Self-assembled S-scheme In_(2.77)S_(4)/K^(+)-doped g-C_(3)N_(4)photocatalyst with selective O_(2) reduction pathway for efficient H_(2)O_(2) production using water and air

The development of an efficient artificial H_(2)O_(2) photosynthesis system is a challenging work using H_(2)O and O_(2) as starting materials.Herein,3D In_(2.77)S_(4) nanoflower precursor was in-situ deposited on K^(+)-doped g-C_(3)N_(4)(KCN)nanosheets using a solvothermal method,then In_(2.77)S_(4)/KCN(IS/KCN)het-erojunction with an intimate interface was obtained after a calcination process.The investigation shows that the photocatalytic H_(2)O_(2) production rate of 50IS/KCN can reach up to 1.36 mmol g^(-1)h^(-1)without any sacrificial reagents under visible light irradiation,which is 9.2 times and 4.1 times higher than that of KCN and In_(2.77)S_(4)/respectively.The enhanced activity of the above composite can be mainly attributed to the S-scheme charge transfer route between KCN and In_(2.77)S_(4) according to density functional theory calculations,electron paramagnetic resonance and free radical capture tests,leading to an expanded light response range and rapid charge separation at their interface,as well as preserving the active electrons and holes for H_(2)O_(2) production.Besides,the unique 3D nanostructure and surface hydrophobicity of IS/KCN facilitate the diffusion and transportation of O_(2) around the active centers,the energy barriers of O_(2) protonation and H_(2)O_(2) desorption steps are ef-fectively reduced over the composite.In addition,this system also exhibits excellent light harvesting ability and stability.This work provides a potential strategy to explore a sustainable H_(2)O_(2) photo-synthesis pathway through the design of heterojunctions with intimate interfaces and desired reac-tion thermodynamics and kinetics.

First-Principles Investigation of Charge Transfer Mechanism of B-Doped 3C-SiC Semiconductor Material

This study delves into the charge transfer mechanism of boron (B)-doped 3C-SiC through first-principles investigations. We explore the effects of B doping on the electronic properties of 3C-SiC, focusing on a 12.5% impurity concentration. Our comprehensive analysis encompasses structural properties, electronic band structures, and charge density distributions. The optimized lattice constant and band gap energy of 3C-SiC were found to be 4.373 Å and 1.36 eV respectively, which is in agreement with previous research (Bui, 2012;Muchiri et al., 2018). Our results show that B doping narrows the band gap, enhances electrical conductivity, and influences charge transfer interactions. The charge density analysis reveals substantial interactions between B dopants and surrounding carbon atoms. This work not only enhances our understanding of the material’s electronic properties, but also highlights the importance of charge density analysis for characterizing charge transfer mechanisms and their implications in the 3C-SiC semiconductors.

Y^(3+)掺杂g-C_(3)N_(4)光催化还原U(Ⅵ)

光催化是一种重要的分离溶液中铀的技术方法。氮化碳(CN)作为一种无金属聚合物半导体,其成本低、制备简单,并具有优异的理化和光电特性,在光催化领域受到越来越多的关注。然而,由于氮化碳活性位点少、载流子分离效率低,其在U(Ⅵ)光催化还原领域的应用受限。本工作通过原位掺杂的方法在氮化碳中引入Y^(3+)构建了Y掺杂氮化碳(YCN),改善氮化碳光催化活性。结果显示,Y^(3+)的引入影响了3-s-三嗪单元的周期性拓扑结构和层间堆积结构,使3-s-三嗪单元在高温条件下发生不完全聚合,显著增加了催化剂活性位点,有效改善了能带结构。与CN相比,YCN_(2)表现出更强的可见光吸收和光生载流子分离效率,且伴随着载流子密度增加,活性氧物种(·O_(2)^(-))数量明显增多,其在20 min内可以去除约95%的U(Ⅵ)。YCN_(2)对U(Ⅵ)的光催化还原速率(0.112 min^(-1))是原始CN(0.021 min^(-1))的5.3倍。光催化反应中,水溶性U(Ⅵ)主要被·O_(2)^(-)还原为难溶的UO_(2+x)沉积于催化剂表面,可实现U(Ⅵ)的高效分离。

Fabrication of Gd_(2)O_(3)-doped CeO_(2)thin films through DC reactive sputtering and their application in solid oxide fuel cells

Physical vapor deposition(PVD)can be used to produce high-quality Gd_(2)O_(3)-doped CeO2(GDC)films.Among various PVD methods,reactive sputtering provides unique benefits,such as high deposition rates and easy upscaling for industrial applications.GDC thin films were successfully fabricated through reactive sputtering using a Gd_(0.2)Ce_(0.8)(at%)metallic target,and their application in solid oxide fuel cells,such as buffer layers between yttria-stabilized zirconia(YSZ)/La0.6Sr0.4Co0.2Fe0.8O_(3−δ)and as sublayers in the steel/coating system,was evaluated.First,the direct current(DC)reactive-sputtering behavior of the GdCe metallic target was determined.Then,the GDC films were deposited on NiO-YSZ/YSZ half-cells to investigate the influence of oxygen flow rate on the quality of annealed GDC films.The results demonstrated that reactive sputtering can be used to prepare thin and dense GDC buffer layers without high-temperature sintering.Furthermore,the cells with a sputtered GDC buffer layer showed better electrochemical performance than those with a screen-printed GDC buffer layer.In addition,the insertion of a GDC sublayer between the SUS441 interconnects and the Mn-Co spinel coatings contributed to the reduction of the oxidation rate for SUS441 at operating temperatures,according to the area-specific resistance tests.

Preparation and photoelectric properties of Ho^(3+)-doped titanium dioxide nanowire downconversion photoanode

Ho^3＋-doped titanium dioxide（TiO2：Ho^3＋） downconversion（DC） nanowires were synthesized through a simple hydrothermal method followed by a subsequent calcination process after being immersed in Ho（NO3）3 aqueous solution. Moreover, TiO2：Ho^3＋ nanowires（HTNWs） were used as the photoanode in dye-sensitized solar cells（DSSCs） to investigate their photoelectric properties. Scanning electron microscopy（SEM） and X-ray diffraction（XRD） were used to characterize the morphology and structure of the material, respectively. The photofluorescence and ultraviolet-visible absorption spectra of HTNWs reveal a DC from the near and middle ultraviolet light to visible light which matches the strong absorbed region of the N719 dye. Compared with the pure TNW photoanode, HTNWs DC photoanodes show greater photovoltaic efficiency. The photovoltaic conversion efficiency（η） of the DSSCs with HTNWs photoanode doped with 4% Ho2O3（mass fraction） is two times that with pure TNW photoanode. This enhancement could be attributed to HTNWs which could extend the spectral response range of DSSCs to the near and middle ultraviolet region and increase the short-circuit current density（Jsc） of DSSCs, thus leading to the enhancement of photovoltaic conversion efficiency.

Preparation and characterization of Eu^(3+)-doped CaCO_3 phosphor by microwave synthesis

A Eu^3＋-doped CaCO3 phosphor with red emission was prepared by microwave synthesis. The scanning electron microscopy （SEM） image and laser particle size analysis show that the CaCO3：Eu^3＋ particles are needle-like in the length range of 5.0-10.0 μm. The results of X-ray diffraction （XRD） analysis, Fourier transform infrared spectroscopy （FT-IR）, and Raman spectroscopy indicate that pure aragonite CaCO3：Eu^3＋ is prepared using microwave irradiation and the Eu^3＋ ion as a luminescence center inhabits the site of Ca^2＋. The photoluminescence excitation （PLE） spectrum shows that the strong broad band at around 270 nm and weak sharp lines in 300-550 nm are assigned to the charge transfer band of Eu^3＋-O^2- and intra-configurational 4f-4f transitions of Eu^3＋, respectively. The photoluminescence （PL） spectrum implies that the red luminescence can be attributed to the transitions from the ^5D0 excited level to the ^7FJ （J = 0, 1, 2, 3, 4） levels of Eu^3＋ ions with the mainly electric dipole transition ^5D0 → ^7F2 （614 and 620 nm）, and the Eu^3＋ ions prefer to occupy the low symmetric site in the crystal lattice.

Characterization of the BaBiO_3-doped BaTiO_3 positive temperature coefficient of a resistivity ceramic using impedance spectroscopy with T_c=155℃

BaBiO3-doped BaTiO3 （BB-BT） ceramic, as a candidate for lead-free positive temperature coefficient of resistivity （PTCR） materials with a higher Curie temperature, has been synthesized in air by a conventional sintering technique. The temperature dependence of resistivity shows that the phase transition of the PTC thermistor ceramic occurs at the Curie temperature, Tc = 155℃, which is higher than that of BaTiO3 （≤ 130 ℃）. Analysis of ac impedance data using complex impedance spectroscopy gives the alternate current （AC） resistance of the PTCR ceramic. By additional use of the complex electric modulus formalism to analyse the same data, the inhomogeneous nature of the ceramic may be unveiled. The impedance spectra reveal that the grain resistance of the BB-BT sample is slightly influenced by the increase of temperature, indicating that the increase in overall resistivity is entirely due to a grain-boundary effect. Based on the dependence of the extent to which the peaks of the imaginary part of electric modulus and impedance are matched on frequency, the conduction mechanism is also discussed for a BB-BT ceramic system.

Green and red up-conversion emissions and thermometric application of Er^(3+) -doped silicate glass

The green and red up-conversion emissions centred at about 534, 549 and 663 nm of wavelength, corresponding respectively to the ^2H11/2 → ^4I15/2, ^4S3/2 → ^4I15/2 and ^4F9/2 → ^4I15/2 transitions of Er^3＋ ions, have been observed for the Er^3＋-doped silicate glass excited by a 978 nm semiconductor laser beam. Excitation power dependent behaviour of the up-conversion emission intensity indicates that a two-photon absorption up-conversion process is responsible for the green and red up-conversion emissions. The temperature dependence of the green up-conversion emissions is also studied in a temperature range of 296-673 K, which shows that Er^3＋-doped silicate glass can be used as a sensor in high-temperature measurement.

Promotional effect for SCR of NO with CO over MnO_(x)-doped Fe_(3)O_(4) nanoparticles derived from metal-organic frameworks

MnO_(x)-Fe_(3)O_(4) nanomaterials were fabricated by using the innovative scheme of pyrolyzing manganesedoped iron-based metal organic framework in inert atmosphere and exhibited extraordinary performance of NO reduction by CO(CO-SCR).Multi-technology characterizations were conducted to ascertain the properties of fabricated materials(e.g.,TGA,XRD,SEM,FT-IR,XPS,BET,H_(2)-TPR and O_(2)-TPD).Moreover,the interaction between reactants and catalysts was ascertained by in situ FT-IR.Experimental results demonstrated that Mn was an ideal promoter for iron oxides,resulting in decrease of crystallite size,improve reducibility property,enhance the mobility and the amount of lattice O^(2-) species,as well as strength the adsorption ability of active NO and CO to form multiple species(e.g.,nitrate and carbonate).The unprecedented enhancement of CO-SCR activity over Mn-Fe nanomaterials follows the Eley-Rideal(E-R)and Langmuir-Hinshelwood(L-H)reaction pathway.

Three-photon-excited fluorescence of Tb^(3+)-doped CaO-Al_2O_3-SiO_2 glass by femtosecond laser irradiation

A near infrared to visible blue, green, and red upconversion luminescence in a Tb^3＋-doped CaO-Al2O3-SiO2 glass was studied, which was excited using 800 nm femtosecond laser irradiation. The upconversion luminescence was attributed to ^5D3→^7F5, ^5D3→^7F4, ^5D3→^7F3, ^5D4→^7F6, ^5D4→^7F5, ^5D4→^7F4, and ^5D4→^7F3 transitions of Tb^3＋. The relationship between upconversion luminescence intensity and the pump power indicated that a three-photon simultaneous absorption process was dominant in this upconversion luminescence. The intense red, green, and blue upconversion luminescence of Tb^3＋-doped CaO-Al2O3-SiO2 glass may be potentially useful in developing three-dimensional display applications.

2 μm mid-infrared optical spectra of Tm3+-doped germanium gallate glasses

Glasses with the composition of 65GeO212Ga2O3-10BaO-8Li2O-5La2O3(molar ratio) doped with 1.526 wt.%, 3.006 wt.%, 5.836 wt.%, 11.028 wt.%, and 15.678 wt.% Tm2O3, respectively, were fabricated by conventional melting method. According to the absorption spectra and the Judd-Ofelt theory, the J-O strength parameters (Ω2,Ω4, Ω6) were calculated, with which the radiative transition probabilities,branching ratios and radiative lifetimes were obtained. The infrared emission spectra (with 808 nm LD excitation) at～1.47 and～1.8 μm of various concentrations of Tm3+-doped glasses were studied. The emission intensity at～1.8 μm reached to the maximum when the Tm2O3-doping concentration was near to be～3.006 wt.% (1.0 mol.%), and then decreased as doping concentration increased further. The mechanism of the fluorescence intensity change was explained with the cross-relaxation effect and the concentration quenching effect of Tm3+. Meanwhile, according to McCumber theory, the absorption and emission cross-sections corresponding to the 3F4→3H6 transitions of Tm3+ at 1.8 μm was obtained. For Tm3+-doped germanate glasses, the maximum emission cross-section reached a value higher than that re-ported for fluorozircoaluminate glasses. It is expected to be a favorable candidate host for～2.0 μm mid-inflated laser because the glass shows favorable optical spectra.

Tm^(3+)-doped tellurite glass with Yb^(3+) energy sensitized for broadband amplifier at 1400–1700 nm bands

A kind of novel experiment was disclosed as it possessed two bands of fluorescence emission at 1.4 and 1.6 μm, which were perfectly complimentary to the current C band of optic communication. The fluorescence was based on energy transfer and up-conversion processes between Tm^3＋ and Yb^3＋ under direct pumping of 975 nm LD. The spectra and lifetimes of Tm^3＋ fluorescence in the tellurite glass were described. The corresponding fluorescence characteristics and energy migration process were analyzed by the method of lifetime and intensity comparison. The mechanism of the up-conversion based IR fluorescence was presented upon analyzing the multi-photon pumping process. The potential advantages of Tm^3＋/Yb^3＋ co-doped tellurite glass as amplifier material were concluded.

Laser Cooling Using Anti-Stokes Fluorescence in Yb^(3+)-Doped Fluorozirconate Glasses

The fluorozirconate glasses ZBLANP( ZrF\-4-BaF\-2-LaF\-3-AlF\-3-NaF-PbF\-2) doped with different Yb\+ 3+ concentration were prepared. The Raman spectra and absorption spectra are measured to substantiate the existence of phonon-assisted emission. After analyzing the normalized absorption spectra of samples with different Yb\+ 3+-doped concentration, we calculated the maximum cooling effect in the 3 wt% Yb\+ 3+-doped sample pumped at 1 012.5 nm. The corresponding cooling capability is about -4.09 ℃/W and the cooling efficiency reaches 1.76%.

Mechanism and behaviors of Cr3+-doped TiO2

TiO2 powder and TiO2 thin film on the surface of glazed ceramic tile were prepared by sol-gel method.The influences of different doping Cr3+ concentration on the photocatalytic activity of TiO2 were discussed, UV-visible and X-ray diffraction analysis were used to test the performance of TiO2 powder and film. The results indicate that photocatalytic activity of doping Cr3+-TiO2 thin film is higher than that of powder, and the interaction between Cr3+-doped and substrate can greatly enhance the photocatalytic activity. The results of X-ray diffraction and photoabsorption show that the Cr3+ -doped energy level in TiO2 is 0. 62 eV high from the top of valence band, which belongs to the type of deep energy level doping. On the basis of the semiconductor energy level theory and Cr3+ dopant energy level, the semiconductor energy level model of Cr3+ in TiO2 powder and thin film were established, and the doping mechanisms of Cr3+-doped in TiO2 powder and thin film were analyzed.

Synthesis of Fe^(3+)-doped Aminated Lignin as A Peroxidase Mimic for Colorimetric Detection of H_(2)O_(2) and Glucose

Peroxidase plays an important role in living systems;however,its storage difficulty and easy inactivation have limited its applications in complex environments.To address these problems,herein,we proposed a method to synthesize peroxidase mimics by amination,carbonization,and Fe^(3+)-doping of industrial alkali lignin.The Fe^(3+)-doped lignin-based peroxidase mimic(Fe-LPM),with active centers of coordination between Fe^(3+)and N atoms,showed higher tolerance to pH value and temperature than natural peroxidase.Using Fe-LPM,10-100 mmol/L of H_(2)O_(2) and glucose could be colorimetrically detected with the lowest detection limits of 80μmol/L and 1.5 mmol/L and visual detection limits of 1.0 mmol/L and 10 mmol/L,respectively.The Fe-LPM maintained peroxidase-like activity after 10 cycles and could even be used for H_(2)O_(2) detection in practical samples.This work not only provides a new approach to synthesize peroxidase mimics using biomass materials but also promotes the high-value utilization of lignin.

Preparation and Spectroscopic Properties of Pr^(3＋)-doped Transparent Glass-ceramic Containing LiYF_4 Nanocrystals

Pr^（3＋）-doped transparent oxyfluoride glass-ceramic containing tetragonal LiYF_4 nanocrystals has been synthesized by melting-quenching method and subsequent thermal treatment and spectroscopic properties of Pr^（3＋） ions were investigated. The crystalline phase and microstructure of the LiYF_4 nanocrystals were studied by X-ray diffraction（XRD） and transmission electron microscopy（TEM）, respectively. Compared with those of Pr^（3＋）-doped glass（Pr^（3＋）：PG）, the sharp absorption and emission bands of Pr^（3＋）-doped glass-ceramic（Pr^（3＋）：GC） reveal parts of Pr^（3＋） ions are incorporated into LiYF_4 nanocrystals. The peak absorption cross-section at 443 nm（~3H_4 → ~3P_2） adds to 110% and the full width at half maximum（FWHM） for the band around 443 nm reduces from 22 to 14 nm after crystallization. The fluorescence lifetime of the ~3P_0 multiplet of Pr^（3＋） ions increases from 5.35 to 11.14 μs after crystallization. The results indicate that this glass-ceramic is promising to be a visible laser material.

Structural and Dielectric Properties of Y_2O_3-Doped Ba_(0.92)Sr_(0.08)Ti_(0.95)Sn_(0.05)O_3 Ceramics

The structural and dielectric properties of Ba0.92Sr0.08Ti0.95Sn0.0503 （BSTS） ＋x（molar ratio, %） Y^3＋ceramics are investigated. Combining the lattice parameters and the distortion of crystal lattice, an alternation of substitution preference of Y^3＋ ion for the host cations in perovskite lattice is found. Owing to Y^3- ion entering the A site, the maximum dielectric constant is 5 627 for 1.25% Y^3＋-doped samples; when Y^3- ion is more than 1.25%, it tends to occupy the B site in perovskite lattice, causing a drop in the dielectric constant. Owing to the appearance of oxygen vacancy, the optimized dielectric loss is 0.004 for 1.25% Y^3＋-doped samples. The thermal stability of BSTS ceramics is significantly improved and the Curie temperature shifts to lower value with the amount of Y2O3 increased, making it a superior candidate for capacitor applications.

Ca_(2)MnO_(4)-layered perovskite modified by NaNO_(3)for chemical-looping oxidative dehydrogenation of ethane to ethylene

Chemical-looping oxidative dehydrogenation(CL-ODH)is a process designed for the conversion of alkanes into olefins through cyclic redox reactions,eliminating the need for gaseous O_(2).In this work,we investigated the use of Ca_(2)MnO_(4)-layered perovskites modified with NaNO_(3) dopants,serving as redox catalysts(also known as oxygen carriers),for the CL-ODH of ethane within a temperature range of 700-780℃.Our findings revealed that the incorporation of NaNO_(3) as a modifier significantly-nhanced the selectivity for-thylene generation from Ca_(2)MnO_(4).At 750℃and a gas hourly space velocity of 1300 h^(-1),we achieved an-thane conversion up to 68.17%,accompanied by a corresponding-thylene yield of 57.39%.X-ray photoelectron spectroscopy analysis unveiled that the doping NaNO_(3) onto Ca_(2)MnO_(4) not only played a role in reducing the oxidation state of Mn ions but also increased the lattice oxygen content of the redox catalyst.Furthermore,formation of NaNO_(3) shell on the surface of Ca_(2)MnO_(4) led to a reduction in the concentration of manganese sites and modulated the oxygen-releasing behavior in a step-wise manner.This modulation contributed significantly to the enhanced selectivity for ethylene of the NaNO_(3)-doped Ca_(2)MnO_(4) catalyst.These findings provide compelling evidence for the potential of Ca_(2)MnO_(4)-layered perovskites as promising redox catalysts in the context of CL-ODH reactions.

Dependence of Thermal Annealing on Transparent Conducting Properties of HoF_3-Doped ZnO Thin Films

A kind of n-type HoF_3-doped zinc oxide-based transparent conductive film has been developed by electron beam evaporation and studied under thermal annealing in air and vacuum at temperatures 100–500℃.Effective substitutional dopings of F to O and Ho to Zn are realized for the films with smooth surface morphology and average grain size of about 50 nm.The hall mobility,electron concentration,resistivity and work function for the asdeposited films are 47.89 cm^2/Vs,1.39×10^(20)cm^(-3),9.37×10^(-4)Ω·cm and 5.069 eV,respectively.In addition,the average transmittance in the visible region(400–700 nm)approximates to 87%.The HoF_3:ZnO films annealed in air and vacuum can retain good optoelectronic properties under 300℃,thereinto,more stable electrical properties can be found in the air-annealed films than in the vacuum-annealed films,which is assumed to be a result of improved nano-crystalline lattice quality.The optimized films for most parameters can be obtained at 200℃ for the air-annealing case and at room temperature for the vacuum annealing case.The advisable optoelectronic properties imply that HoF_3:ZnO can facilitate carrier injection and has promising applications in energy and light sources as transparent electrodes.

Spectroscopic Properties of Nd^(3+)-Doped Tellurite Glasses

The Nd^3＋-doped pared. The absorption and tellurite glasses were preemission spectra of Nd^3 ＋- doped tellurite glasses at room temperature were measured. The Judd-Ofelt parameters （Ω2, Ω4, Ω6） of the glasses were calculated from measured absorption spectra. The calculation results of luminescence properties （A, β, τrad, σ） of Nd^3＋ ions in the tellurite were glasses were given. Spectroscopic properties, concentration quenching in these kinds of the glasses were investigated. The results indicate that the tellurite glasses with composition of 70% TeO2, 20% ZnO, （ 10 - x ） % La2O3, x % Nd2O3 （ mol% ） show high emission cross section and low phonon energy. The fluorescent intensity and the emission cross section have a maxi- mum value at x = 0.5, namely, the optimum Nd^3 ＋ ion concentration in the tellurite glass is 0.5% （1.93 × 10^20 ions·cm^-3）. The fluorescence properties of Nd^3＋ measured are basically in accord with the calculated results.