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Abstract As the cyclable sodium ions' primary suppliers, O3‐type layer‐structured manganese‐based oxides are recognized as one of the most competitive cathode candidates for sodium‐ion batteries. Suffering from complex structural transformations and transition metal migration during the sodium intercalation/deintercalation process, particularly at high voltage, the energy density and lifespan cannot satisfy the increasing demand. The orbital and electronic structure of the octahedral center metal element plays an important role in maintaining the octahedral structural integrity and improving the Na+ diffusivity by the introduced heterogeneous [Me–O] (Me: transition metals) chemical bonding. Herein, inspired by the 4f and 5d orbital bonding possibility from the abundant configuration of extranuclear electrons and large ion radius, O3‐type Na[La0.01Ni0.3Mn0.54Cu0.1Ti0.05]O2 was synthesized with a nearly single crystal structure. Based on the experimental and computational results, the introduced heterogeneous [La–O] chemical bond with larger bond strength can not only ensure the stability of the lattice oxygen framework and the reversibility of oxygen redox but also optimize the oxygen local electronic structure resulting from La 5d and O 2p orbital mixing due to O 2p → La 5d charge transfer. It delivers an optimal electrochemical performance with a high energy density and cycling lifespan.

Abstract Novel phase of nano materials that break the traditional structural constraints are highly desirable, particularly in the field of mechanocatalysis, offering versatile applications ranging from energy to medical diagnosis and treatment. In this work, a distinct layered barium dititanate (BaTi2O5) nanocrystals using a pH‐modulated hydrothermal method is successfully synthesized. These nanocrystals exhibit outstanding hydrogen generation capability (1160 µmol g−1 h−1 in pure water) and demonstrate remarkable performance in organic dye degradation using ultrasonication. The crystal structure of this newly discovered BaTi2O5 phase, is determined by a combination of synchrotron Powder Diffraction refinement and X‐ray adsorption techniques, including X‐ray Absorption Near Edge Structure (XANES) and Extended X‐ray Absorption Fine Structure (EXAFS). Density Functional Theory calculations revealed that the newly‐discovered BaTi2O5 phase demonstrates dipole moments along the z‐axis, distributed in an antiparallel direction within a single unit cell. These inherent dipoles induce a surface polarization and a ferroelectric‐flexoelectric response under mechanical stimuli when the materials go to nano dimension. With a band alignment well‐suitable for hydrogen and reactive oxygen species generation, this BaTi2O5 phase demonstrates promising potential for Mechanocatalysis. The discovery of this distinct phase not only enriches the material candidates for mechanocatalysis but also provides valuable insights.

Abstract The effective flow of electrons through bulk electrodes is crucial for achieving high-performance batteries, although the poor conductivity of homocyclic sulfur molecules results in high barriers against the passage of electrons through electrode structures. This phenomenon causes incomplete reactions and the formation of metastable products. To enhance the performance of the electrode, it is important to place substitutable electrification units to accelerate the cleavage of sulfur molecules and increase the selectivity of stable products during charging and discharging. Herein, we develop a single-atom-charging strategy to address the electron transport issues in bulk sulfur electrodes. The establishment of the synergistic interaction between the adsorption model and electronic transfer helps us achieve a high level of selectivity towards the desirable short-chain sodium polysulfides during the practical battery test. These finding indicates that the atomic manganese sites have an enhanced ability to capture and donate electrons. Additionally, the charge transfer process facilitates the rearrangement of sodium ions, thereby accelerating the kinetics of the sodium ions through the electrostatic force. These combined effects improve pathway selectivity and conversion to stable products during the redox process, leading to superior electrochemical performance for room temperature sodium-sulfur batteries.

Potassium metal batteries (PMBs) have become a paramount alternative energy storage technology to lithium-ion batteries, due to their low cost and potential energy density. However, uncontrolled dendrite growth interferes with the stability of the interfacial anode, leading to significant capacity degradation and safety hazards. Herein, a facile reactive prewetting strategy is proposed to discourage dendrite growth by constructing a functional KF/Zn-rich hybrid interface layer on K metal. The KF/Zn@K anode design functions like an interconnected paddy field, stabilizing the anode interface through the preferential redistribution of K+ flux/electrons, continuous transport paths, and enhanced transport dynamics. As anticipated, symmetrical batteries exhibit an extended cycling lifetime of over 2000 ​h, with reduced voltage hysteresis at 0.5 ​mA ​cm−2 and 0.5 mAh cm−2. Furthermore, when the KF/Zn@K anode is applied to full batteries coupled with PTCDA, a boosted reversible capacity of 61.6 mAh g−1 at 5 ​C is present over 3000 cycles. This interfacial control creates rational possibilities for constructing high-efficiency, stable K metal anodes.

The negative thermal expansion (NTE) phenomenon is of great significance in fabricating zero thermal expansion (ZTE) materials to avoid thermal shock during heating and cooling. NTE is observed in limited groups of materials, e.g., metal cyanides, oxometallates, and metal-organic frameworks, but has not been reported in the family of metal hydrides. Herein, a colossal and continuous negative thermal expansion is firstly developed in the low-temperature phases of LT1- and LT2-Mg2NiH4 between 488 K and 733 K from in-situ transmission electron microscope (TEM) video, with the volume contraction reaching 18.7% and 11.3%, respectively. The mechanisms for volume contraction of LT1 and LT2 phases are elucidated from the viewpoints of phase transformation, magnetic transition, and dehydrogenation, which is different from common NTE materials containing flexible polyhedra units in the structure. The linear volume shrinkage of LT2 in the temperature of 488–553 K corresponds to the phase transition of LT2→HT with a thermal expansion coefficient of –799.7 × 10–6 K–1 revealed by in-situ synchrotron powder X-ray diffraction. The sudden volume contraction in LT1 between 488 and 493 K may be caused by the rapid dehydrogenation of LT1 to Mg2Ni. The revealed phenomenon in single composite material with different structures would be significant for preparing zero thermal expansion materials by tuning the fraction of LT1 and LT2 phases.

Abstract While multiple external stimuli (e.g., temperature, light, pressure) have been reported to regulate gas adsorption, limited studies have been conducted on controlling molecular admission in nanopores through the application of electric fields (E-field). Here we show gas adsorption capacity and selectivity in zeolite molecular sieves can be regulated by an external E-field. Through E-field pre-activation during degassing, several zeolites exhibited enhanced CO2 adsorption and decreased CH4 and N2 adsorptions, improving the CO2/CH4 and CO2/N2 separation selectivity by at least 25%. The enhanced separation performance of the zeolites pre-activated by E-field was maintained in multiple adsorption/desorption cycles. Powder X-ray diffraction analysis and ab initio computational studies revealed that the cation relocation and framework expansion induced by the E-field accounted for the changes in gas adsorption capacities. These findings demonstrate a regulation approach to sharpen the molecular sieving capability by E-fields and open new avenues for carbon capture and molecular separations.

Abstract Covalent modification is commonly used to tune the channel size and functionality of 2D membranes. However, common synthesis strategies used to produce such modifications are known to disrupt the structure of the membranes. Herein, we report less intrusive yet equally effective non-covalent modifications on Ti3C2T x MXene membranes by a solvent treatment, where the channels are robustly decorated by protic solvents via hydrogen bond network. The densely functionalized (-O, -F, -OH) Ti3C2T x channel allows multiple hydrogen bond establishment and its sub-1-nm size induces a nanoconfinement effect to greatly strengthen these interactions by maintaining solvent-MXene distance and solvent orientation. In sub-1-nm ion sieving and separation, as-decorated membranes exhibit stable ion rejection, and proton-cation (H+/Mn+) selectivity that is up to 50 times and 30 times, respectively, higher than that of pristine membranes. It demonstrates the feasibility of non-covalent methods as a broad modification alternative for nanochannels integrated in energy-, resource- and environment-related applications.

This study describes the capabilities and limitations of carrying out total scattering experiments on the Powder Diffraction (PD) beamline at the Australian Synchrotron, ANSTO. A maximum instrument momentum transfer of 19 Å−1 can be achieved if the data are collected at 21 keV. The results detail how the pair distribution function (PDF) is affected by Qmax, absorption and counting time duration at the PD beamline, and refined structural parameters exemplify how the PDF is affected by these parameters. There are considerations when performing total scattering experiments at the PD beamline, including (1) samples need to be stable during data collection, (2) highly absorbing samples with a μR > 1 always require dilution and (3) only correlation length differences >0.35 Å may be resolved. A case study comparing the PDF atom–atom correlation lengths with EXAFS-derived radial distances of Ni and Pt nanocrystals is also presented, which shows good agreement between the two techniques. The results here can be used as a guide for researchers considering total scattering experiments at the PD beamline or similarly setup beamlines.

Abstract Catalytic conversion of CO2 into high value‐added chemicals using renewable energy is an attractive strategy for the management of CO2. However, achieving both efficiency and product selectivity remains a great challenge. Herein, a brand‐new family of 1D dual‐channel heterowires, Cu NWs@MOFs are constructed by coating metal–organic frameworks (MOFs) on Cu nanowires (Cu NWs) for electro‐/photocatalytic CO2 reductions, where Cu NWs act as an electron channel to directionally transmit electrons, and the MOF cover acts as a molecule/photon channel to control the products and/or undertake photoelectric conversion. Through changing the type of MOF cover, the 1D heterowire is switched between electrocatalyst and photocatalyst for the reduction of CO2 with excellent selectivity, adjustable products, and the highest stability among the Cu‐based CO2RR catalysts, which leads to heterometallic MOF covered 1D composite, and especially the first 1D/1D‐type Mott–Schottky heterojunction. Considering the diversity of MOF materials, the ultrastable heterowires offer a highly promising and feasible solution for CO2 reduction.

Selective CO2 adsorption for efficient carbon capture from flue gas (CO2/N2 - 15/85, v/v) and biogas (CO2/CH4 - 50/50, v/v) is important for achieving global energy and climate goals but remains a challenge due to the lack of effective adsorbents. To address this issue, we attempted to develop zeolite adsorbents by systematically investigating the effect of different extra-framework metal cations (i.e., Na+, Ca2+, Mn2+, and Ce3+-exchanged in LTA zeolites) on selective CO2 adsorption from CO2/N2 and CO2/CH4. Analyzing the isosteric heat of adsorption results showed that CO2 adsorption at moderate pressure (e.g., 15 and 50 kPa relevant to the compositions of flue gas and biogas, respectively) is governed by the gas-framework interaction. On the other hand, the adsorption of N2 and CH4 was found to be dominated by the gas-cation interaction. Therefore, we concluded that metal cations with a small charge-to-size ratio are beneficial for selective CO2 adsorption from flue gas and biogas because they tend to induce strong CO2-framework interaction (due to the enhanced charge induction to zeolite framework O) and weak N2 or CH4-cation interaction (due to the weakened gas-cation electrostatic interaction). Specifically, LTA zeolites in the form of Na+, with the smallest charge-to-size ratio of cation in this study, exhibit the highest CO2 uptake and separation factor of CO2/N2 and CO2/CH4, as demonstrated by both static single-component adsorption and dynamic binary adsorption results. In addition, the potential of metal cation-exchanged LTA zeolites for VSA and PSA processes was evaluated. Our study provides valuable insights for designing small-pore zeolites as adsorbents for carbon capture.

NO2 as a toxic air pollutant causes serious health problems and contributes to environmental damages, which needs to be abated to a harmless level urgently. However, the abatement of low-concentration NO2 pollution under ambient temperature is challenging due to the ineffectiveness of the state-of-the-art deNOx technologies which are only efficient at elevated temperatures (>300 °C). Adsorption is herein studied as an alternative approach for ambient temperature NO2 removal, using transition metal (i.e., Ag+, Cu2+, Co2+, Ni2+, Zn2+, In3+, and Ce3+) ion-exchanged chabazite (CHA) zeolites with different Si/Al ratios (Si/Al = 2, 6, and 12). NO2 is dominantly physiosorbed on the as-prepared samples, which enables the reversible adsorption in cyclic adsorption process. Ni2+ and Co2+ as active adsorption sites showed elevated affinity to NO2 molecules, which was attributed to the formation of Pi-back bonding via the donation of the electrons in dz2 orbital of the metal ions to Pi × orbitals of NO2 molecule, as evidenced by the changes in the electron occupancies in the orbitals of both transition metal ions and NO2 molecule upon NO2 adsorption (DFT calculation). Co2+ ion-exchanged CHA with Si/Al ratio of 2 (Co2+-2-L) showed an outstanding NO2 capacity of 4.65 mmol/g, with a stable NO2 removal performance verified by the adsorption-desorption cycles. The NO release amount of our adsorbents (

Transition metal dissolution from cathode materials limits the cycle life of Li-ion batteries. Here, the authors report an atomic-thin protecting layer on the surface of a high-voltage cathode material, enabling long-term Li-ion battery cycling.

The reaction between solid Fe and liquid Al occupies the important position due to its wide application in industrial processes. However, it is still unclear now which intermetallic compounds will form and the formation mechanism of Fe–Al intermetallic phases. In present work, the Fe–Al solid-liquid reaction by using iron wire as Fe resource is traced by in-situ synchrotron powder X-ray-diffraction. With Fe4Al13 as the dominant phase, two intermetallic phases named Fe4Al13 and Fe2Al5 are found. This phenomenon is different with the result obtained from the diffusion couple of Fe block and melt Al. Thermodynamic calculation and molecular dynamics simulation are performed to verify the underlying mechanism. Related events such as interfacial diffusion and nucleation driving force are analyzed and discussed.

Incomplete conversion of sodium polysulfides represents a significant issue in room-temperature sodium-sulfur batteries. Here, the authors propose Mo5N6 as an electrocatalyst for efficient Na2S electrodeposition and improved cell cycling performances.

The mechanism for the enhanced piezoelectricity in (K,Na)NbO3 based ceramics has not been fully understood. Here, the authors find that the dopants induced tetragonal phase and the accompanying high-density nanoscale heterostructures are responsible for the high dielectric and piezoelectric properties.

Room temperature rechargeable sodium sulfur batteries are promising for next-generation energy storage systems, but their development is limited by polysulfide dissolution and slow kinetics. Here the authors report a cathode that serves as a multifunctional sulfur host and imparts enhanced performance.

Full utilization of ZSM-5 shape-selectivity is restricted by crystal external surface acid sites and co-existence of two different sized channels. Here, the authors synthesize reverse Al zoned ZSM-5 with sinusoidal channel preferentially opened to its inert external surface to achieve 99.3% p-xylene selectivity.

Here Chou and co-authors demonstrate a NASICON-type low-cost Fe-based cathode material for sodium ion batteries. Na4Fe3(PO4)2(P2O7) allows for long-term cycling and high-power density and is featured by its air stability and all-climate property with 3D diffusion pathways for Na+ ions.

Regulating guest access and release in porous materials remains an important goal. Here, May and colleagues elucidate the mechanism by which guest admission can be temperature-regulated in typical microporous materials, and experimentally exploit this process to achieve appreciable and reversible hydrogen storage.

High hydrostatic pressure (HHP) has been employed to gelatinize or physically modify starch dispersions. In this study, waxy maize starch, normal maize starch, and two high amylose content starch were processed by a HHP of the order of 600 MPa, at 25°C for 15min. The effect of HHP processing on the crystallization of maize starches with various amylose content during storage at 4°C was investigated. Crystallization kinetics of HHP treated starch gels were investigated using rheology and FTIR. The effect of crystallization on the mechanical properties of starch gel network were evaluated in terms of dynamic complex modulus (G*). The crystallization induced increase of short-range helices structures were investigated using FTIR. The pressure releasing rate does not affect the starch retrogradation behaviour. The rate and extent of retrogradation depends on the amylose content of amylose starch. The least retrogradation was observed in HHP treated waxy maize starch. The rate of retrogradation is higher for HHP treated high amylose maize starch than that of normal maize starch. A linear relationship between the extent of retrogradation (phase distribution) measured by FTIR and G* is proposed.