Effect of Elastic Strains on Adsorption Energies of C,H and O on Transition Metal Oxides

Platinum(Pt)-based noble metal catalysts(PGMs)are the most widely used commercial catalysts,but they have the problems of high cost,low reserves,and susceptibility to small-molecule toxicity.Transition metal oxides(TMOs)are regarded as potential substitutes for PGMs because of their stability in oxidizing environments and excellent catalytic performance.In this study,comprehensive investigation into the influence of elastic strains on the adsorption energies of carbon(C),hydrogen(H)and oxygen(O)on TMOs was conducted.Based on density functional theory(DFT)calculations,these effects in both tetragonal structures(PtO_(2),PdO_(2))and hexagonal structures(ZnO,CdO),along with their respective transition metals were systematically explored.It was identified that the optimal adsorption sites on metal oxides pinpointed the top of oxygen or the top of metal atom,while face-centered cubic(FCC)and hexagonal close-packed(HCP)holes were preferred for the transition metals.Furthermore,under the influence of elastic strains,the results demonstrated significant disparities in the adsorption energies of H and O between oxides and transition metals.Despite these differences,the effect of elastic strains on the adsorption energies of C,H and O on TMOs mirrored those on transition metals:adsorption energies increased under compressive strains,indicating weaker adsorption,and decreased under tension strains,indicating stronger adsorption.This behavior was rationalized based on the d-band model for adsorption atop a metallic atom or the p-band model for adsorption atop an oxygen atom.Consequently,elastic strains present a promising avenue for tailoring the catalytic properties of TMOs.

Predicting the Degradability of Bioceramics through a DFT-based Descriptor

Bioceramics have attracted extensive attention for bone defect repair due to their excellent bioactivity and degradability.However,challenges remain in matching the rate between bioceramic degradation and new bone formation,necessitating a deeper understanding of their degradation properties.In this study,density functional theory(DFT)calculations was employed to explore the structural and electronic characteristics of silicate bioceramics.These findings reveal a linear correlation between the maximum isosurface value of the valence band maximum(VBM_(Fmax))and the degradability of silicate bioceramics.This correlation was subsequently validated through degradation experiments.Furthermore,the investigation on phosphate bioceramics demonstrates the potential of this descriptor in predicting the degradability of a broader range of bioceramics.This discovery offers valuable insights into the degradation mechanism of bioceramics and holds promise for accelerating the design and development of bioceramics with controllable degradation.

Microstructure and Oxidation Behavior of ZrB_(2)-SiC Ceramics Fabricated by Tape Casting and Reactive Melt Infiltration

ZrB_(2)-based ceramics typically necessitate high temperature and pressure for sintering,whereas ZrB_(2)-SiC ceramics can be fabricated at 1500℃using the process of reactive melt infiltration with Si.In comparison to the conventional preparation method,reactive synthesis allows for the more facile production of ultra-high temperature ceramics with fine particle size and homogeneous composition.In this work,ZrSi_(2),B4C,and C were used as raw materials to prepare ZrB_(2)-SiC via combination of tape casting and reactive melt infiltration herein referred to as ZBC ceramics.Control sample of ZrB_(2)-SiC was also prepared using ZrB_(2) and SiC as raw materials through an identical process designated as ZS ceramics.Microscopic analysis of both ceramic groups revealed smaller and more uniformly distributed particles of the ZrB_(2) phase in ZBC ceramics compared to the larger particles in ZS ceramics.Both sets of ceramics underwent cyclic oxidation testing in the air at 1600℃for a cumulative duration of 5 cycles,each cycle lasting 2 h.Analysis of the oxidation behavior showed that both ZBC ceramics and ZS ceramics developed a glassy SiO_(2)-ZrO_(2) oxide layer on their surfaces during the oxidation.This layer severed as a barrier against oxygen.In ZBC ceramics,ZrO_(2) is finely distributed in SiO_(2),whereas in ZS ceramics,larger ZrO_(2) particles coexist with glassy SiO_(2).The surface oxide layer of ZBC ceramics maintains a dense structure because the well-dispersed ZrO_(2) increases the viscosity of glassy SiO_(2),preventing its crystallization during the cooling.Conversely,some SiO_(2) in the oxide layer of ZS ceramics may crystallize and form a eutectic with ZrO_(2),leading to the formation of ZrSiO_(4).This leads to cracking of the oxide layer due to differences in thermal expansion coefficients,weakening its barrier effect.An analysis of the oxidation resistance shows that ZBC ceramics exhibit less increase in oxide layer thickness and mass compared to ZS ceramics,suggesting superior oxidation resistance of ZBC ceramics.

Performance of Lateral 4H-SiC Photoconductive Semiconductor Switches by Extrinsic Backside Trigger

Photoconductive semiconductor switch(PCSS)can be applied in pulsed high power systems and microwave techniques.However,reducing the damage and increasing the lifetime of silicon carbide(SiC)PCSS are still faced severe challenges.In this study,PCSSs with various structures were prepared on 4-inch diameter,500μm thick high-purity semi-insulating 4H-SiC substrates and their on-state resistance and damage mechanisms were investigated.It was found that the PCSS of an Au/TiW/Ni electrode system annealed at 950℃had a minimum on-state resistance of 6.0Ωat 1 kV bias voltage with a 532 nm and 170 mJ pulsed laser by backside illumination single trigger.The backside illumination single trigger could reduce on-state resistance and alleviate the damage of PCSS compared to the frontside trigger when the diameter of the laser spot was larger than the channel length of PCSS.For the 200 s trigger test by a 10 Hz laser,the black branch-like ablation on Au/TiW/Ni PCSS was mainly caused by thermal stress owing to hot carriers.Replacing metal Ni with boron gallium co-doped zinc oxide(BGZO)thin films annealed at 400℃,black branch-like ablation was alleviated while concentric arc damage was obvious at the anode.The major causes of concentric arc are both pulsed laser diffraction and thermal effect.

Hot Isostatic Pressing and Characterizations of Eu^(3+)-doped(Gd,Lu)_(2)O_(3) Transparent

(Gd,Lu)_(2)O_(3)∶Eu scintillation ceramics have promising applications in the high-energy X-ray imaging.Eu0.1Gd0.6Lu1.3O3 nano-powders with pure phase were prepared from the precursor calcined at 1050℃for 4 h by the co-precipitation method.Using the synthesized nano-powders as initial material,Eu_(0.1)Gd_(0.6)Lu_(1.3)O_(3)ceramics were fabri-cated by vacuum pre-sintering at different temperatures for 2 h and hot isostatic pressing(HIP)at 1750℃for 3 h in ar-gon.The influence of pre-sintering temperature on the microstructure,optical and luminescence properties was investi-gated.The Eu_(0.1)Gd_(0.6)Lu_(1.3)O_(3)ceramics pre-sintered at 1625℃for 2 h combined with HIP post-treatment show the high-est in-line transmittance of 75.2%at 611 nm.The photoluminescence(PL)and X-ray excited luminescence(XEL)spectra of the Eu_(0.1)Gd_(0.6)Lu_(1.3)O_(3)transparent ceramics demonstrate a strong red emission peak at 611 nm due to the^(5)D_(0)→^(7)F_(2) transition of Eu^(3+).The PL,PLE and XEL intensities of the HIP post-treated Eu_(0.1)Gd_(0.6)Lu_(1.3)O_(3)ceramics show a trend of first ascending and then descending with the increase of pre-sintering temperature.The thermally stimulated lumines-cence(TSL)curve of the HIP post-treated Eu_(0.1)Gd_(0.6)Lu_(1.3)O_(3)ceramics presents one high peak at 178 K and two peaks with lower intensities at 253 K and 320 K.The peak at 320 K may be related to oxygen vacancies,and the lumines-cence peak at 178 K is related to defects caused by the valence state changes of Eu^(3+)ions.

Induced antibacterial capability of TiO2 coatings in visible light via nitrogen ion implantation

In order to enhance the antibacterial ability of titanium components,an antibacterial coating was fabricated on Ti surface by micro-arc oxidation(MAO)and further nitrogen plasma immersion ion implantation(N-PIII).The XPS spectra demonstrated that nitrogen was incorporated into TiO2 coatings by N-PIII and the nitrogen content on the surface of TiO2 coatings increased as the N-PIII time increased.Nitrogen-incorporated samples exhibited remarkably increased absorbance in the visible region and the light absorption edge of nitrogen-incorporated samples showed a redshift compared to MAO samples.Escherichia coli and Staphylococcus aureus were seeded on the samples to assess their antibacterial ability.The bacterial experiment demonstrated that nitrogen-incorporated TiO2 could effectively reduce the bacterial viability in visible light.Thus,the antibacterial TiO2 coatings fabricated by MAO and further N-PIII might have large potential in the medical and marine fields.

An efficient strategy for photocatalytic hydrogen peroxide production over oxygen-enriched graphitic carbon nitride with sodium phosphate

Photocatalytic hydrogen peroxide(H_(2)O_(2))production is a promising strategy to replace the traditional production processes;however,the inefficient H_(2)O_(2) productivity limits its application.In this study,oxygen-rich g-C_(3)N_(4) with abundant nitrogen vacancies(OCN)was synthesized for photocatalytic H_(2)O_(2) production.X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy indicated that oxygen-containing functional groups(–COOH and C–O–C)were obtained.Electron paramagnetic resonance confirmed the successful introduction of nitrogen vacancies.OCN exhibited efficient photocatalytic H_(2)O_(2) production performance of 1965μmol L^(−1) h^(−1) in air under visible-light irradiation.The high H_(2)O_(2) production was attributed to the enhanced adsorption of oxygen,enlarged specific surface area,and promoted carrier separation.An increased H_(2)O_(2) production rate(5781μmol L^(−1) h^(−1))was achieved in a Na_(3)PO_(4) solution.The improved performance was attributed to the changed reactive oxygen species.Specifically,the adsorbed PO_(4)^(3−) on the surface of the OCN promoted the transfer of holes to the catalyst surface.•O_(2)−obtained by O_(2) reduction reacted with adjacent holes to generate 1O_(2),which could efficiently generate H_(2)O_(2) with isopropanol.Additionally,PO_(4)^(3−),as a stabilizer,inhibited the decomposition of H_(2)O_(2).

Li_2B_4O_7单晶的加速坩埚旋转Bridgman生长

本文的工作首次应用加速坩埚旋转(ACRT)的 Bridgman(BR)方法生长了 Li_2B_4O_7(LBO)晶体,获得直径为52mm,长为60mm 的宏观完整单晶。ACRT 将 LBO 晶体生长速度提高到 BR 生长速度的1.5～2倍。并增强了生长系统抵御熔体中温度波动的能力。与 BR^(?) 生长的固液界面相比,ACRT 所产生的强迫对流没有对固液界面的形状产生明显的影响。本工作还对实际坩埚内的液流进行了模拟观察。

Microstructure,formation mechanism and properties of plasma-sprayed Cr_(7)C_(3)−CrSi_(2)−Al_(2)O_(3)coatings

The Cr_(7)C_(3)−CrSi_(2)−Al_(2)O_(3)composite coatings were prepared by plasma spraying Cr_(7)C_(3)−CrSi_(2)−Al_(2)O_(3)and Al−Cr2O3−SiC composite powders,respectively.The microstructure,formation mechanism and properties of the two Cr_(7)C_(3)−CrSi_(2)−Al_(2)O_(3)composite coatings obtained by plasma spraying were investigated,and the reaction mechanism of the Al−Cr_(2)O_(3)−SiC system was explored.The results show that the coating obtained by plasma spraying Al−Cr_(2)O_(3)−SiC composite powders had thinner lamella and more tortuous interlayer interface,and the in-situ synthesized Cr_(7)C_(3),CrSi_(2) and Al_(2)O_(3) in the coating were all nano-crystallines.Compared with the Cr_(7)C_(3)−CrSi_(2)−Al_(2)O_(3)coating prepared by plasma spraying Cr_(7)C_(3)−CrSi_(2)−Al_(2)O_(3)composite powders,the plasma-sprayed Cr_(7)C_(3)−CrSi_(2)−Al_(2)O_(3)coating obtained from Al−Cr_(2)O_(3)−SiC composite powders had higher density,higher microhardness(increased by 20%),better fracture toughness and lower wear rate(reduced by 28%).

Spin regulation on(Co,Ni)Se_(2)/C@FeOOH hollow nanocage accelerates water oxidation

Spin engineering is recognized as a promising strategy that modulates the association between d‐orbital electrons and the oxygenated species,and enhances the catalytic kinetics.However,few efforts have been made to clarify whether spin engineering could make a considerable enhancement for electrocatalytic water oxidation.Herein,we report the spin engineering of a nanocage‐structured(Co,Ni)Se_(2)/C@FeOOH,that showed significant oxygen evolution reaction(OER)activity.Magnetization measurement presented that the(Co,Ni)Se_(2)/C@FeOOH sample possesses higher polarization spin number(μb=6.966μB/f.u.)compared with that of the(Co,Ni)Se_(2)/C sample(μb=6.398μB/f.u.),for which the enlarged spin polarization number favors the adsorption and desorption energy of the intermediate oxygenated species,as confirmed by surface valance band spectra.Consequently,the(Co,Ni)Se_(2)/C@FeOOH affords remarkable OER product with a low overpotential of 241 mV at a current of 10 mA cm^(-2) and small Tafel slope of 44 mV dec^(-1) in 1.0 mol/L KOH alkaline solution,significantly surpassing the parent(Co,Ni)Se_(2)/C catalyst.This work will trigger a solid step for the design of highly‐efficient OER electrocatalysts.

Rate and Cycling Performance of Ti and Cu Dopedβ-NaMnO_(2) as Cathode of Sodium-ion Battery

Sodium-ion batteries are economical and environmentally sustainable energy storage batteries.Among them,β-NaMnO_(2),a promising sodium-ion cathode material,is a manganese-based oxide with a corrugated laminar structure,which has attracted significant attention due to its structural robustness and relatively high specific capacity.However,it has short cycle life and poor rate capability.To address these issues,Ti atoms,known for enhancing structural stability,and Cu atoms,which facilitate desodiation,were doped intoβ-NaMnO_(2) by first-principles calculation and crystal orbital Hamilton population(COHP)analysis.β-NaMn_(0.8)Ti_(0.1)Cu_(0.1)O_(2) exhibits a notable increase in reversible specific capacity and remarkable rate properties.Operating at a current density of 0.2C(1C=219 mA·g^(–1))and within a voltage range of 1.8–4.0 V,the modified material delivers an initial discharge capacity of 132 mAh·g^(–1).After charge/discharge testing at current densities of 0.2C,0.5C,1C,3C,and 0.2C,the material still maintains a capacity of 110 mA h·g^(–1).The doping of Ti atoms slows down the changes in the crystal structure,resulting in only minimal variation in the lattice constant c/a during the desodiation process.Mn and Cu engage in reversible redox reactions at voltages below 3.0 V and around 3.5 V,respectively.The extended plateau observed in the discharge curve below 3.0 V signifies that Mn significantly contributes to the overall battery capacity.This study provides insights into modifyingβ-NaMnO_(2) as a cathode material,offering experimental evidence and theoretical guidance for enhancing battery performance in Na-ion batteries.

In-situ Growth of Conformal SnO_(2) Layers for Efficient Perovskite Solar Cells

Significant progress has recently been made in enhancing the power conversion efficiency(PCE)of perovskite solar cells(PSCs).The electron transport layer(ETL),as an essential component of PSCs,significantly influences the performance of devices.Traditional spin-coating method for preparing the ETL fails to fully cover the cusp of FTO transparent conductive glass substrate,leading to direct contact between perovskite film and FTO substrate,which induces charge recombination and reduces the performance of PSCs.To address this issue,an in-situ growth method was proposed to prepare conformal SnO_(2) films on FTO glass substrates in this study.The resulting SnO_(2) films are not only dense and uniform,fully covering the cusp of the FTO glass substrates and reducing the contact area between the FTO substrates and the perovskite films,but also facilitating the formation of perovskite films with large grain sizes.Moreover,the conformal SnO_(2) films can improve the charge extraction at the SnO_(2)/perovskite interface,reduce the trap density and trap-assisted recombination in PSCs,and thus enhance the PCE of PSCs.Through comparative experiments,it is found that the PSCs with in-situ grown SnO_(2) films show an improved PCE of 21.97%,which significantly increased compared to that with spin-coated SnO_(2) films(20.93%).All above data demonstrate that the as-prepared SnO_(2) film can serve as an ideal ETL.It is worth mentioning that this method avoids the use of corrosive hydrochloric acid and toxic thioglycolic acid,and it can also be extended to ITO flexible transparent conductive substrates in the future.