining cyclability.

To evaluate the fire resistance of a structural member, the temperature profile in the cross section of the member needs to be obtained first. Full-scale fire tests have not been conducted on floor systems with steel-plate composite structures, termed SC floors. The traditional finite element analysis does not yield reliable temperature predictions in the steel and concrete of the SC floor under a standard fire. In this paper, the effective thermal properties of concrete in an SC floor are proposed for evaluating the transient temperature field according to the special heat transfer mechanism found by test data. The validity of these effective thermal properties is established by incorporating them into a finite element model and comparing the temperature predictions with data from fire tests. It is shown that the proposed effective thermal properties of concrete provide a good prediction of the temperature field in an SC floor under fire. The derivation process of the effective thermal properties based on the heat transfer analysis makes it possible to expand the scope of its application when the situation is similar to an SC floor.

VO2 is a highly correlated electron system which has a metal-to-insulator transition (MIT) with a dramatic change of conductivity accompanied by a first-order structural phase transition (SPT) near room temperature. The origin of the MIT is still controversial and there is ongoing debate over whether an SPT induces the MIT and whether the Tc can be engineered using artificial parameters. We examined the electrical and local structural properties of Cr- and Co-ion implanted VO2 (Cr-VO2 and Co-VO2) films using temperature-dependent resistance and X-ray absorption fine structure (XAFS) measurements at the V K edge. The temperature-dependent electrical resistance measurements of both Cr-VO2 and Co-VO2 films showed sharp MIT features. The Tc values of the Cr-VO2 and Co-VO2 films first decreased and then increased relative to that of pristine VO2 as the ion flux was increased. The pre-edge peak of the V K edge from the Cr-VO2 films with a Cr ion flux ≥ 1013 ions/cm2 showed no temperature-dependent behavior, implying no changes in the local density of states of V 3d t2g and eg orbitals during MIT. Extended XAFS (EXAFS) revealed that implanted Cr and Co ions and their tracks caused a substantial amount of structural disorder and distortion at both vanadium and oxygen sites. The resistance and XAFS measurements revealed that VO2 experiences a sharp MIT when the distance of V–V pairs undergoes an SPT without any transitions in either the VO6 octahedrons or the V 3d t2g and eg states. This indicates that the MIT of VO2 occurs with no changes of the crystal fields.

Although liquid mercury (Hg) has been known since antiquity, the formation of stable solid nano forms of Hg at room temperature has not been reported so far. Here, for the first time, we report a simple sonochemical route to obtain solid mercury nanoparticles, stabilized by reduced graphene oxide at ambient conditions. The as-formed solid Hg nanoparticles were found to exhibit remarkable rhombohedral morphology and crystallinity at room temperature. Extensive characterization using various physicochemical techniques revealed the unique properties of the solid nanoparticles of Hg compared to its bulk liquid metal phase. Furthermore, the solid nature of the Hg nanoparticles was studied electrochemically, revealing distinctive properties. We believe that solid Hg nanoparticles have the potential for important applications in the fields of electroanalytical chemistry and electrocatalysis., Formation of the stable solid mercury nanoparticles by acoustic cavitation and their electrochemical activity compared to its bulk liquid metal.

The construction of favorable photoanode configurations is of great importance to enhance the performance of dye-sensitized solar cells (DSSCs). In this work, a double-layer photoanode architecture consisting of a top layer of hierarchical TiO2 networks (HTNs) and a bottom layer of commercial P25 nanoparticles (NPs) was designed and prepared by a facile one-step hydrothermal method. This unique double-layer structure not only affords stronger light scattering and faster electron transport relative to the single-layer P25 photoanode, but also ensures more close contact between different functional layers in contrast to commonly used multistep mechanical coated photoanodes. Furthermore, Au NPs with particle sizes of around 20 nm were incorporated to decorate the HTN photoanode. The localized surface plasmon resonance effect of such Au NPs significantly enhances the light absorption of N719 dye molecules. Benefitted from the splendid light harvesting and superior electron collection, the Au-HTN photoanode configuration delivers an enhanced power conversion efficiency of 5.97%, yielding ∼19% improvement compared to the device based on the conventional P25 photoanode. This work highlights the design of photoanodes with unique nanostructures for enhancing the photovoltaic performance of DSSCs.

The Hf(OTf)4-catalyzed three-component reaction (3CR) was employed as a powerful tool for facile access to a library of 23 pyrimido[2,1-b][1,3]benzothiazole (PBT)-based AIEgens with full-color tunability, solid-state fluorescence quantum yields of up to 86.8%, and high crystallizability. As atypical propeller-shaped molecules, PBT AIEgens were experimentally determined to dissipate the energy of the excited state via the rotation of the exocyclic carbonyl (ester/ketone) rather than the commonly known phenyl group. Theoretical calculations and crystallographic analysis of PBT AIEgens provide insights into their unique structure–property relationships and AIE mechanism from orbital and molecular aspects, respectively.

Efficient electrocatalysts for the oxygen evolution reaction (OER) are paramount to the development of electrochemical devices for clean energy and fuel conversion. However, the structural complexity of heterogeneous electrocatalysts makes it a great challenge to elucidate the surface catalytic sites and OER mechanisms. Here, we report that catalytic single-site Co in a well-defined brookite TiO2 nanorod (210) surface (Co-TiO2) presents turnover frequencies that are among the highest for Co-based heterogeneous catalysts reported to date, reaching 6.6 ± 1.2 and 181.4 ± 28 s−1 at 300 and 400 mV overpotentials, respectively. Based on grand canonical quantum mechanics calculations and the single-site Co atomic structure validated by in situ and ex situ spectroscopic probes, we have established a full description of the catalytic reaction kinetics for Co-TiO2 as a function of applied potential, revealing an adsorbate evolution mechanism for the OER. The computationally predicted Tafel slope and turnover frequencies exhibit exceedingly good agreement with experiment. The rational design of efficient water oxidation electrocatalysts is paramount to the development of electrochemical devices. Now, a Co-TiO2 single-site catalyst is presented for alkaline water oxidation with high intrinsic activity, and its mechanism has been studied by grand canonical quantum mechanics calculations and in situ techniques.

Sodium-ion batteries (SIBs) have been attracting an ever-growing research interest, mainly ascribed to their cost-effectiveness. However, SIBs have been significantly hindered by lack of a suitable anode. Herein, an exceptional Cu2S-based composite anode is developed via a facile ball-milling method, in which Cu2S particles are wrapped by nitrogen-doped graphene sheets (Cu2S@NG). This Cu2S@NG composite anode enables extremely long cycling life, ultra-stable cyclability with high capacity, and excellent rate capability. The superior performance of the Cu2S@NG composite is owing to its intriguing core-shell structure and the exceptional properties of both the Cu2S and NG. In this study, it is found that the NG shell yields multiple merits in improving the performance of Cu2S: (i) mitigating the loss of active materials, (ii) constituting a stable interface, (iii) providing improved electrical conductivity and good ionic transfer, and (iv) enhancing mechanical integrity. Additionally, the vital effects of different voltage windows and a surface coating via atomic layer deposition on further enhancing performance are clarified. Significantly, the electrochemical mechanism of Cu2S during sodiation/desodiation is unveiled using advanced synchrotron-based in-situ X-ray diffraction and X-ray adsorption spectroscopy. This work represents a great advance in seeking high-performance anodes in SIBs.

Lithium–sulfur batteries are attractive alternatives to lithium-ion batteries because of their high theoretical specific energy and natural abundance of sulfur. However, the practical specific energy and cycle life of Li–S pouch cells are significantly limited by the use of thin sulfur electrodes, flooded electrolytes and Li metal degradation. Here we propose a cathode design concept to achieve good Li–S pouch cell performances. The cathode is composed of uniformly embedded ZnS nanoparticles and Co–N–C single-atom catalyst to form double-end binding sites inside a highly oriented macroporous host, which can effectively immobilize and catalytically convert polysulfide intermediates during cycling, thus eliminating the shuttle effect and lithium metal corrosion. The ordered macropores enhance ionic transport under high sulfur loading by forming sufficient triple-phase boundaries between catalyst, conductive support and electrolyte. This design prevents the formation of inactive sulfur (dead sulfur). Our cathode structure shows improved performances in a pouch cell configuration under high sulfur loading and lean electrolyte operation. A 1-A-h-level pouch cell with only 100% lithium excess can deliver a cell specific energy of >300 W h kg−1 with a Coulombic efficiency >95% for 80 cycles. The shuttling effect in Li–S batteries can be drastically suppressed by using a single-atom Co catalyst and polar ZnS nanoparticles embedded in a macroporous conductive matrix as a cathode. Using this strategy, Li–S pouch cells show stable cycling and high energy performances.

Alloy-based materials are promising anodes for rechargeable batteries because of their higher theoretical capacities in comparison to graphite. Unfortunately, the huge volume changes during cycling...

The ability to precisely engineer the doping of sub-nanometer bimetallic clusters offers exciting opportunities for tailoring their catalytic performance with atomic accuracy. However, the fabrication of singly dispersed bimetallic cluster catalysts with atomic-level control of dopants has been a long-standing challenge. Herein, we report a strategy for the controllable synthesis of a precisely doped single cluster catalyst consisting of partially ligand-enveloped Au4Pt2 clusters supported on defective graphene. This creates a bimetal single cluster catalyst (Au4Pt2/G) with exceptional activity for electrochemical nitrogen (N2) reduction. Our mechanistic study reveals that each N2 molecule is activated in the confined region between cluster and graphene. The heteroatom dopant plays an indispensable role in the activation of N2 via an enhanced back donation of electrons to the N2 LUMO. Moreover, besides the heteroatom Pt, the catalytic performance of single cluster catalyst can be further tuned by using Pd in place of Pt as the dopant., The fabrication of singly dispersed metal cluster catalysts with atomic-level control of dopants is a long-standing challenge. Here, the authors report a strategy for the synthesis of a precisely doped single cluster catalyst which shows exceptional activity for electrochemical dinitrogen reduction.

Achieving stable, low-cost electrocatalysts represents a daunting challenge towards practical water oxidation reactions. Here, we report that a degraded electrocatalyst can be revivified under catalytic operating conditions by manipulating reversible phase segregation. Under the oxygen evolution reaction conditions, Fe segregation develops in the Ni–Fe hydroxide host lattice, with the formation of FeOOH, resulting in an interface between the FeOOH and the host lattice. A dynamic metal dissolution–redeposition process accelerates the Fe segregation and formation of the FeOOH secondary phase, resulting in catalyst deactivation. Operando synchrotron spectroscopic and microscopic analyses suggest that the phase segregation is reversible between the water oxidation potential and the catalyst reduction potential. Therefore, we have developed an intermittent reduction methodology to revivify the catalytic activity under the operating conditions, enhancing catalyst durability. The present study highlights that tailoring phase segregation at the catalyst/electrolyte interface constitutes an important strategy for revivifying and stabilizing catalytic activity. Achieving long-term stability of water oxidation electrocatalysts remains a formidable challenge. Now, an in situ electrochemical reduction strategy to revivify mixed Ni–Fe hydroxide catalysts by reversible phase segregation is presented.

The oxygen octahedral rotation around out-of-plane axis is explored to study its effect on metastable status, magnetic cluster glass in manganite. The antiphase rotation around the out-of-plane axis (TiO6 a0a0c-) of SrTiO3 enhances the Mn-O bond anisotropy along in-plane and out-of-plane directions, and weakens the ferromagnetic interactions in 12 nm Pr0.67Sr0.33MnO3 film on (001) SrTiO3 substrate, which together promote the formation of magnetic cluster-glassiness and enlarges the irreversible magnetoresistance effect with enhanced relaxation time of charge carrier. The effect of TiO6 a0a0c- in SrTiO3 substrate on materials properties is obvious with large irreversible magnetoresistance effect for thin film, which fades away with the increase of film thickness. At 10 K, the irreversible magnetoresistance is 0.91 for 12 nm film, and 0.22 for 30 nm film. This work extends current understanding on interfacial coupling to metastable status, and could help to explore other systems in perovskite structure with octahedral rotation.

The further improvement of sodium ion batteries requires the elucidation of the mechanisms pertaining to reversibility, which allows the novel design of the electrode structure. Here, through a hydrogel-embedding method, we are able to confine the growth of few-layer SnS2 nanosheets between a nitrogen- and sulfur-doped carbon nanotube (NS-CNT) and amorphous carbon. The obtained carbon-sandwiched SnS2 nanosheets demonstrate excellent sodium storage properties. In operando small-angle X-ray scattering combined with the ex situ X-ray absorption near edge spectra reveal that the redox reactions between SnS2/NS-CNT and the sodium ion are highly reversible. On the contrary, the nanostructure evolution is found to be irreversible, in which the SnS2 nanosheets collapse, followed by the regeneration of SnS2 nanoparticles. This work provides operando insights into the chemical environment evolution and structure change of SnS2-based anodes, elucidating its reversible reaction mechanism, and illustrates the significance of engineered carbon support in ensuring the electrode structure stability.

To reveal the formation and evolution behavior of inclusions during magnesium treatment and resulfurization in Al-killed free-cutting steel, both laboratory experiments and thermodynamic calculations were carried out. The extracted samples were polished and analyzed by scanning electron microscopy and energy-dispersive spectroscopy. The results indicated that MgO formed immediately and then transferred to MgO·Al2O3 with the homogenization of [Mg] in steel in the case of low magnesium addition (w[Mg]

Doping chemistry has been regarded as an efficient strategy to overcome some fundamental challenges facing the “no-cobalt” LiNiO2 cathode materials. By utilizing the doping chemistry, we evaluate t...

A central theme of nanocrystal (NC) research involves synthesis of dimension-controlled NCs and studyof size-dependent scaling laws governing their optical, electrical, magnetic, and thermodynamic properties. Here, we describe the synthesis of monodisperse CdO NCs that exhibit high quality-factor (up to 5.5) mid-infrared (MIR) localized surface plasmon resonances (LSPR) and elucidate the inverse scaling relationship between carrier concentration and NC size. The LSPR wavelength is readily tunable between 2.4 and ∼6.0 μm by controlling the size of CdO NCs. Structural and spectroscopic characterization provide strong evidence that free electrons primarily originate from self-doping due to NC surface-induced nonstoichiometry. The ability to probe and to control NC stoichiometry and intrinsic defects will pave the way toward predictive synthesis of doped NCs with desirable LSPR characteristics.

Nickel-iron layered double hydroxide (NiFe LDH) is a promising oxygen evolution reaction (OER) electrocatalyst under alkaline conditions. Much research has been performed to understand the structure-activity relationship of NiFe LDH under OER conditions. However, the specific role of the Fe species remains unclear and under debate. Herein, based on DFT calculations, it was discovered that the edge Fe sites show higher activity towards OER than either the edge Ni sites or lattice sites. Therefore, a facile acid-etching method was proposed to controllably induce the formation of edge Fe sites in NiFe LDH, and the obtained sample exhibited higher OER activity. X-ray absorption near edge structure and extended X-ray absorption fine structure analyses further revealed that the interaction of the edge Fe species with Ni is believed to contribute to the enhancement of the OER performance. This work provides a new understanding of the structure-activity relationship in NiFe LDH and offers a facile method for the design of efficient electrocatalysts in an alkaline environment.

The methane activation and methane dry reforming reactions were studied and compared over 4 wt % Ni/CeO2 and 4 wt % Ni/CeZrO2 (containing 20 wt % Zr) catalysts. Upon the incorporation of Zr into th...

Titanium-based layered oxides (TLOs) are one of the most promising electrode material families for sodium-ion batteries (NIBs) due to their smooth charge/discharge profiles and excellent cycle performance. However, the reaction mechanism of these materials, especially the reason for the disappearance of multiple voltage plateaus, is still not clear. Herein, two representative TLOs (Na2/3Ni1/3Ti2/3O2 and Na2/3Co1/3Ti2/3O2) with the same P2 crystal structure have been studied to scrutinize those unexplained issues. In situ synchrotron high-energy X-ray diffraction revealed a solid solution reaction mechanism for both, suggesting the absence of rigid phase transitions upon electrochemical cycling. An interesting “spring effect” of the TiO6 octahedron, i.e., the reversible vibration of the central Ti atom inside the local octahedron upon electrochemical redox, was demonstrated by advanced X-ray absorption spectroscopy and theoretical calculations. Such an effect could suppress the rigid phase transitions, and result in smooth charge/discharge profiles and enhanced cycle stability. This work not only accounts for the disappearance of multiple voltage plateaus of TLOs for NIBs, but also provides an effective local-structure viewpoint to increase the cycle stability of electrode materials for other advanced battery systems.

To understand the effect of selenium doping on the good cycling performance and rate capability of a Ge0.9Se0.1 electrode, the dynamic morphological and phase changes of the Ge0.9Se0.1 electrode were investigated by synchrotron-based operando transmission X-ray microscopy (TXM) imaging, X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS). The TXM results show that the Ge0.9Se0.1 particle retains its original shape after a large volume change induced by (de)lithiation and undergoes a more sudden morphological and optical density change than pure Ge. The difference between Ge0.9Se0.1 and Ge is attributed to a super-ionically conductive Li–Se–Ge network formed inside Ge0.9Se0.1 particles, which contributes to fast Li-ion pathways into the particle and nano-structuring of Ge as well as buffering the volume change of Ge. The XRD and XAS results confirm the formation of a Li–Se–Ge network and reveal that the Li–Se–Ge phase forms during the early stages of lithiation and is an inactive phase. The Li–Se–Ge network also can suppress the formation of the crystalline Li15Ge4 phase. These in situ and operando results reveal the effect of the in situ formed, super-ionically conductive, and inactive network on the cycling performance of Li-ion batteries and shed light on the design of high capacity electrode materials.

Enhancing the oxygen evolution reaction (OER) performance of NiO materials will greatly expand their applications as low-cost, bifunctional electrocatalysts for water splitting reactions. Introducing stress into the surface layer of catalysts represents an effective method to enhance their catalytic reactivity. Herein, we create compressive stress at the NiOOH/NiO interface using the battery conversion chemistry and in situ Ni to NiOOH transformation. As a result, the OER performance is enhanced by 20 fold compared with that of pure NiO. However, due to the corrosive environment that the electrocatalyst experiences under OER conditions, the stress is released after several CV cycles. The present study demonstrates the importance of interfacial stress that can be produced from in situ surface phase transformation of the electrocatalyst, as well as highlights the challenge of maintaining the mechanical stress under OER conditions during long-term applications.

A superstructure can elicit versatile new properties of materials by breaking their original geometrical symmetries. It is an important topic in the layered graphene-like two-dimensional transition-metal dichalcogenides (TMDs), but its origin remains unclear. Using diamond-anvil cell techniques, synchrotron x-ray diffraction, x-ray absorption, and the first-principles calculations, we show that the evolution from the weak Van der Waals bonding to the Heisenberg covalent bonding between layers induces an isostructural transition in quasi-two-dimensional 1$\textit{T}$-type VSe$_2$ at high pressure. Furthermore, our results show that high-pressure induce a novel superstructure at 15.5 GPa, rather than suppress as it would normally, which is unexpected. It is driven by the Fermi surface nesting, enhanced by the pressure-induced distortion. The results suggest that the superstructure not only appears in the two-dimensional structure but also can emerge in the pressure-tuned three-dimensional structure with new symmetry and develop superconductivity., Comment: 17 pages, 5 figures

The practical implementation of Co-free, LiNiO2-derived cathodes has been prohibited by their poor cycle life and thermal stability, resulting from the structural instability, phase transformations...

Atomic-level understanding of the active sites and transformation mechanisms under realistic working conditions is a prerequisite for rational design of high-performance photocatalysts. Here, by using correlated scanning fluorescence X-ray microscopy and environmental transmission electron microscopy at atmospheric pressure, in operando, we directly observe that the (110) facet of a single Cu2O photocatalyst particle is photocatalytically active for CO2 reduction to methanol while the (100) facet is inert. The oxidation state of the active sites changes from Cu(i) towards Cu(ii) due to CO2 and H2O co-adsorption and changes back to Cu(i) after CO2 conversion under visible light illumination. The Cu2O photocatalyst oxidizes water as it reduces CO2. Concomitantly, the crystal lattice expands due to CO2 adsorption then reverts after CO2 conversion. The internal quantum yield for unassisted wireless photocatalytic reduction of CO2 to methanol using Cu2O crystals is ~72%. Photocatalytic reduction of CO2 to methanol offers a promising route to storage of solar energy in the form of chemical fuels. Here, Wu et al. use in operando microscopy to identify the active facets for CO2 reduction on Cu2O and exploit this to obtain high conversion efficiency and selectivity to methanol.

Developing stable cathode materials represents a crucial step toward long-life sodium-ion batteries. P2-type layered oxides are important as cathodes for their reversibility, but their long-term pe...

As a promising alternative to the market-leading lithiumion batteries, low-cost sodium-ion batteries (SIBs) are attractive for applications such as large-scale electrical energy storage systems. The energy density, cycling life, and rate performance of SIBs are fundamentally dependent on dynamic physiochemical reactions, structural change, and morphological evolution. Therefore, it is essential to holistically understand SIBs reaction processes, degradation mechanisms, and thermal/mechanical behaviors in complex working environments. The recent developments of advanced in situ and operando characterization enable the establishment of the structure-processing-property- performance relationship in SIBs under operating conditions. This Review summarizes significant recent progress in SIBs exploiting in situ and operando techniques based on X-ray and electron analyses at different time and length scales. Through the combination of spectroscopy, imaging, and diffraction, local and global changes in SIBs can be elucidated for improving materials design. The fundamental principles and state-of-the-art capabilities of different techniques are presented, followed by elaborative discussions of major challenges and perspectives. U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences program [DE-SC0019121]; National Science Foundation [CBET 1912885]; USDA AFRI Foundational and Applied Program [2020-67021-31139]; U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-06CH11357]; U.S. DOE [DE-AC02-06CH11357]; Canadian Light Source Published version D.H., E.G., J.R., K.G., Y.L., and H.X. acknowledge the funding support by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences program under Award Number DE-SC0019121. The work at Virginia Tech was supported by the National Science Foundation under no. CBET 1912885 and the USDA AFRI Foundational and Applied Program (grant number 2020-67021-31139). Use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. This research used resources of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, and was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357, and the Canadian Light Source, and its funding partners.

Proton exchange membrane fuel cell converts hydrogen and oxygen into electricity with zero emission1. The high cost and low durability of Pt-based electrocatalysts for oxygen reduction reaction hinder its wide applications2,3. The development of non-precious metal electrocatalysts also reaches the bottleneck because of the low activity and durability4,5. Here we rationally design a hybrid electrocatalyst consisting of atomically dispersed Pt and Fe single atoms and intermetallic PtFe alloy nanoparticles. The Pt mass activity of the hybrid catalyst is 3.5 times higher than that of commercial Pt/C in a fuel cell. More importantly, the fuel cell with an ultra-low Pt loading in the cathode (0.015 mgPt cm-2) shows unprecedented durability, with 93.6% activity retention after 100,000 cycles and no noticeable current drop at 0.6 V for at least 206 h. These results highlight the importance of the synergistic effects among active sites in hybrid electrocatalysts and provide an alternative way to design more active and durable low-Pt electrocatalysts for electrochemical devices.

Zinc-blende CdS nanoplatelets with atomically flat and very large {100} basal planes terminated solely by one type of element (either Cd or S atoms) are synthesized. Optical spectroscopy, X-ray diffraction, X-ray absorption, and transmission electron microscopy confirm that the surface structures of newly developed S-terminated CdS nanoplatelets are at least as well-defined as the original Cd-terminated nanoplatelets. Band gaps of the nanoplatelets are found to depend on not only the quantum-confined dimension (thickness) but also the nature of the surface termination. The facet structure dictates the packing of the ligands (carboxylate for Cd-terminated nanoplatelets and alkyl for S-terminated nanoplatelets), which causes a difference in the lattice strain and significantly affects the optical spectral width. Experimental and theoretical results reveal that engineering the exciton spatial distribution by the tailored synthesis of semiconductor nanocrystals with a precisely controlled surface structure is fully possible, which should open a new door for delivering the long-promised potential of semiconductor nanocrystals.

${\mathrm{PdCoO}}_{2}$, belonging to a family of triangular oxides called delafossite, is one of the most conducting oxides. Its in-plane conductivity is comparable to those of the best metals and exhibits hydrodynamic electronic transport with an extremely long mean free path at cryogenic temperatures. Nonetheless, it is nonmagnetic despite the presence of the cobalt ion. Here, we show that a mild hydrogenation process reduces ${\mathrm{PdCoO}}_{2}$ thin films to an atomically mixed alloy of PdCo with strong out-of-plane ferromagnetism and sign-tunable anomalous Hall effect. Considering that many other compounds remain little affected under a similar hydrogenation condition, this discovery may provide a route to creating novel spintronic heterostructures combining strong ferromagnetism, involving oxides and other functional materials.

Iron and nitrogen co-doped carbon (Fe-N-C) catalysts hold great promise to replace platinum group metal used for the oxygen reduction reaction (ORR) in low-temperature fuel cells. However, general synthesis routes require tedious acid washing and extensive heat treatment, usually resulting in uncontrollable morphologies and undesirable compounds. In this work, a zeolitic imidazolate framework (ZIF-8) was employed as a self-template for one-pot synthesis of a Fe-N-C catalyst consisting of uniformly dispersed Fe single atoms. Atomically dispersed Fe atoms were well distributed along the edges of the porous carbon matrix. Each of the Fe atoms was coordinated with four N atoms in the plane and two O atoms in the axial direction. The optimized Fe-N-C catalyst showed excellent ORR activities with half-wave potentials of 0.81 and 0.90 V in acidic and alkaline solutions, respectively. The results may be important for the optimization of single-atom-based catalysts for various reactions.

The electronic excitation of 3d transition metal oxide depends on the hybridization between orbitals of different ions, and is related to the materials properties. In this work, we systematically study the effect of hydrostatic pressure up to ∼20 GPa on the crystal structure and electronic structure of Pr0.67Sr0.33MnO3 powder, using Mn K-edge X-ray absorption near edge structure and X-ray diffraction at room temperature. With the increase of pressure, the energy position of non-local screened feature moves towards feature without screening due to the enhanced transition energy; however, the intensity (probability) of non-local screened feature increases with the pressure. Further study suggests that the pressure-induced antiferromagnetic phase, affecting hybridization between neighboring Mn ions with spin sensitivity, increase the probability of non-local charge transfer and corresponding intensity of non-local screened feature. The spin-sensitivity of non-local screening may be a useful parameter for characterization of material properties.

Purpose The purpose of this paper is to study the effects of single parameters for temperature characteristics of oil film in port plate pair and the relationship of calculated results and experimental results under different viscosity. Design/methodology/approach The paper established the mathematical model of oil film of port plate pair, calculated the energy equation of port plate pair, simulated for the oil film and temperature distribution and selected different kinds of lubricants to analyze the calculated value and the experimental value. Findings The results show: temperature rise of port plate pair is reduced with the increase of oil viscosity; temperature rise of port plate pair is decreased with rise of initial oil film thickness; temperature rise of port plate pair is increased with the rise of cylinder body speed, inclination angle and sealing belt width; and through the comparison of calculated value and experimental value, under the same viscosity and cylinder speed, experimental results are bigger. Originality/value This paper used the methods that the temperature of port plate pair was calculated numerically, and the results were consistent with experimental results, so it can get high precision.

Batteries with conversion-type electrodes exhibit higher energy storage density but suffer much severer capacity fading than those with the intercalation-type electrodes. The capacity fading has been considered as the result of contact failure between the active material and the current collector, or the breakdown of solid electrolyte interphase layer. Here, using a combination of synchrotron X-ray absorption spectroscopy and in situ transmission electron microscopy, we investigate the capacity fading issue of conversion-type materials by studying phase evolution of iron oxide composited structure during later-stage cycles, which is found completely different from its initial lithiation. The accumulative internal passivation phase and the surface layer over cycling enforce a rate−limiting diffusion barrier for the electron transport, which is responsible for the capacity degradation and poor rate capability. This work directly links the performance with the microscopic phase evolution in cycled electrode materials and provides insights into designing conversion-type electrode materials for applications., Conversion electrodes possess high energy density but suffer a rapid capacity loss over cycling compared to their intercalation equivalents. Here the authors reveal the microscopic origin of the fading behavior, showing that the formation and augmentation of passivation layers are responsible.

The rhenium-based transition metal dichalcogenides (TMDs), as new members in the TMDs family, have raised great interests recently. Due to the anisotropic structure and unique photoelectric properties, they have potential applications for electrochemical energy conversion and storage. In this work, we performed density functional theory (DFT) calculations on pristine 1T′-ReSe2 toward hydrogen evolution reaction (HER). The results indicated that the Gibbs free energy of the 1T′-ReSe2 edge site for HER could be as small as 0.01 eV, superior to other reported TMDs. Experimentally, we developed a strategy to fabricate sub-5 nm sized 1T′-ReSe2 nanoflakes on carbon nanotubes. Such a small size for the nanoflakes brought abundant edge exposure, which boosted the catalytic activity in the HER. Specifically, the 1T′-ReSe2 nanoflakes needed only 23 and 60 mV overpotentials to achieve −1 and −10 mA cm−2 current densities, along with a low Tafel slope of 37 mV dec−1 and a high exchange current density of 0.3 mA cm−2. The edge-rich and layered 1T′-ReSe2 was also explored as an anode for sodium ion battery. The in operando X-ray absorption near edge structure (XANES) technique was applied to investigate the TMD behavior in real-time during the sodiation/desodiation process. The in situ results revealed that the nanosized 1T′-ReSe2 is electrchemically reversible during discharge/charge cycles. The electrochemical test results demonstrated that 1T′-ReSe2 could be a promising anode material for alkaline batteries.

Nickel-rich transition-metal (TM) layered oxides, particularly those with high Ni content, attract worldwide interest for potential use as high-capacity cathodes in next-generation Li-ion batteries. However, as Ni loading increases, Li and Ni sitting at octahedra tend to mix, resulting in reduced electrochemical activity, which has been one major obstacle to their practical applications. Herein, we investigate the kinetic and thermodynamic aspects of Li/Ni mixing in LiNi0.7MnxCo0.3–xO2 (0 ≤ x ≤ 0.3) as they are synthesized, through quantitative determination of structural ordering and comparison to ab initio calculations. Results from this study elucidate the role of Co/Mn-substitution in tuning Li/Ni ordering, intrinsically through local magnetic interaction. Specifically, Co substitution facilitates Li/Ni ordering by relieving the intra-plane magnetic frustration and reducing the inter-plane super-exchange (SE) interaction; in contrast, Mn exacerbates magnetic frustration and strengthens SE, thereby agg...

We developed a general platform for the fabrication of transition metal oxide nanoparticles supported by a graphene foam (GF) by first coating it with a methacrylated gelatin (GelMA) hydrogel, which served as a 3D matrix for nanoparticle dispersion. The engineered GelMA/GF matrix was hydrophilic with good mechanical strength and high conductivity, therefore providing a good platform for the dispersion of a variety of metal/oxide precursors. Due to this platform, well-dispersed Co3O4 nanoparticles with the smallest size of 3 nm assembled on the nitrogen-doped graphene foam (Co3O4/NGF). The crystalline transformation from a CoCl2[H2O]2 precursor to Co3O4 was revealed by in operando X-ray diffraction and absorption techniques. After applying Co3O4/NGF as a free-standing electrocatalyst for water splitting, the nanoparticles of size 3 nm exhibited optimal catalytic activity in alkaline media; the corresponding cell could promote water splitting at a current density of 10 mA cm-2 with only 1.63 V and exhibited excellent stability in a 25 h long-term operation. Our results demonstrate that the GelMA hydrogel-coated 3D graphene foam can be a promising platform for the design and fabrication of graphene-based multifunctional materials.

This paper reports a comparative study of the magnetization, magnetocaloric effects, and crystal lattices of an as-cast sample and an annealed sample of the CoMnSi compound. Magnetic measurements showed that the annealed sample has high magnetization and a doubled maximum magnetic entropy change with respect to the as-cast sample. X-ray diffraction studies determined that both samples crystallize into an orthorhombic lattice. However, there are remarkable differences in the lattice parameters and one of the nearest Mn–Mn distances between the samples. Spectroscopic measurements of the X-ray absorption near-edge structure revealed that Co–Si bonds of the annealed sample are shorter than those of the as-cast sample due to stronger ${p}$ – ${d}$ hybridization of Co and Si atoms, while other chemical bonds do not show any difference. It is concluded that high-temperature annealing enhances ferromagnetic interactions in the lattice of CoMnSi by chemical ordering of Co atoms.