Electronegativity Difference Research Articles

Control of sensitivity in metal oxide electrolyte gated field-effect transistor-based glucose sensor by electronegativity modulation

In this study, the sensitivity of electrolyte-gated field-effect transistor-based glucose sensors using oxide semiconductor materials was controlled via electronegativity modulation. By controlling the enzymatic reaction between glucose and glucose oxidase, which is affected by the surface potential, the sensitivity of the glucose sensor can be effectively adjusted. To evaluate the sensitivity characteristics of the glucose sensor according to electronegativity control, devices were fabricated based on InO through Ga and Zn doping. The results confirmed that the specific sensitivity range could be adjusted by increasing the electronegativity. In addition, density functional theory calculations, confirmed that the attachment energy of the surface-functionalized material and the enzyme binding energy in the surface-functionalized thin film can be modulated depending on the electronegativity difference. The dissociation constant was controlled in both directions by doping with metal cations with larger(Ga, 1.81) or smaller(Zn, 1.65) electronegativities in InO(In, 1.78). We expect that this study will provide a simple method for the gradual and bidirectional control of the glucose sensitivity region.

Structure, Synthetic Pathway, and Properties of Metastable Phosphorus Carbide, P4C3.

Due to electronegativity (EN) differences, changing from C3N4 to P4C3 is not as trivial as simply replacing nitrogen by phosphorus in the C3N4 structure. Hence, the nonexistent P4C3 phase is nominally the higher-homologue analogue of the well-known C3N4, but its structure and properties are practically unknown for fundamental reasons. Here we predict, by means of an extensive structure search, three energetically favorable yet metastable P4C3 phases adopting space groups P1̅, Cm, and Cmmm, followed by designing their synthetic routes. Different from the planar structural motifs of C3N4, P4C3 is likely to adopt various "puckered" (as regards the P atoms) forms, mainly related to the EN difference between nitrogen and phosphorus, the difference in atomic size, and also less favorable sp orbital mixing for phosphorus related to primogenic repulsion; hence, the P substructures are characterized by single and fractional P-P bonds with rectangular/linear motifs or those resembling simple-cubic P, including multicenter bonding as a function of the large electron count. As regards the carbon substructures, infinite polyacetylene-like motifs, carbon dimers, and infinite chains of cyclopentadienyl-like and polyphenyl-like units are predicted, with C-C bond orders larger than one. Band structure analyses indicate the metallic character of these three phases. The P1̅ polymorph exhibits a Dirac cone, whereas the Cmmm phase, being composed of metallic "phosphorene" units and infinite polyphenyl units, might show potential in applications, e.g., battery electrodes. Moreover, the monolayer of the P1̅ polymorph should be easy to exfoliate and exhibit a large anisotropy with regard to mechanical and electronic properties. The synthesis of P4C3 defining a new class of IV3V4 compounds should be attempted due to its predicted structural and physicochemical properties.

Exploring the thermoelectric performance of NiFeMnAl and ZnFeVAl as novel quaternary Heusler compounds

Quaternary Heusler (QH) compounds, characterized by the chemical formula XX’YZ, are highly regarded in the energy materials sector due to their versatile electronic structures. The current study focuses on synthesizing novel QH compounds, NiFeMnAl and ZnFeVAl, through arc-melting followed by hot-pressing at 1073 K. Maximum Seebeck coefficients were exhibited ∼ −20.48 μV/K and ∼ −17.25 μV/K at 773 K for ZnFeVAl and NiFeMnAl, respectively. The evaluated power factor was ∼ 0.058 mWm−1K−2 for NiFeMnAl and ∼ 0.020 mWm−1K−2 for ZnFeVAl at 773 K. Furthermore, the lattice thermal conductivity (κl) was exhibited ∼ 8.73 Wm−1K−1 for NiFeMnAl and ∼ 6.92 Wm−1K−1 for ZnFeVAl at 773 K, with ZnFeVAl exhibiting a ∼ 20.73 % lower κl attributed to chemical bonding distortion arising from differences in constituent element electronegativity. Hence, these novel compounds offer a promising avenue for further research in TE materials, aiming to realize higher-performance materials for practical TE device applications.

Construction of electron-deficient Co on the nanoarrays enhances absorption and direct electron transfer to accelerate electrochemical nitrate reduction

Electrochemical nitrate reduction is a promising remediation strategy for nitrate-contaminated wastewater treatment, in which nitrate adsorption is a prerequisite step in the overall process. Herein, the iron-induced cobalt phosphide was grown in situ on porous nickel foam (Fe-CoP/NF) for the electrochemical nitrate reduction. Structural characterization verified doping of Fe and the uniform nanotube arrays of Fe0.03CoP/NF. Remarkably, the Fe0.03CoP/NF exhibited a high efficiency nitrate removal efficiency (99.3%) and excellent ammonia selectivity (100% selectivity and 0.485mg·h-1cm-2 NH3 yield rate). Both experimental and theoretical results reveal that Fe doping alters the local charge distribution of the Co active centers to form electron-deficient Co. The Co electron-deficient regions were constructed due to the difference in electronegativity between Co and Fe. Furthermore, the formation of electron-deficient centers facilitates the reduction of charge transfer resistance. In particular, Fe0.03CoP/NF maintained an excellent conversion efficiency of nitrate to N2 (99.8%) with 60mM Cl−, and the selectivity of N2 is maintained above 99.1% during long-term operation. This system possesses a low electrical consumption of 1.79 kWh·molN-1. This study designed an enhanced electrocatalyst through enhanced nitrate absorption and direct electron transfer strategies, thus providing a promising and low-power consumption approach for addressing nitrate pollution.

Effect of carbon on microstructure and mechanical properties of TiZrNb0.5V0.5 lightweight refractory high entropy alloy

The single-phase body-centered cubic TiZrNb0.5V0.5 lightweight refractory high entropy alloy exhibits good plasticity but poor strength. Therefore, C is added to this alloy to enhance its strength and improve its mechanical properties in this paper. The influence of varying C content on the microstructure, phase composition, and mechanical behavior of TiZrNb0.5V0.5C x RHEAs is investigated in detail. The results indicate that C addition leads to the dissolution of alloying dendrites and induces the formation of the FCC – MC carbides phase. The carbide volume fraction increases in proportion to the carbon content, thereby enhancing the alloy's yield strength and hardness. The yield strength increases by 36%, while the hardness increases by 39%. The physical parameters of the alloy are analyzed, which reveals that the introduction of C increases the alloy's electronegativity and atomic radius difference, thus promoting the formation of carbides.

Cleavage of Homonuclear Chalcogen‐Chalcogen Bonds in a Hybrid Platform in Response to X‐Ray Radiation Potentiates Tumor Radiochemotherapy

AbstractChalcogens are used as sensitive redox‐responsive reagents in tumor therapy. However, chalcogen bonds triggered by external ionizing radiation, rather than by internal environmental stimuli, enable site‐directed and real‐time drug degradation in target lesions. This approach helps to bypass chemoresistance and global systemic toxicity, presenting a significant advancement over traditional chemoradiotherapy. In this study, we fabricated a hybrid monodisperse organosilica nanoprodrug based on homonuclear single bonds (disulfide bonds (S−S, approximately 240 kJ/mol), diselenium bonds (Se−Se, approximately 172 kJ/mol), and tellurium bonds (Te−Te, 126 kJ/mol)), including ditelluride‐bond‐bridged MONs (DTeMSNs), diselenide‐bond‐bridged MONs (DSeMSNs) and disulfide‐bond‐bridged MONs (DSMSNs). The results demonstrated that differences in electronegativities and atomic radii influenced their oxidation sensitivities and reactivities. Tellurium, with the lowest electronegativity, showed the highest sensitivity, followed by selenium and sulfur. DTeMSNs exhibited highly responsive cleavage upon exposure to X‐rays, resulting in oxidation to TeO32−. Furthermore, chalcogen‐hybridized organosilica was loaded with manganese ions (Mn2+) to enhance the release of Mn2+ during radiotherapy, thereby activating the the stimulator of interferon genes (STING) pathway and enhancing the tumor immune response to inhibit tumor growth. This investigation of hybrid organosilica deepens our understanding of chalcogens response characteristics to radiotherapy and enriches the design principles for nanomedicine based on prodrugs.

Dual metal centers within a water-stable Co/Ni bimetallic metal-triazolate framework contribute to durable photocatalysis for water treatment.

Bimetallic metal-organic frameworks (MOFs) have been studied extensively in various fields, including photocatalytic and electrocatalytic applications. The enhanced catalytic activity is typically attributed to the synergistic effect of the two metals, often without further explanation. Here, we demonstrate a CoNi-bimetallic triazolate MOF with fixed metal occupancy within the MOF's secondary building unit. Due to the difference in electronegativity and so on, the charge redistribution between the two metal centers could be responsible for the enhanced photocatalytic activity. In addition, the metal(II)-triazolate MOFs we synthesized exhibit unique metal-N coordination and a strong bond between the metal center and triazole ring. Therefore, their crystal structure and high porosity are highly retained even after exposure to humid environments for several months or stirring in water for several days. Overall, the CoNi-bimetallic triazolate MOF combines the excellent water stability and high surface area of its two monometallic counterparts. It can be further tailored to yield the highest colloidal stability during photocatalytic water treatment. As a result, the dual metal centers within the bimetallic MOF, combined with boosted colloidal stability, demonstrate the highest reactive oxygen species generation and promising antibacterial performance compared to their Ni- or Co-based counterparts. These findings shed light on the future design of robust MOF-based photocatalysts, particularly bimetallic ones.

Revisiting Stability Criteria in Ball‐Milled High‐Entropy Alloys: Do Hume–Rothery and Thermodynamic Rules Equally Apply?

Stability descriptors for the formation of solid solutions can be divided into two categories: inspired by Hume–Rothery rules (HRR) and derived from thermodynamic approaches. Herein, HRRs are extended from binary to high‐entropy alloys (HEAs) focusing on compositions prepared by ball milling. Parameters describing stability criteria are interrelated and implicitly account for the microstrains’ storage energy, more determinant than entropy increase in stabilization of HEAs and more effective in bcc structures than close‐packed ones (fcc and hcp). An effective temperature, Teff, is defined as the ratio between increase in metallic bonding energy of solid solutions with respect to segregated pure constituents and configurational entropy. This versatile parameter is used as a threshold for stabilization of HEAs at equilibrium and out of equilibrium. When Teff is below room temperature, HEA would be stable at equilibrium. When Teff is below melting temperature, HEA would be obtained by rapid quenching. Limitations related to electronegativity differences remain valid in mechanically alloyed solid solutions. However, ball milling broadens the allowed differences in atomic size to form HEA. Moreover, thermodynamic criteria can be surpassed in these systems, allowing the formation of single‐phase solid solutions beyond the compositional range predicted by those criteria.

Prediction of stable structure and unique charge transfer in Li–Pt intermetallic compounds under pressure

The exploration of new intermetallic compounds is of great significance for basic research and practical application. There is a huge electronegativity difference between Li and Pt, and the metals exhibit interesting and diverse properties; however, the structural behavior of Li–Pt intermetallics with different ratios under high pressure has not been systematically studied. In this study, an intelligent structure search method based on a particle swarm optimization algorithm combined with first-principles calculations was used to extensively explore the stable structures and unique conditions governing charge transfer in Li–Pt intermetallic compounds under different pressures. In addition to reproducing the known LiPt (P6‾m2) and Li2Pt (P6/mmm), the simulation was consistent with the experimental results. New phases were also found by calculation: LiPt3(Cmmm), Li2Pt (P3‾m1), and Li4Pt (I4/m) at ambient pressure; Li3Pt (Fm3‾m), Li4Pt (R3‾m), and Li5Pt (P6/mmm) at 10 GPa; and Li5Pt (P3‾m1) at 20 GPa. Bader charge analysis and electron localization function (ELF) mapping showed that the transition metal (Pt) atoms exhibit unusual oxidation states both under ambient and high pressure, and more electrons were localized on Pt as the Li content increased. The highest negative valence state was approximately −4. Intermetallic compounds LiPt3 (Cmmm) and Li2Pt (P6/mmm) were prepared successfully by arc melting furnace. The reliability of structure prediction method and pseudo potential selection was verified. This work demonstrates that tuning the pressure and stoichiometry is an effective means of forming novel, stable intermetallic compounds.

Intrinsic Electron Transfer in Heteronuclear Dual‐Atom Sites Facilitates Selective Electrocatalytic Carbon Dioxide Reduction

AbstractThe metal–metal (M1–M2) interactions in heteronuclear dual‐atom catalysts (HNDACs) significantly optimize the electronic properties of the active sites, resulting in the promotion of the reaction kinetics in electrocatalysis. However, the regulation mechanisms in these M1–M2 dual‐atom sites still remain unclear. Herein, the intrinsic electron transfer in Fe–Zn dual‐atom sites are revealed for facilitating electrocatalytic carbon dioxide reduction (ECO2R) to carbon monoxide (CO). The electronegativity difference between the Fe and Zn centers induces the specific electron transfer from Zn to Fe, which regulates the electron structures of the active Zn sites, leading to the optimized reaction pathway of CO2‐to‐CO conversion on these sites. The Fe–Zn HNDAC (FeZnNC) exhibits superior ECO2R performances than the single‐atom Fe/Zn catalysts (FeNC and ZnNC) in the typical H‐cell system, the maximum CO partial current density on FeZnNC reaches more than 3.3 and 1.8 folds of those on FeNC and ZnNC, respectively. More importantly, in a strongly acidic medium (pH = 1), FeZnNC achieves CO Faradaic efficiencies greater than 94% in the current density range of 100–400 mA cm−2. This work uncovers the intrinsic electron transfer at the heteronuclear diatomic sites, providing new insights for the rational design of high‐performance HNDACs toward industrial electrocatalysis.

Tip-like copper sites on high curvature supports for non-covalent to covalent interaction tuning in CO2 photoreduction

Single-atom engineering offers a promising method to transform CO2 into high-value chemicals. The local coordination structure design of the metal-support is crucial for overcoming slow reaction kinetics. In this study, Cu single atoms are immobilized on curved Bi12O17Br2 surface to create a tip-like metal site structure named Cutip-Bi12O17Br2. Due to the high curvature Bi12O17Br2 surface with tensile strain, the tip Cu creates significant electronegativity differences between adjacent Bi atomic sites, creating the vigorous polarization centers. The strong charge redistribution character of tip asymmetric Cu-Bi site favor the polarization of CO bond in nonpolar CO2 and adjust the noncovalent to covalent interaction of reaction intermediates. Benefiting from these features, the optimized Cutip-Bi12O17Br2 enhance the CO production rate by a factor of 34 relative to bulk-Bi12O17Br2, reaching a rate of 96.99 μmol g−1 h−1. This work provides a comprehensive understanding of the structural regulation of single-atom on high curvature surface for CO2 photoreduction.

Aromaticity in Isoelectronic Analogues of Benzene, Carborazine and Borazine, from Electronic Structure and Magnetic Property.

Carborazine (B2C2N2H6) and borazine (B3N3H6) are isoelectronic analogues of benzene (C6H6). The aromatic character of borazine have basically reached a consensus after a long period of controversy, but the related properties of carborazine are even rarely reported. In this work, we systematically investigated the geometric structure, charge distribution, frontier molecular orbital characteristics, bonding, electronic delocalization, magnetic shielding effect, and induced ring current of carborazine and borazine, and compared the studied characteristics with those of benzene to determine the aromatic character of the two analogues. The combination of multiple properties shows that although they are isoelectronic, carborazine is evidently aromatic, while borazine only exhibits rather weak aromaticity. The C atom acting as a connecting bridge between B and N atoms in carborazine reduces the electronegativity difference on the molecular backbone and enhances the electronic delocalization over the conjugated path, which is the essence of the distinct disparity of aromaticity between carborazine and borazine.

Surface morphology evolution, microstructural response and mechanical property variation of Au-ion irradiated CrNbZrMoV, TiCrZrMoV, TiNbCrMoV, TiNbZrCrV and TiNbZrMoCr high-entropy alloy coatings

In this work, the CrNbZrMoV, TiCrZrMoV, TiNbCrMoV, TiNbZrCrV and TiNbZrMoCr refractory high-entropy alloy (RHEA) coatings (1.67∼2.77 μm of thickness) were prepared by magnetron sputtering. Then, 6 MeV Au-ion irradiations with 2.5 × 1015 to 1.0 × 1016 ions/cm2 fluences were performed on these coatings at 473 K, and the surface morphology, microstructure and mechanical property were investigated. The peak damage of the CrNbZrMoV, TiCrZrMoV, TiNbCrMoV, TiNbZrCrV and TiNbZrMoCr coatings under 1.0 × 1016 ions/cm2 fluence are 48, 48, 44, 48 and 48 dpa, respectively. The peak Au concentration of the CrNbZrMoV, TiCrZrMoV, TiNbCrMoV, TiNbZrCrV and TiNbZrMoCr coatings under 1.0 × 1016 ions/cm2 fluence are 4.27 × 103, 4.12 × 103, 4.13 × 103, 4.16 × 103 and 4.37 × 103 appm, respectively. The surface morphology of the CrNbZrMoV, TiCrZrMoV, TiNbZrCrV and TiNbZrMoCr coatings were smoothed obviously. For BCC TiNbCrMoV coating, irradiation caused the growth of the nanocrystalline. For amorphous coatings, the crystallization occurred in the CrNbZrMoV, TiCrZrMoV and TiNbZrMoCr coatings after 2.5 × 1015 fluence irradiation (≥12 dpa), while the TiNbZrCrV coating remain mainly amorphous structure after all irradiation. It was found that irradiation induced continuous crystallization occurred not only at the surface but also in the peak damage zone of the coating, and then grew inside the irradiated region. Apparent irradiation hardening was observed in all the coatings except the TiNbZrCrV coating. The structural stability of these coatings under the current irradiation condition was discussed. Preliminary study shows that the great irradiation tolerance of amorphous TiNbZrCrV coating may be related to the lowest electronegativity difference (Δχ = 0.121) and large atomic size difference (δ = 9.042 %) that stabilize the structure and inhibit atomic diffusion, respectively. These findings provide the guidance for the development of high irradiation tolerance materials for future nuclear energy applications with great structural stability.

Prediction of phases and mechanical properties of magnesium-based high-entropy alloys using machine learning

ObjectivesTo predict phases and mechanical properties of Mg-Al-Cu-Mn-Zn alloys and to validate the results. MethodsIn this study, 29 predictor features of the alloys were examined based on dataset drawn from relevant publications. The correlation of selected predictor features with mechanical properties of Mg-Al-Cu-Mn-Zn alloys were evaluated. New features specific to vehicle and aerospace applications were used. Feature selection schemes involving four machine learning (ML) classifiers that included artificial neural networks (ANN), linear discriminant analysis (LDA), random forest regression (RF) and k-nearest neighbours (k-NN) were adopted. Tensile test was carried out based on ASTM E8 standard. ResultsResults of correlation of features showed that specific strengths and specific modulus of the alloys were strongly and positively correlated with composition of alloying elements but strongly and negatively correlated with composition of magnesium. The results also revealed that homogenization temperatures and time were weakly correlated with the mechanical properties and phases while electronegativity difference and VEC had significant positive correlation. ANN was the best performing classifier followed by k-NN, LDA, and lastly RF with prediction accuracy on test data of 98.7%, 98.1%, 97.9% and 97.8%, respectively. The validity and applicability of the model was tested with three magnesium-based alloys: Mg-80-Al-10-Cu-5-Mn-5-Zn-0, Mg-80-Al-5-Cu-5-Mn-5-Zn-5 and Mg-91.2-Al-8.3-Cu-0-Mn-0.15-Zn-0.35 and compared with findings in literature. The model had higher prediction accuracies compared to previous ML models used on magnesium alloys. The model was then used to predict phases in the Mg-89.43-Al-8.16-Cu-0.34-Mn-0.25-Zn-1.81 alloy and it accurately predicted presence of Mg17Al12, Mg2Si, MgZn and MgZn2. Results of simulation in MatCalc version 6.04 also verified presence of the phases. The phases were further confirmed through SEM/EDS analysis.Conclusions.Dominant strengthening phases were Mg17Al12, Mg2Si, MgZn and MgZn2. Predicted yield strength, ultimate tensile strength and Young’s modulus were within the range of experimental results. Specific strengths and specific modulus were also within the range.

Machine learning-assisted design of refractory high-entropy alloys with targeted yield strength and fracture strain

In order to improve the traditional “trial and error” material design method, machine learning-yield strength and machine learning-fracture strain models are incorporated into one system to predict yield strength and fracture strain in refractory high-entropy alloys (RHEAs) under compression. The ML-yield strength model and ML-fracture strain model achieve excellent predictions (R2 = 0.942, RMSE=0.35) and (R2 = 0.892, RMSE=0.41) in the testing set, respectively. Based on the machine learning model, Nb0.22Ta0.22Ti0.24V0.23W0.09, Nb0.24Ta0.22Ti0.26V0.04W0.24, Nb0.26Ta0.24Ti0.21V0.24W0.05, and Nb0.18Ta0.26Ti0.22V0.21W0.13 RHEAs in the Nb-Ta-Ti-V-W RHEA system were screened and synthesized. The yield strength (1915 MPa, 1983 MPa) of the Nb0.22Ta0.22Ti0.24V0.23W0.09 and Nb0.24Ta0.22Ti0.26V0.04W0.24 RHEAs are higher than that (1689 MPa) of the NbTaTiVW RHEA. The unfractured Nb0.18Ta0.26Ti0.22V0.21W0.13 and Nb0.26Ta0.24Ti0.21V0.24W0.05 RHEAs under compression exhibit superior performance than the fracture strain (16.6 %) of the NbTaTiVW RHEA. The mixing enthalpy of RHEAs is negatively correlated with the yield strength, whereas a negative relationship exists between electronegativity difference and fracture strain through the SHAP analysis. Decreasing the mixing enthalpy and increasing the electronegativity difference promote the formation of the precipitated phase. The electron probe microanalysis reveals that the differences in mechanical properties (yield strength and fracture strain) in the NbTaTiVW RHEAs primarily stem from the fraction of the precipitated phase.

Microstructure evolution and catalytic activity of AlCo1−xFeNiTiMox high entropy alloys fabricated by powder metallurgy route

This investigation presents the synthesis of equiatomic and non-equiatomic AlCo1−xFeNiTiMox (x = 0, 0.1, 0.25 and 1.0) high entropy alloys fabricated by mechanical alloying. Mo partially replaced Co. Classic thermodynamic calculations, such as mixing enthalpy (ΔHmix), configurational entropy (ΔSmix), the atomic size difference (δ), entropy to enthalpy ratio (Ω), electronegativity difference (△χ), and valence electron concentration (VEC) were used. Considering δ, Ω and VEC parameters, a BCC solid solution and an intermetallic phase can be predicted due to the partial replacement of Co by Mo. X-ray and electron diffraction of equiatomic HEA without Mo content revealed that after 35 h of milling, a Fe-type BCC lattice phase was formed in the alloy and two L21 phases, in addition to a minimal amount of FCC phase. As the Mo content increased, the Fe-type BCC phase was steadily replaced by the Mo-type BCC phase and the Fe-type FCC phase, and two L21 phases were also developed. When the 5 at% Mo-containing (x = 0.25) alloy was further milled for 80 h, the amount of phases remained almost the same; only the grain size was strongly reduced. The influence of the Mo addition on the properties of studied alloys was also confirmed in the decolourisation of Rhodamine B using a modified photo-Fenton process. The decolourisation efficiency within 20 min was 72% for AlCoFeNiTi and 87% for AlCo0.75FeNiTiMo0.25 using UV light with 365 nm wavelength.

Revealing the role of B-site cations in the antiferroelectricity of NaNbO3-based perovskites

The promising prospects of antiferroelectric perovskite oxides in the realm of energy storage applications hinge on the unique field-induced phase transitions. Once the transition is triggered by the application of an electric field, characteristic double polarization loops appear. However, NaNbO3-based materials that exhibit a reversible phase transition are still rare, which hinders the practical applications of lead-free antiferroelectrics. Here, the impact of materials chemistry on the competition between antiferroelectric and ferroelectric states is demonstrated in a series of NaNbO3-based solid solutions with varying perovskite B-site cations, while the A-site is fixed as strontium. The crystal structure is analyzed on the basis of Rietveld refinement of high-energy X-ray diffraction data. The phase transition behavior as well as the antiferroelectric and ferroelectric properties are probed by a series of electrical measurements. The antiferroelectric phase is universally observed for all investigated materials in the virgin state. The SrTiO3-substituted system shows an irreversible phase transition similar to that of pure NaNbO3. In contrast, double polarization hysteresis loops are observed in the SrHfO3-, SrZrO3-, and SrSnO3-substituted systems. It is confirmed that compounds that can reduce the tolerance factor of the system contribute to the stabilization of the antiferroelectric order, while those that can reduce the electronegativity difference lead to more pronounced double loops. The competition between antiferroelectricity and ferroelectricity is linked to the competition between covalent and ionic bonding in perovskites.

Thermophysical properties of Yb3+-doped nonstoichiometric gadolinium zirconate ceramics

Low thermal conductivities and high thermal expansion coefficients are desirable for rare-earth zirconate thermal barrier coating materials. Introduction of cation doping and adjustment of the nonstoichiometry are efficient methods for enhancing the thermophysical characteristics of materials. Herein, the thermophysical properties of Yb3+-doped nonstoichiometric gadolinium zirconate ceramic materials were investigated using first-principles calculations and solid-state reaction techniques. As the Yb3+ content increases, additional cations enter the interstitial spaces (for excess Gd3+ gadolinium zirconate) and form vacancy defects (for excess Zr4+ gadolinium zirconate), which serve as phonon scattering centres to decrease the thermal conductivity. When Yb3+ is doped at the same concentration, gadolinium zirconate with excess Zr4+ exhibits a lower thermal conductivity. Specifically, Gd1.875Yb0.25Zr2.125O7 shows the lowest minimum thermal conductivity of 1.133 W/(m⸱K) (according to the Clark model) and 1.241 W/(m⸱K) (according to the Cahill model). In addition, the experimental results also suggest that the optimal content of Yb3+ is 0.25 excess Zr4+ gadolinium zirconate, which has the lowest intrinsic thermal conductivity of 1.037 W/(m⸱K) at 1300 K. Moreover, the thermal expansion coefficient of the Yb3+-doped excess Gd3+ nonstoichiometric material is greater than that of the doped excess Zr4+ material, this is due to the greater electronegativity difference between Yb3+ and Zr4+ than that between Yb3+ and Gd3+ and the lower binding energy of Gd-O than that of Zr-O. The experimental results and the calculated results are in good agreement. The aim of this work is to enhance the thermophysical characteristics of gadolinium zirconate ceramics for use as thermal barrier coating materials.

Intramolecular Charge Transfer and Spin-Orbit Coupled Intersystem Crossing in Hypervalent Phosphorus(V) and Antimony(V) Porphyrin Black Dyes.

Porphyrin dyes with strong push-pull type intramolecular charge transfer (ICT) character and broad absorption across the visible spectrum are reported. This combination of properties has been achieved by functionalizing the periphery of hypervalent and highly electron-deficient phosphorus(V) and antimony(V) centered porphyrins with electron-rich triphenylamine (TPA) groups. As a result of the large difference in electronegativity between the porphyrin ring and the peripheral groups, their absorption profiles show several strong charge transfer transitions, which in addition to the porphyrin-centered π → π* transitions, make them panchromatic black dyes with high absorption coefficients between 200 and 800 nm. Time-resolved optical and electron paramagnetic resonance (EPR) studies show that the lowest triplet state also has ICT character and is populated by spin-orbit coupled intersystem crossing.

Free-standing FeNiCuCoBMo high-entropy alloy bifunctional electrocatalysts for efficient pH-universal water electrolysis

Utilizing the synergistic effects of multi-components has been proven to be a feasible approach to enhance water splitting electrocatalytic activity, since developing efficient and stable bifunctional electrocatalysts within a wide pH range remains a significant challenge. Herein, we report a FeNiCuCoBMo high-entropy alloy (HEA) prepared by dealloying, showing outstanding bifunctional electrocatalytic performance for HER and OER in a pH-universal electrolyte. After dealloying for 7 h, the HER and OER overpotentials of the HEA strips in 1.0 M KOH decreased by 22 mV and 25 mV, respectively.Impressively, the free-standing strips with the optimal compositions achieve low HER (82 mV in acid and 101 mV in alkali at 10 mA·cm−2) and OER (311 mV in acid and 245 mV in alkali at 10 mA·cm−2) overpotentials. In a full hydrolysis experiment, a current of 10 mA·cm−2 can run for 100 h with only 1.58 V, which is attributed to the ample exposure of highly active sites resulting from the synergistic effect of each element. Theoretical calculations further support these findings, showing that the electronegativity differences of the metallic elements in FeNiCuCoBMo result in abnormal activity at specific locations (Fe and Mo).Additionally, charge rearrangement and enhanced electronic conduction at the interface reduce the activation energy barrier, thereby improving the performance of the electrocatalysts.