Low Activation Energy Research Articles

Enhancing interfacial stability in lithium orthosilicate/polymer blended novel hybrid solid-state electrolytes for all-solid-state lithium metal batteries

Hybrid solid-state electrolyte (HSSE) is a key component for the advancement of all-solid-state lithium metal batteries. The key challenges with the existing HSSEs are to ensure high ionic conductivity, activate dead inorganic/organic interface, and stimulate interfacial stability with electrodes. In this study, a novel HSSE is fabricated by integration of appropriately engineered end-of-life photovoltaic recycled high purity silicon derived nano size inorganic lithium orthosilicate and poly (vinylidene fluoride-co-hexafluoropropylene) polymer matrix through entrapping ionic liquid electrolytes. The obtained lithium orthosilicate-polymer blended HSSE is self-standing, soft, and flexible which delivers a low activation energy, leading a high ionic conductivity of 4.4 × 10−4 Scm−1. A critical lithium plating/stripping behaviour shows improved interfacial stability (both inorganic/organic interface and interfaces of HSSE/electrodes) under different current densities (0.05 mA cm−2 to 0.13 mA cm−2) when a drop of ionic liquid electrolyte is added, permitting cycling of an all-solid-state full cell (Li/HSSE/LiFePO4) at room temperature with high capacity (132 mAh g−1), stable cycle life and high Coulombic efficiency (initial ∼98 %; subsequent >99.5 %). Shaping the interfaces between inorganic/organic phases in the HSSE as well as the interfaces between electrodes/HSSE appears to be a workable path towards constructing very effective HSSE for the advancement of all-solid-state lithium metal batteries.

Active and stable Ni-Cr oxide catalysts for oxidative dehydrogenation of ethane using CO2: Carbon cycle-assisted oxygen cycle

The CO2-assisted oxidative dehydrogenation of ethane (CO2-ODHE) is known as an ecologically beneficial process for ethylene generation and CO2 utilization. However, the quick deactivation of traditional Cr-based catalysts remains a considerable challenge. Herein, we report that a 1Ni1CrOx/ZrO2 catalyst could be high active and stable for the CO2-ODHE reaction; it showed CO2 conversion of 15.4 % and kept stable for 38 h at 600 °C, while the productivity of ethylene approached 325 μmol·min−1·gcat−1. Kinetic evaluations found a low apparent activation energy of 87.2 kJ/mol on the 1Ni1CrOx/ZrO2 catalyst. Surface Cr6+ and oxygen species were enriched to form Cr2O72− with the introduction of NiO. In addition, NiO improved the surface alkalinity and the affinity for oxygen, promoting the strong adsorption and easy activation of CO2. Importantly, Niδ+ species catalyzed the reaction between CO2 and surface-deposited carbon by redox cycling (carbon cycle), promoting Mars-van Krevelen-type carbon elimination and Cr6+ regeneration. The carbon cycle-assisted oxygen cycle on the Ni-Cr oxide catalysts could obviously enhance the carbon resistance and stable ethylene production, demonstrating potential application of Cr-based catalysts for CO2-ODHE reaction.

Dissolution Mechanisms and Surface Charge of Clay Mineral Nanoparticles: Insights from Kinetic Monte Carlo Simulations

The widespread use of clay minerals and clays in environmental engineering, industry, medicine, and cosmetics largely stems from their adsorption properties and surface charge, as well as their ability to react with water. The dissolution and growth of minerals as a function of pH are closely related to acid–base reactions at their surface sites and their surface charge. The vivid tapestry of different types of surface sites across different types of clay minerals generates difficulties in experimental studies of structure–property relationships. The aim of this paper is to demonstrate how a mesoscale stochastic kinetic Monte Carlo (kMC) approach altogether with atomistic acid-base models and empirical data can be used for understanding the mechanisms of dissolution and surface charge behavior of clay minerals. The surface charge is modeled based on equilibrium equations for de/protonated site populations, which are defined by the pH and site-specific acidity constants (pKas). Lowered activation energy barriers for these sites in de/protonated states introduce pH-dependent effects into the dissolution kinetics. The V-shaped curve observed in laboratory experiments is reproduced with the new kMC model. A generic rate law for clay mineral dissolution as a function of pH is derived from this study. Thus, the kMC approach can be used as a hypothesis-testing tool for the verification of acid–base models for clay and other minerals and their influence on the kinetics of mineral dissolution and growth.

Lewis Acidic VOx Engineered PdAu Nanocatalysts for Efficient Formic Acid Dehydrogenation

AbstractThe development of high‐performance catalysts for formic acid (FA) dehydrogenation is of extreme significance to the successful production of hydrogen under ambient conditions. Despite some encouraging progress, their activity is still unsatisfied than needed. In this work, it is presented that Lewis acidic VOx sites engineered ultrafine PdAu nanoclusters (PdAu‐VOx) perform perfectly for hydrogen production from FA dehydrogenation. Strikingly, the best catalyst — PdAu‐VOx embed in amino‐functionalized hollow mesoporous support (PdAu‐VOx/NHMS) discloses an impressive initial turnover frequency of 14155 h−1 and a low activation energy of 31.2 kJ mol−1 without additives at room temperature, and maintains 100% selectivity and conversion in the tenth cycle reaction. Mechanistic investigations illustrate that VOx species can serve as the Lewis acid sites, which not only regulate the adsorption strength of reactant and intermediate on PdAu, but also reinforce the C─H bond activation within FA molecule, thereby promoting the reaction kinetics for efficient hydrogen production. This work thus provides a strategy for the development of new‐style heterogeneous catalysts with Lewis acid‐base sites applied to a variety of energy‐related catalytic reactions.

CoMo/g-C3N4 as a highly effective, reusable, non-noble metal-based catalyst for H2 production via NaBH4 hydrolysis focused on stationary application under mild conditions: A kinetic study

Among hydrogen storage chemicals for proton exchange membrane fuel cells (PEMFCs), sodium borohydride stands out for yielding exceptionally pure hydrogen. This study synthesized cobalt-molybdenum catalysts supported on g-C3N4 using an ultrasonic-assisted impregnation method. Various CoMo/g-C3N4 catalysts with different CoMo mass ratios were created, all showing high hydrogen production and complete NaBH4 conversion under mild conditions. Catalytic activity depends on the cobalt-molybdenum mass ratio, with optimal performance at a 1:1 ratio (w/w), maintaining up to 83% activity over 5 cycles. The effect of operating conditions on hydrogen release was explored, resulting in the rate law: rH2 = 1.708 × 10-3 [NaBH4]1.25 [Catalyst dosage]1.39 [NaOH]0.44 at 298 K, with a low activation energy of 22.9 kJ mol−1. Molybdenum's promoting effect prevented significant deactivation of the cobalt catalyst, ensuring complete NaBH4 conversion to H2 and good stability over multiple cycles.

Kinetics of N2O decomposition over bulk and supported LaCoO3 perovskites

For the first time, kinetic data on the decomposition of N2O over mixed oxide LaCoO3 with a perovskite structure have been obtained. Bulk LaCoO3 synthesized using microwave activation exhibited an increased intrinsic reaction rate with a 30 kJ mol–1 lower activation energy. Perovskite samples supported on ZrO2-La demonstrated lower intrinsic reaction rates due to the lower content of the LaCoO3 phase, but the activation energies were also lower by 50–80 kJ mol–1.

Kinetics of hydrogen isotope exchange in kaolinite and the prediction of δD signature retention over geological time

Retention of the pristine hydrogen isotope composition (expressed as δD) formed during mineral formation in equilibrium with water is the basis for any paleoenvironmental reconstructions and for tracing mineral reactions using hydrogen (or H and O) isotope composition in kaolinite. Not only do post-formation reactions cause partial equilibration with ambient water, altering the pristine signature, but also result in the decoupling of H and O diffusion.In this study, kaolinite samples of different structural order (expressed, for example, as the Hinckley Index) were tested for their susceptibility to H isotope exchange under D2O vapor in an open system. The H isotope exchange was detected by recording the kaolinite’s structural OH and OD stretching mode using infrared spectroscopy. A number of different in-situ and ex-situ testing protocols under diverse temperature ranges (90 °C, 125–275 °C, 300–700 °C), show consistent kinetics and mechanism. In each kaolinite sample, the H isotope exchange rate increases with temperature; however, the major control on the reaction rate is the kaolinite crystallite’s structural order, not the particle (agglomerated crystallites) size. The hydrogen isotope composition in kaolinite can be altered independently of oxygen atoms, likely via proton hopping mechanism through structural defects. The H isotope exchange reaction under vapour shows a two-mode kinetics: the time-to-the-quarter (TTTQ; t1/4) dependence dominates in the first part of the reaction or in low-temperature reactions, transitioning to the log10t (Elovich) relationship and with lower activation energy, in advanced stages and in higher temperatures. Extrapolating the TTTQ model to temperatures < 90 °C allows estimating the rate of H isotope exchange between water vapor and kaolinite. The paper presents the prediction of preservation of pristine δD signature and thus reliability of using isotope data in kaolinites of different origins and structural order when exposed to pore water / water vapor over geological timescales.

The influence of the dopant concentration and sintering parameters on properties of antimony doped barium stannate ceramics

In this paper, the influence of antimony concentration and different sintering techniques on the structural, microstructural, and electrical properties of antimony-doped barium stannate, BaSn1-xSbxO3 (BSSO, x = 0.00, 0.04, 0.06, 0.08 and 0.10) was investigated. BSSO-based ceramic samples were obtained by conventional and spark plasma sintering. The XRD analysis confirmed the single-phase, cubic BaSnO3 lattice system in all conventionally sintered samples. Apart from the dominant cubic phase, the spark plasma sintering conditions led to the formation of a secondary phase, Ba2SnO4, in all samples. FESEM analysis revealed the presence of low angle grain boundaries (LAGBs) in BSSO samples with high antimony concentration (x = 0.08), independently of the sintering technique. However, the fraction of LAGBs is significantly higher in the BaSn0.92Sb0.08O3-SPS sample due to the simultaneous exposure of the conductive sample to the effects of high temperature and pressure during sintering process. These boundaries have low activation energy and allow free charge carrier transport through the grain boundary region. The high dopant concentration and the presence of large fraction of LAGBs in BaSn0.92Sb0.08O3-SPS sample reflected on its electrical properties through low and almost temperature-independent electrical resistivity in the temperature range of 25–150 °C.

Enriching Nano-Heterointerfaces in Proton Conducting TiO2-SrTiO3@TiO2 Yolk-Shell Electrolyte for Low-Temperature Solid Oxide Fuel Cells.

A challenging task in solid oxide fuel cells (SOFCs) is seeking for an alternative electrolyte, enabling high ionic conduction at relatively low operating temperatures, i.e., 300-600°C. Proton-conducting candidates, in particular, hold a significant promise due to their low transport activation energy to deliver protons. Here, a unique hierarchical TiO2-SrTiO3@TiO2 structure is developed inside an intercalated TiO2-SrTiO3 core as "yolk" decorating densely packed flake TiO2 as shell, creating plentiful nano-heterointerfaces with a continuous TiO2 and SrTiO3 "in-house" interfaces, as well the interfaces between TiO2-SrTiO3 yolk and TiO2 shell. It exhibits a reduced activation energy, down to 0.225eV, and an unexpectedly high proton conductivity at low temperature, e.g., 0.084 S cm-1 at 550°C, confirmed by experimentally H/D isotope method and proton-filtrating membrane measurement. Raman mapping technique identifies the presence of hydrogenated HO─Sr bonds, providing further evidence for proton conduction. And its interfacial conduction is comparatively analyzed with a directly-mixing TiO2-SrTiO3 composite electrolyte. Consequently, a single fuel cell based on the TiO2-SrTiO3@TiO2 heterogeneous electrolyte delivers a good peak power density of 799.7mW cm-2 at 550°C. These findings highlight a dexterous nano-heterointerface design strategy of highly proton-conductive electrolytes at reduced operating temperatures for SOFC technology.

DSC analysis of dissolution reaction in an as-cast and HPT-processed Mg-Gd alloy

The dissolution reaction kinetics were determined by differential scanning calorimetry (DSC) analysis for Mg-0.6Gd (wt.%) in an as-cast condition and after processing by high-pressure torsion (HPT) at room temperature for 20 turns. For the as-cast condition, the dissolution temperature was in the range of 634–658 K with an activation energy of 135 ± 9 kJ/mol. After HPT, the range of dissolution temperature decreased to 601–633 K, with a lower activation energy of 118 ± 10 kJ/mol. In both conditions, the Avrami and growth exponents are around 1.5, which suggests that the dissolved precipitates exhibit polyhedron-like morphology and that the dissolution process is dominated by bulk dissolution with a constant rate controlled by diffusion.

Drying kinetics of CeO2-ZrO2 ceramic powders under microwave heating based on a thin-layer drying model

Volume change of ZrO2 during martensitic phase transformation can cause cracking of material and limit the application of ZrO2.Agglomeration of CeO2-ZrO2 ceramic powders can be effectively reduced by choosing the correct drying method. Microwave drying of CeO2-ZrO2 powder can effectively reduce the cracking of zirconia materials and improve powder uniformity. Microwave heating is used to dry CeO2-ZrO2 ceramic powders, and results demonstrate that Modified Page fits experimental data rather well. FT-IR spectra revealed a remarkable decrease in the intensity of the -OH bond's stretching vibration peak, and H-O-H bond's bending vibration. Utilizing Fick's second law, the diffusion coefficient of water molecules in CeO2-ZrO2 ceramic powders with a mass of 20 g and a moisture content of 6.6 % is calculated to be 5.820 × 10−15 m2/s under microwave power of 400 W. Experimental results prove that microwave heating has low activation energy, improves drying efficiency, and realizes fast and efficient drying.

Highly active nitrogen-doped biochar for catalytic reduction of 4-nitrophenol: Kinetic, thermodynamic and mechanism investigation

Biomass derived metal-free carbon catalysts are urgently needed in wastewater remediation and organic transformation, due to their environmental friendliness, low cost. In this respect, a series of nitrogen-doped hierarchically porous carbons (NHPCs) derived from cheap and abundant eggplant were fabricated via a one-pot strategy under different temperatures from 600 to 900°C, and employed as metal-free catalysts for the reduction of aromatic nitrophenols. Benefiting from the synergistic effects of the hierarchically porous structure, large specific surface area and abundant structural defects, NHPCs obtained from 800 °C has the highest reduction rate of 2.072 min−1 and maximal turnover frequency (TOF) for 4-nitrophenol of 1.23 × 10−2 mM·mg−1·min−1, which is superior to most of the reported metal-free catalysts. In addition, the NHPC-800 also exhibits satisfactory practicality and universality. The kinetic and thermodynamic studies were also conducted, finding that the obtained kinetics data over NHPC-800 fit well to L-H model with a low apparent activation energy (Ea = 18.96 kJ·mol−1). Furthermore, the mechanism was also elucidated by experimental investigation and theoretical calculations, which revealed that the pore creation and doping nitrogen can promote the adsorption of 4-NP and NaBH4 onto NHPC. This study make a significant contribution to the advancement of catalytic reduction of 4-NP by N-doped biochar catalysts.

Factorial Analysis and Thermal Kinetics of Chemical Recycling of Poly(ethylene terephthalate) Aided by Neoteric Imidazolium-Based Ionic Liquids.

Poly(ethylene terephthalate) (PET) waste accumulation poses significant environmental challenges due to its persistent nature and current management limitations. This study explores the effectiveness of imidazolium-based neoteric solvents [Emim][OAc] and [Bmim][OAc] as catalytic co-solvents in the glycolysis of PET with ethylene glycol (EG). Reaction thermal kinetics showed that both ionic liquids (ILs) significantly enhanced the depolymerization rate of PET compared to traditional methods. The use of [Emim][OAc] offered a lower activation energy of 88.69 kJ·mol-1, thus making the process more energy-efficient. The contribution of key process parameters, including temperature (T), plastic-to-ionic liquid (P/IL) mass ratio, and plastic-to-solvent (P/S) mass ratio, were evaluated by means of a factorial analysis and optimized to achieve the maximum PET conversion for both neoteric solvents. The relevance sequence for both ionic liquids involved the linear factors T and P/S, followed by the interaction factors T×P/S and T×P/IL, with P/IL being the less significant parameter. The optimal conditions, with a predicted conversion of 100%, involved a temperature of 190 °C, with a P/IL of 1:1 and a P/S of 1:2.5, regardless of the IL used as the catalytic co-solvent.

Elucidating the improved properties of defect engineered lanthanum-doped nickel oxide as hole-transport layer in triple-cation perovskite solar cells

Charge recombination at the interface between the hole transport layer (HTL) and perovskite (PVK) has been a performance bottleneck for perovskite solar cells (PSCs). We present a detailed examination for the solar cell efficiency of the device using lanthanum (La)-doped nickel oxide (NiOx) as an HTL. The NiOx and La-doped NiOx films were prepared using the spray pyrolysis process. We employed low-temperature photoluminescence (LT-PL) to estimate the defect activation energy and utilized SCAPS 1D software to simulate the interface defect density. According to the data obtained, the interface between La:NiOx and PVK shows a lower activation energy for defects, indicating that it is more advantageous for charge transfer compared to the interface between NiOx and PVK. Utilizing SCAPS simulations the experimental JV curves closely match the simulated JV curves obtained from SCAPS simulations. These simulations were performed using optimal parameters, obtained by increasing the Rsh values and reducing the interface density in La:NiOx based PSCs. The interface defect densities are estimated to be La:NiOx/PVK and NiOx/PVK interfaces are 1 × 1012 cm−2 and 1.7 × 1012 cm−2, respectively. This indicates ≈70 % reduction in defect density at the La:NiOx/PVK interface compared to the NiOx/PVK interface. The conductivity values obtained from linear sweep voltammetry (LSV) are 1.01 × 10−3 S cm−1 for NiOx films and 1.21 × 10−3 S cm−1 for La:NiOx films. This indicates a significant enhancement of ≈20 % in the conductivity of La:NiOx films compared to undoped films. This leads to improvements in VOC and ultimately enhances the PCE. The calculating defect density at the HTL/PVK interface can contribute to the fabrication of futuristic highly efficient PSCs.

The influence of ferrite content, ferrite-austenite morphology, and orientation relationship on bainite transformation in intercritically annealed bainitic steels

This manuscript elucidates the influence of varying ferrite/tempered martensite (TM) content, morphology and orientation relationship (OR) between ferrite/TM with reverted austenite (γ) resulting at different intercritical temperatures on the subsequent bainite transformation behaviour. A comprehensive analysis was conducted using scanning electron microscopy, electron backscattered diffraction, and dilatometry. TM/bainite and ferrite/bainite steels were produced through intercritical annealing at 735 °C, 745 °C, and 765 °C, followed by austempering at 310 °C, using initially quenched and cold-deformed martensite, respectively. In samples without cold rolling, TM and bainite are alternately distributed at all intercritical temperatures. The γ reversion process in these samples led to the formation of acicular γ at prior martensite blocks and laths while globular γ was formed at prior γ boundaries and packet boundaries. Notably, a lower TM content correlated with increased globular γ formation. The acicular γ exhibited a Kurdjumov–Sachs (K-S) OR with prior γ. The globular γ formed at prior γ grain boundaries showed the K-S OR with the prior γ where it grows. However, globular γ formed at packet boundaries maintained the K-S OR with one of its surrounding blocks in prior γ where it lies. In the subsequent austempering process, bainite formed from reversed γ followed the K-S OR with TM. The TM and bainite shared the same variant in the same block. In samples with cold rolling, polygonal ferrite and bainite were distributed at all intercritical temperatures. Decreasing the ferrite content showed a coarsening of the microstructure. All polygonal samples revealed an irrational OR between bainite/martensite and ferrite. In samples with and without cold rolling, the bainitic formation rate decreased with increasing ferrite/TM, likely due to the high C and Mn content at the α/γ interface. Comparatively, the samples without cold rolling showed faster bainitic transformation than samples with cold rolling at similar ferrite/TM percentages, particularly noticeable at higher ferrite/TM content. The alternately arranged elongated TM and reversed γ lamellae increased the α/γ interfacial density for bainitic nucleation. Moreover, K–S oriented α/γ interfaces exhibited a lower activation energy for bainite nucleation. In samples without cold rolling, both high density of α/γ interfaces and K–S oriented α/γ interfaces collectively facilitate the bainitic transformation.

The diffusion and desorption of tritium on Li2TiO3 (-133) surface from first-principles calculations

Li2TiO3 is one of the most promising solid breeder materials for nuclear fusion reactor. Diffusion on the surface is a vital step of the tritium release process. In this work, the diffusion behavior of tritium atoms on the (-133) surface and the desorption of T2 molecules from the (-133) surface are systematically investigated. Possible adsorption sites, local diffusion pathways, and their corresponding activation energies have been identified using first-principles calculations and the climbing image nudged elastic band (CI-NEB) method. The diffusivity and effective activation energy for tritium diffusion on the (-133) surface have been determined using kinetic Monte Carlo (KMC) simulations. The activation energy for T2 desorption from the (-133) surface has also been investigated. The effective activation energy for tritium diffusion on the (-133) surface is found to be 1.06 eV, whereas the activation energy for T2 molecule desorption is 1.46 eV. The (-133) surface exhibits a higher activation energy for tritium diffusion but a lower activation energy for T2 desorption compared to the (001) surface.

Hierarchical nanoarchitectonics of hollow hexanitrostilbene (HNS) microspheres to improve safety and combustion performance

Hollow structures have great potential in the field of energetic materials due to their excellent properties. In this study, nitrocellulose (NC) was used as a binder, and hollow-structured HNS/NC microspheres were prepared in the form of a suspension using the microjet droplet technology. The effects of spray velocity, suspension concentration, and receiving liquid temperature on the morphology, particle size, cavity structure, and pore size of the microspheres were systematically investigated. Subsequently, the effects of shell thickness and pore size on the dispersibility, specific surface area, crystal structure, thermal performance, mechanical sensitivity, and combustion performance of the microspheres were further studied. The results show that compared with the raw HNS, the hollow HNS/NC microspheres have good dispersibility, while retaining the crystal structure and chemical structure of the raw HNS, and have a lower activation energy, which is expected to achieve a rapid energy release reaction. In addition, compared with the solid HNS/NC microspheres, the hollow HNS/NC microspheres have a higher specific surface area (19.658 m2·g−1 vs 31.335 m2·g−1) and better safety performance (6 J vs 50 J). The ignition experiment results show that the hollow structure significantly enhances the combustion performance of HNS (305 ms vs 92 ms), improving the energy release efficiency. This preparation method is simple, efficient, and easy to scale up, providing a more universal and environmentally-friendly technical approach for the multi-structural design of energetic microspheres.

Surface ion-exchange induced Bi-rich Bi12O17Cl2/BiOCOOH/Bi2MoO6 heterojunction with oxygen vacancies for enhanced photocatalytic nitrogen fixation

Photocatalytic nitrogen reduction presents a promising technology for environmentally friendly ammonia synthesis under mild conditions. However, the performance of photocatalysts is often hindered by high charge carrier recombination and insufficient adsorption and activation of nitrogen molecules. A novel Bi12O17Cl2/BiOCOOH/Bi2MoO6 heterojunction photocatalyst was successful synthesis through surface ion-exchange technique by potassium chloride. The introduction of Bi-rich Bi12O17Cl2 on BiOCOOH/Bi2MoO6 heterojunction not only improves electron transfer efficiency due to the dual type-II heterojunction effect but also facilitates on-site N2 adsorption and activation for solar ammonia production by promoting oxygen vacancies. The high photocatalytic nitrogen fixation activity of the Bi12O17Cl2/BiOCOOH/Bi2MoO6 was 107.78 μmol g−1 h−1 without any sacrificial agent. DFT calculations indicate that oxygen vacancies serve as the active site for adsorbed N2, the hydrogenation process preferentially forms on the distal N2 atom with a lower activation energy about 0.6 eV. Therefore, the combination of oxygen vacancies and band engineering accelerates the production of ammonia. This endeavor holds the potential to unleash the capabilities of engineering for Bi-rich heterojunctions materials with oxygen vacancies, thereby achieving high-efficiency solar-driven N2-to-NH3 conversion in aqueous environments.

Superionic halide solid electrolyte Li1.7Zr0.7Ta0.3Cl6 for durable all-solid-state lithium batteries

Zirconium-based halide solid electrolyte, Li2ZrCl6, with low raw-material cost and high oxidative stability is a promising candidate for next-generation energy storage devices. However, the low ionic conductivity hinders its practical applicability. Herein, we report a new zirconium-based superionic conductor based on high-valence Ta5+ doping strategy. The optimized Li1.7Zr0.7Ta0.3Cl6 (LZTC) exhibits excellent ionic conductivity of 1.42 mS cm-1 at 25 °C. Moreover, it can be further increased up to 1.68 mS cm-1 with a low activation energy of 0.28 eV by slightly tuning Li+ concentration. In addition, LZTC possesses a big compact density of 2.67 g cm-3 under 250 MPa and is compatible with 4V-class cathodes. Density function theory (DFT) and bond valence site energy (BVSE) calculations reveal Ta5+ substitution significantly reduces the migration energy barrier of lithium ions due to the distortions and defects of local structural environment. The assembled all-solid-state batteries with Li1.7Zr0.7Ta0.3Cl6 as electrolyte and scNCM811 as cathode show excellent cycling performance for 600 cycles at 1C with a high-capacity retention of 85.7%.

Ligand-Coordinated Pt Single-Atom catalyst facilitates Support-Assisted Water-Gas shift reaction

The water–gas shift (WGS) reaction (CO+H2O→CO2+H2,ΔH=-41.1kJ/mol) is an essential process in the production of hydrogen and has grown significantly in usage over time. In this study, we further explore a novel strategy that can create single-atom catalysts (SACs) from metal-ligand single-sites on high surface area oxide supports for catalyzing the WGS reaction. The metal–ligand approach results in high metal loading, exhibits an ultimate dispersion of metal species and maximizes atom efficiency. 1,10-phenanthroline-5,6-dione (PDO) was chosen as the ligand for its oxidative potential for stabilizing Pt metal cations via two different binding pockets. The single-atom nature of the Pt-ligand is characterized with extended X-ray absorption fine structure (EXAFS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and transmission electron microscopy (TEM) techniques. The catalytic activity is evaluated for the WGS reaction, revealing that Pt-ligand SACs supported on defective TiO2 show higher inherent catalytic activity than Pt NPs and a significantly lower activation energy. This characteristic is generally desirable for the redox mechanism. Density functional theory (DFT) calculations reveal that metal–ligand SACs allow CO interaction with oxygen atoms from the TiO2 surface. The redox mechanism of the WGS reaction demonstrates a lower effective activation barrier than the associative mechanism for Pt-ligand SAC. Moreover, the metal–ligand strategy, according to DFT results, facilitates the reaction redox mechanism by reducing the CO binding energy and promoting CO2 and H2 formation process.