Excess Vacancies Research Articles

Durable electrocatalysts based on barium niobates doped with Ca, Fe, and Y: Enhancing catalytic activity and selectivity for oxidative coupling of methane

Effective conversion of methane into value added products such as olefins, is a major research area for the past 40 years. Electrochemical oxidative coupling of methane (E-OCM) is recently gaining attention due to its ability to control the product selectivity by oxide ion flux and applied potential. We report a new series of catalysts, Ca, Fe, and Y co-doped barium niobate perovskites (BCNFY) for E-OCM application. BCNFY perovskites show chemical stability under 4 % H2, CH4, and high CH4-O2 mixtures at high temperatures up to 900 °C. Under reducing conditions, BCNFY perovskites form excess oxygen vacancies that is supported by Nb4+/5+ oxidation state changes that help retain the crystal structure. Temperature programmed reaction (TPR) measurements under 95 % CH4:5% O2 reveal methane activation properties from 600 °C with a high C2+ selectivity of 82 % at 850 °C. TPR measurements further reveal the nature of active sites for methane activation. Cyclic voltammetry measurements show a unique relationship between product selectivity and applied potential as at applied biases close to open circuit potential, CO and H2 are the major products while at high applied biases ethylene and CO2 are the major products. Our results show the advantages of E-OCM over conventional OCM although improvements in terms of electronic conductivity of the electrode and overall current densities are required for commercial viability for these perovskite electrodes.

SrCoO3-based perovskites with enhanced electrochemical performance through structural tailoring induced by B-site substitution

The progression of supercapacitor technology hinges on the discovery of high-performance electrode materials to enhance energy storage. SrCoO3-δ perovskite holds considerable promise potential as an anion intercalation electrode material. To elucidate the structural and electrochemical performance modulation rules of SrCoO3-based perovskites, this study synthesized SrCo0.875M0.125O3-δ (M = Ti, Ta, Nb, Fe) perovskites with different B-site ion substitutions. The structural tailoring induced by B-site substitution were thoroughly investigated alongside their corresponding electrochemical performance. Notably, SrCo0.875Ti0.125O3-δ exhibited a simple cubic structure, while the other samples displayed a tetragonal structure. Additionally, SrCo0.875Fe0.125O3-δ displayed numerous oxygen vacancies and significant distortion in the [CoO6] octahedron, which is attributed to the lower valence state of Fe. At a current density of 1 A g−1, the specific capacities of SrCo0.875M0.125O3-δ (M = Nb, Ti, Fe, Ta) perovskites were 984.43, 853.33, 503.53, and 452.00C/g, respectively. SrCo0.875Nb0.125O3-δ demonstrated the highest specific capacity and capacity retention rate across various current density, owing to its relatively stable structure with appropriate oxygen vacancies and multivalent state changes of Nb. In contrast, SrCo0.875Fe0.125O3-δ, with excessive oxygen vacancies and severe structural distortions, exhibited restricted electrochemical performance, particularly at higher current densities. Integrating structural and performance analysis, this work proposes an optimization strategy for the electrochemical performance of SrCoO3-δ-based perovskite electrode materials, emphasizing the importance of tailoring multivalent B-site elements to achieve a stable perovskite structure with appropriate oxygen vacancies.

Water-Driven Surface Lattice Oxygen Activation in MnO2 for Promoted Low-Temperature NH3-SCR.

Water is ubiquitous in various heterogeneous catalytic reactions, where it can be easily adsorbed, chemically dissociated, and diffused on catalyst surfaces, inevitably influencing the catalytic process. However, the specific role of water in these reactions remains unclear. In this study, we innovatively propose that H2O-driven surface lattice oxygen activation in γ-MnO2 significantly enhances low-temperature NH3-SCR. The proton from water dissociation activates the surface lattice oxygen in γ-MnO2, giving rise to a doubling of catalytic activity (achieving 90% NO conversion at 100 °C) and remarkable stability. Comprehensive in situ characterizations and calculations reveal that spontaneous proton diffusion to the surface lattice oxygen reduces the orbital overlap between the protonated oxygen atom and its neighboring Mn atom. Consequently, the Mn-O bond is weakened and the surface lattice oxygen is effectively activated to provide excess oxygen vacancies available for converting O2 into O2-. Therefore, the redox property of Mn-H is improved, leading to enhanced NH3 oxidation-dehydrogenation and NO oxidation processes, which are crucial for low-temperature NH3-SCR. This work provides a deeper understanding and fresh perspectives on the water promotion mechanism in low-temperature NOx elimination.

Optimizing the mechanical and corrosion properties of an ultrafine-grained Al-Cu-Mg alloy through cyclic deformation: Clusters and lattice defects

To optimize its corrosion and mechanical properties, an Al-Cu-Mg alloy is cyclically processed by high-pressure torsion (HPT), involving a 1/2 turn clockwise and a 1/2 turn counter-clockwise per cycle. The dislocation density increases to 3.04×1014 m−2 on 1 cycle HPT and decreases gradually to 2.23×1014 m−2 for higher cyclic rotations (i.e. 5 cycle HPT). Due to the rapid elimination of the geometrically necessary dislocations, the refinement of grain size in cyclic HPT is more efficient than the monotonic HPT (i.e. it decreases from 2.48 μm to 112 nm on 1 cycle HPT). The HPT samples are electrochemically corroded in a simulated seawater environment. 1-cycle HPT process causes a strong increase in hardness (to 232 HV) and an increase in corrosion potential (to −0.517 V). The trade-off between hardness/strength and corrosion resistance is broken on cyclic HPT processing. Aided by excess vacancies induced by HPT, Cu-Mg clusters form on and near grain boundaries through a ‘vacancy-pump’ mechanism, causing solute depleted zones (SDZ) adjacent to GBs. The combined effects of ultrafine grains, solute cluster segregation and SDZs enhance the strength and corrosion resistance of the Al-Cu-Mg alloys. This study provides a potential strategy to design the microstructures of an Al alloy, and to achieve a higher hardness and a better corrosion performance of that material.

Grain boundary segregation of B and microstructure evolution in a hot-drawn Fe–B alloy

The grain boundary segregation (GBS) of boron and microstructure evolution in a hot-drawn Fe–B alloy are investigated utilising the Gleeble-1500, Auger electron spectrometer, time-of-flight secondary ion mass spectrometry, electron back-scattered diffraction, and transmission electron microscopy techniques. The results suggest substantial boron segregation at grain boundaries of the Fe–B alloy during the hot drawing process. In comparison to the contribution of dislocations to boron diffusion coefficients, the influence of vacancies is predominant. With the increase in hot-drawing temperature, the ratio of excess vacancy content to thermal equilibrium vacancy content [Formula: see text] decreases, and the content of low [Formula: see text] (low Sigma coincidence site lattice) boundaries increases, resulting in a reduction in boron GBS content. Additionally, elevating the hot-drawing temperature promotes dynamic recrystallisation and refines the grains. The volume fraction of the <110>//RD (rolling direction) texture component initially increases and then decreases with increasing temperature, reaching a maximum value of 64.6% at 830 °C, while the percentage of the <100>//RD + <111>//RD texture components exhibits the opposite trend, with a peak value of 27.4% observed at 1000 °C.

Effective Non-Precious Metal Oxide Supported Carbon as a High Performance Bifunctional Electrocatalyst for All Vanadium Redox Flow Batteries

As one of the most promising electrochemical energy storage systems, vanadium redox flow batteries (VRFBs) have received increasing attention owing to their attractive features for large-scale storage applications. However, their high production cost and relatively low energy efficiency still limit their feasibility. One of the critical components of VRFBs that can significantly influence the effectiveness and final cost is the electrode. Therefore, the development of an ideal electrocatalyst with low cost, large active surface area, good chemical stability, and excellent electrochemical activity toward the VO2+/VO2 + and V2+/V3+ redox reactions is essential for the design of VRFBs. Hence, we prepared a stable, high catalytic activity and uniformly distributed non-precious metal oxide nanoparticles on the surface graphene sheets via two step routes, hydrothermal followed by annealing at optimum temperature for VRFB applications. Among the samples, the prepared electrocatalyst shows the best electrochemical activity with lowest peak potential separation and highest peak current density toward VO2 +/VO2+ and V2+/V3+ redox reactions. This observation is due to the synergistic effects related to the presence of excess oxygen vacancies on the metal oxide, the high content of oxygen functional groups, and the high electrical conductivity of the graphene sheets. Hence, the prepared electrocatalyst grown on the surface of graphite felt (GF) support demonstrates the optimal electrochemical activity with the energy and voltage efficiencies of 76.8% and 80.9%, respectively, which are much greater than those of the 59.8% and 63.2% attained from pristine GF at 100 mA cm–2. Moreover, the electrode presented good stability and durability in acidic electrolyte during long-term operations for 100 cycles at a higher current density of 100 mA cm–2.

Transiently controlled emission from ZnO surface

We report on a photon (∼3.08 eV equivalent to 402 nm) controlled optical emission from ZnO (10 1¯ 0). Under below band gap excitation (∼2.33 eV equivalent to ∼532 nm), significant photoluminescence (PL) overlapped with Raman response is observed. The broad PL consists of three bands (629 (A), 690 (B), and 751 (C) nm) attributed to the defects arising due to excess zinc and charged oxygen vacancy. By employing a second excitation source at 402 nm, we demonstrate about 50% reduction in the overall PL. We utilize the doubly positive oxygen vacancy state to control the PL emission while transiently reducing its density.

Selective Activation of Lattice Oxygen Site Through Coordination Engineering to Boost the Activity and Stability of Oxygen Evolution Reaction.

Although Ru-based materials are among the outstanding catalysts for the oxygen evolution reaction (OER), the instability issue still haunts them and impedes the widespread application. The instability of Ru-based OER catalysts is generally ascribed to the formation of soluble species through the over-oxidation of Ru and structural decomposition caused by involvement of lattice oxygen. Herein, an effective strategy of selectively activating the lattice oxygen around Ru site is proposed to improve the OER activity and stability. Our synthesized spinel-type electrocatalyst of Ru and Zn co-doped Co3O4 showed an ultralow overpotential of 172 mV at 10 mA cm-2 and a long-term stability reaching to 100 hours at 10 mA cm-2 for alkaline OER. The experimental results and theoretical simulations demonstrated that the lattice oxygen site jointly connected with the octahedral Ru and tetrahedral Zn atoms became more active than other oxygen sites near Ru atom, which further lowered the reaction energy barriers and avoided generating excessive oxygen vacancies to enhance the structural stability of Ru sites. The findings hope to provide a new perspective to improve the catalytic activity of Ru-incorporated OER catalysts and the stability of lattice-oxygen-mediated mechanism.

Selective Activation of Lattice Oxygen Site Through Coordination Engineering to Boost the Activity and Stability of Oxygen Evolution Reaction

AbstractAlthough Ru‐based materials are among the outstanding catalysts for the oxygen evolution reaction (OER), the instability issue still haunts them and impedes the widespread application. The instability of Ru‐based OER catalysts is generally ascribed to the formation of soluble species through the over‐oxidation of Ru and structural decomposition caused by involvement of lattice oxygen. Herein, an effective strategy of selectively activating the lattice oxygen around Ru site is proposed to improve the OER activity and stability. Our synthesized spinel‐type electrocatalyst of Ru and Zn co‐doped Co3O4 showed an ultralow overpotential of 172 mV at 10 mA cm−2 and a long‐term stability reaching to 100 hours at 10 mA cm−2 for alkaline OER. The experimental results and theoretical simulations demonstrated that the lattice oxygen site jointly connected with the octahedral Ru and tetrahedral Zn atoms became more active than other oxygen sites near Ru atom, which further lowered the reaction energy barriers and avoided generating excessive oxygen vacancies to enhance the structural stability of Ru sites. The findings hope to provide a new perspective to improve the catalytic activity of Ru‐incorporated OER catalysts and the stability of lattice‐oxygen‐mediated mechanism.

Rational Regulation of Optimal Oxygen Vacancy Concentrations on VO2 for Superior Aqueous Zinc-Ion Battery Cathodes.

VO2 with its special tunnel structure and high theoretical capacity is an ideal candidate for cathode materials for aqueous zinc-ion batteries (ZIBs). However, the slow kinetics and structural instability due to the strong electrostatic interactions between the host structure of VO2 and Zn2+ hinder its application. Defect engineering is a well-recognized strategy for improving the intrinsic ion-electron dynamics and structural stability of this material. However, the preparation of oxygen vacancies poses significant difficulties, and it is challenging to control their concentration effectively. Excessive or insufficient vacancy concentration can have a negative effect on the cathode material. Herein, we propose electrode materials with controlled oxygen vacancies prepared in situ on carbon nanofibers (CNF) by a simple, one-step hydrothermal process (Ov-VO2@CNF). This method can balance the adsorption energy and migration energy barrier easily, and we maximized the adsorption energy of Zn2+ while minimizing the adsorption energy barrier. Notably, the Ov2-VO2@CNF electrode delivered a high specific capacity (over 450 mAh g-1 at 0.1 A g-1) and excellent cycle stability (318 mAh g-1 at 5 A g-1 capacity after 2000 cycles with a capacity retention of 85%). This rational design of precisely regulated defect engineering provides a way to obtain advanced electrode materials with excellent comprehensive properties.

Effective sunlight photodegradation of methylene blue dye using zinc oxide doped with mono- and bi-metals of Ag and Ce

Nanosized spherical particles of pure ZnO and their doped ZnO photocatalysts with mono- or bi- Ag and Ce-metal oxides at different weight portions (i.e., 2 and 4 wt%) through the sol-gel route followed by a calcination at 500 °C for 2 h were employed for exploring the photodegradation of methylene blue (MB) dye under direct sunlight. The produced photocatalysts were characterized by X-ray diffraction (XRD), Brunauer, Emmett and Teller (BET) surface area, scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscope (TEM), fourier transform infrared (FTIR), and UV-Vis diffuse reflectance spectroscopy (DRS). XRD patterns confirmed the formation of hexagonal wurtzite polycrystalline structure of ZnO with good crystallinity. Bi-doped ZnO photocatalysts with smaller particle sizes showed efficient improving in the photocatalytic activity of ZnO under direct sunlight irradiation. The enhanced photodegradation performance of doped samples could be attributed to the reduction in the crystallite size and band gap, as well as the presence of excess oxygen vacancies and Zn interstitial sites in the nanoparticles obtained. The calculated band gap of pure ZnO decreased from 3.07 to 2.79 eV for 2 %Ag-4 %Ce/ZnO. This doped sample degraded the MB dye completely at 60 min, whereas pure ZnO exhibited 100 % degradation of MB at 180 min. Moreover, 2 % Ag-4 %Ce/ZnO photocatalyst has the highest kinetic rate of photodegradation as compared to other samples over two initial concentrations of MB dye (0.09667 min−1 at Co= 10 mg/L and 0.04433 min−1 at Co= 20 mg/L). Hence, the obtained 2 % Ag-4 % Ce doped ZnO showcased the superb breakdown of MB dye under sunlight irradiation for positioning it as a promising material for water remediation.

Extension of a phase-field KKS model to predict the microstructure evolution in LPBF AlSi10Mg alloy submitted to non isothermal processes

The out-of-equilibrium heterogeneous microstructure typical of AlSi10Mg processed by Laser Powder Bed Fusion (LPBF) is often modified by further heat treatment to improve its ductility. According to literature, extensive experimental investigations are generally required in order to optimize these heat treatments. In the present work, a phase-field approach is developed based on an extended Kim–Kim–Suzuki (KKS) model to guide and accelerate the post-treatment optimization. Combined with CALculation of PHAse Diagrams (CALPHAD) data, this extended KKS model predicts microstructural changes under anisothermal conditions. To ensure a more physical approach, it takes into account the enhanced diffusion by quenched-in excess vacancies as well as the elastic energy due to matrix/precipitate lattice mismatch. As the developed model includes the computation of the evolution of the thermo-physical properties, its results are validated through comparison with experimental DSC curves measured during the non-isothermal loading of as-built LPBF AlSi10Mg. The computed microstructure evolution reproduces the microstructural observation and successfully explains the peaks in the DSC heat flow curve. It thus elucidates the detailed microstructural evolution inside the eutectic silicon phase by considering the growth and coalescence of silicon precipitates and the matrix desaturation.

Remarkably Boosting Piezocatalytic Performance of Sr0.5Ba0.5Nb2O6 Piezoceramics via Size Optimization and Oxygen Vacancy Engineering

AbstractPiezocatalysis is capable of harnessing mechanical energy for environmental remediation, which is regarded as a green and promising technology to be exploited. Piezoceramics are struggling to be used as highly efficient piezocatalysts due to their grain size reaching tens of micrometers usually. Herein, a feasible and straightforward method is proposed to turn piezoceramic powders into highly efficient piezocatalysts by integrating size optimization and oxygen vacancy modulation. This strategy is validated by treating lead‐free Sr0.5Ba0.5Nb2O6 (SBN) piezoceramic powders with high‐energy ball‐milling (hBM). The rate constant k value of 46.95 × 10−3 min−1 for rhodamine B (RhB) piezocatalytic degradation of SBN‐hBM‐12h is almost 18 times higher than that of pristine SBN. Besides, the SBN‐hBM‐12 h catalyst performed superior antibacterial properties against Escherichia coli. The enhanced piezocatalytic efficiency is attributed to the introduced abundant oxygen vacancies absorbing and activating O2 into reactive oxygen species. Well‐modulated oxygen vacancy concentration can effectively accelerate the generation and separation of free carriers. However, the excess oxygen vacancies in SBN render the weakened piezoresponse thus suppressing the piezocatalytic activity. This study elucidates the critical role of oxygen vacancies in piezocatalysis and provides insights into the development of efficient piezocatalysts.

On the theory of nucleation of coherent inclusions in irradiated crystals

Based on a critical analysis of the existing model for the effect of excess vacancies and interstitials on the nucleation of coherent particles under irradiation, a new nucleation model is developed that uses the Brailsford-Bullough model for the steady state occupation probabilities of vacancies and interstitials at the particle interface, recently refined by the author. It is shown that, depending on the surface tension γ of a coherent particle, the nucleation mechanism can be qualitatively different. In the case of a relatively small γ, an instability can arise in the irradiated solid solution leading to the barrier-free nucleation of coherent precipitates. In the opposite case of a relatively large γ, the classical one-dimensional theory of homogeneous nucleation is applicable. In order to eliminate the uncertainty in the magnitude of surface tension (from the literature) and to better understand the underlying mechanisms of coherent particle nucleation in irradiation tests, additional atomistic studies are recommended.

Influence of atmosphere-induction and synergistic effect on the dielectric property of rutile-type (Ge0.2Mn0.2Ti0.2Sn0.2Mo0.2)O2 high-entropy oxides

A new high-entropy oxide, (Ge0.2Mn0.2Ti0.2Sn0.2Mo0.2)O2 with rutile structure, was successfully synthesized using solid-state reaction method. The phase structure of the ceramic samples prepared forming a range of binary to quinary phase with increasing entropy were investigated, and the effects of atmosphere-induction and high-entropy synergistic behavior on the dielectric performance were studied. As the type of the cations increases, the temperature required to form a single rutile structure gradually decreases, while the dielectric properties of the ceramics gradually improved. The dielectric constant of the (Ge0.2Mn0.2Ti0.2Sn0.2Mo0.2)O2 high-entropy oxide ceramics sintered in the nitrogen atmosphere at 1350°C is nearly 20 times higher of the ceramics sintered in the air. This significant enhancement can be attributed to the occurrence of two rutile structures and the generation of excessive oxygen vacancies as a result of high-entropy synergistic behavior under the nitrogen sintering atmosphere.

Influence of entropy on catalytic performance of high-entropy oxides (NiMgZnCuCoOx) in peroxymonosulfate-mediated acetaminophen degradation

Developing a high-performance activator is crucial for the practical application of peroxymonosulfate-based advanced oxidation processes (PMS-AOPs). High-entropy oxides (HEOs) have attracted increasing attention due to their stable crystal structure, flexible composition and unique functionality. However, research into the mechanisms by which HEOs function as PMS activators for degrading organic pollutants remains insufficient, and the relationship between entropy and the catalytic performance of HEOs has yet to be clarified. In this study, we synthesized NiMgZnCuCoOx with different levels of entropy as PMS activators for acetaminophen (APAP) degradation, and observed a significant effect for entropy on the catalytic performance. Sulfate radicals (SO4•‒) were identified as the primary reactive oxygen species (ROS), while hydroxyl radicals (•OH) and singlet oxygen (1O2) act as secondary ROS during APAP degradation. Both the Co2+ contents and the oxygen vacancy concentration in NiMgZnCuCoOx are found to increase with the entropy. An increase in the Co2+ sites leads to more activation sites for PMS activation, while excessive oxygen vacancies consume PMS, producing weak oxidation species, and affect the electron-donating ability of Co2+. Consequently, the NiMgZnCuCoOx with middle level of entropy exhibits the optimal performance with APAP degradation rate and mineralization rate reaching 100% and 74.22%, respectively. Furthermore, the degradation intermediates and their toxicities were assessed through liquid chromatography-mass spectrometry and quantitative structure-activity relationship analysis. This work is expected to provide critical insight into the impact of the HEOs entropy on the PMS activation and guide the rational design of highly efficient peroxymonosulfate activators for environmental applications.

Nanoprecipitation induced giant magnetostriction: A time-resolved small-angle neutron scattering study of the vacancy-assisted kinetics

Solid-state precipitation is an effective strategy for tuning the mechanical and functional properties of advanced alloys. Structure design and modification necessitate good knowledge of the kinetic evolution of precipitates during fabrication, which is strongly correlated with defect concentration. For Fe-Ga alloys, giant magnetostriction can be induced by the precipitation of the nanoscale tetragonal L60 phase. By introducing quenched-in vacancies, we significantly enhance the magnetostriction of the aged Fe81Ga19 polycrystalline alloys to ∼305 ppm, which is close to the level of single crystals. Although vacancies were found to facilitate the generation of the L60 phase, their impact on the precipitation mechanism and kinetics has yet to be revealed. This study combined transmission electron microscopy (TEM) and time-resolved small-angle neutron scattering (SANS) to investigate the precipitation of the L60 phase during the isothermal aging at 350 and 400 °C, respectively. The evolution of L60 nanophase in morphology and number density in as-cast (AC) and liquid nitrogen quenched (LN) Fe81Ga19 alloys with aging time were quantitatively compared. Interestingly, the nucleation of the L60 phase proceeds progressively in AC while suddenly in LN specimens, indicating the homogenous to heterogeneous mechanism switching induced by concentrated vacancies. Moreover, excess vacancies can change the shape of nanoprecipitates and significantly accelerate the growth and coarsening kinetics. The magnetostrictive coefficient is optimized when the size (long-axis) of L60 precipitates lies between 100 and 110 Å with a number density between 3.2–4.3 × 10–7 Å–3. Insight from this study validates the feasibility of achieving high magnetoelastic properties through precise manipulation of the nanostructure.

Electric field/current enhanced grain growth behavior of 8mol% Y2O3 stabilized cubic ZrO2 (8Y-CSZ) polycrystals

The effect of the flash event on grain growth behavior was examined in 8 mol% yttria-stabilized cubic zirconia (8Y-CSZ) polycrystals under direct and alternating electric fields/currents. Even at the same specimen temperature, the rate of the grain growth is accelerated in the flash event than in the heat treatment without electric field/current (0 V), suggesting that the non-thermal effect caused additionally under the flash event contributes to the acceleration of the grain growth. Although the grain growth behavior can be characterized by the empirical equation (dtn –d0n = kt) with the same grain growth exponent of n = 3 irrespective of the electric field/current, the activation energy for the grain growth is lowered under the flash event. This suggests that the non-thermal effect caused by the flash event does not affect the mechanism of the grain growth, but would accelerate the rate-controlling process of the grain growth. The non-thermal effects can be further accelerated in fine-grained specimens under the alternating current flash and/or by increasing the input power density. Since the grain growth is rate-controlled by the grain boundary cation diffusivity, the non-thermal effect under the flash event would accelerate the grain boundary cation diffusivities through the formation of excess oxygen vacancies depending on the polarity and the power density.

Phase-field determination of NaSICON materials in the quaternary system Na2O-P2O5-SiO2-ZrO2: II. Glass-ceramics and the phantom of excessive vacancy formation

This work focuses on a very narrow region in the quaternary system Na2O-P2O5-SiO2-ZrO2 to explore the occasionally proposed deficiency in zirconium and oxygen content of Na+ super-ionic conductor (NaSICON) materials. In addition, this region is known for the formation of glass-ceramics, but a systematic study of such materials has not been carried out yet. For this purpose, 2 series of compositions were defined and synthesized: Na3.4Zr2-3x/4Si2.4-x/4P0.6+x/4O12-11x/8 and Na3.4Zr2-3x/4Si2.4+x/4P0.6+1.5x/4O12-x/16. They only differ in the silicate and phosphate content. In the first series the molar content is constant, nSi+ nP = 3. The latter series allows an excess of the 2 cations to meet the composition Na3.1Zr1.55Si2.3P0.7O11 or alternatively re-written as Na3.4Zr1.7Si2.52P0.77Ol2, which was formerly regarded as a superior material to the frequently reported composition Na3Zr2Si2POl2.Several characterization techniques were applied to better understand the relationships between phase formation, processing, and properties of the obtained glass ceramics in the context of the quasi-quaternary phase diagram. The investigations gave clear evidence that a glass phase is progressively formed with increasing x. Therefore, compounds with x > 0.2 have to be regarded as glass-ceramic composites. The resulting NaSICON materials revealed a very limited Zr deficiency with charge compensation by Na ions and a non-detectable amount of oxygen vacancies verified by neutron scattering and atomistic simulations.Hence, this work is the first systematic investigation of pretended Zr-deficient NaSICON materials, which clearly show the chemistry of a 2-phase region. The 2 investigated series are directed toward a region that is orthogonal to the series Na3Zr3-ySi2PyO11.5+y/2 reported in the first part of this series of publications.

Modulation of Sulfur Vacancies in ZnIn2S4/MXene Schottky Heterojunction Photocatalyst Promotes Hydrogen Evolution

AbstractThe sustainable production of hydrogen utilizing solar energy is a pivotal strategy for reducing reliance on fossil fuels. ZnIn2S4 (ZIS), as a typical metal sulfide semiconductor, has received extensive attention in photocatalysis. Although the introduction of sulfur (S) vacancies in ZIS to enhance photocatalytic hydrogen production by creating defect energy levels has been explored, detailed studies on the control and modulation of S‐vacancies in ZIS are sparce. This study demonstrates that while moderate levels of S‐vacancies can enhance hydrogen evolution, excessive vacancies may hinder the process, underscoring the importance of S‐vacancy modulation. Guided by theoretical calculations, We have designed and synthesized ZIS with modulated S‐vacancies to realize favorable hydrogen adsorption‐free energy and integrated in a Schottky‐heterojunction with MXene co‐catalysts for enhanced hydrogen evolution. The optimized hydrogen evolution performance of ZnIn2S4/MXene (ZMX) reaches 14.82 mmol g−1 h−1 under visible light irradiation, surpassing many reported ZnIn2S4‐based photocatalysts. The enhanced performance is ascribed to widened light absorption and enhanced carrier transportation realized by S‐vacancy modulation and the co‐catalytic effect. Femtosecond ultrafast absorption (fs‐TA) spectra and other in‐situ/ex‐situ characterizations further prove an efficient separation and transfer in an as‐prepared ZMX catalyst. These findings open up new perspectives for designing catalysts with vacancy modulation.