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 In2.77S_(4)nanoflower precursor was in-situ deposited on K^(+)-doped g-C_(3)N_(4)(KCN)nanosheets using a solvothermal method,then In2.77S_(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 In2.77S_(4),respectively.The enhanced activity of the above composite can be mainly attributed to the S-scheme charge transfer route between KCN and In2.77S_(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.

不同元素掺杂ZrO_(2)基固体氧化物燃料电池电解质电性能研究进展

固体氧化物燃料电池(SOFC)是未来的清洁能源技术之一,电解质是核心部件。ZrO_(2)基SOFC电解质中含有氧空位是氧离子传导的基础,通过在ZrO_(2)中掺杂低价金属离子能够制造氧空位。综述了不同元素掺杂ZrO_(2)基SOFC电解质电性能的研究进展,按照掺杂元素的多少分为一元、二元及多元掺杂ZrO_(2)电解质三大类,在每一大类下,根据掺杂元素的种类特点进行了细分与论述。归纳了ZrO_(2)电解质的性能和掺杂金属离子的关系,以及不同金属离子掺杂的优缺点,展望了ZrO_(2)基电解质的发展趋势。

固体酸SO42-/ZrO2催化果糖制备5-羟甲基糠醛

通过共沉淀-浸渍法制备了SO_(4)^(2-)/ZrO_(2)固体酸催化剂,探究了5种不同焙烧温度(450~650℃)对催化剂活性的影响,并采用X射线衍射(XRD)、透射电镜(TEM)、傅里叶红外光谱(FT-IR)等表征手段对催化剂的结构及理化性质进行了分析。研究表明:当焙烧温度高于450℃时,固体酸SO_(4)^(2-)/ZrO_(2)在2θ为30.1°均存在较为明显的四方相晶体结构;随着焙烧温度的升高,催化剂的孔径存在一定程度的增大,但比表面积总体呈降低趋势,酸强度也存在一定程度的降低。在焙烧温度为550℃焙烧3 h时制备的固体酸SZ-550表现出较好的催化性能,用于催化果糖脱水制备5-羟甲基糠醛(5-HMF)时,在反应温度为120℃,反应时间为90 min,催化剂用量为30 mg的最佳反应条件下,以二甲基亚砜(DMSO)为反应溶剂,果糖转化率为99.91%,5-HMF的得率为76.01%。XRD分析结果表明:固体酸SO_(4)^(2-)/ZrO_(2)明显的四方相ZrO_(2)结构是其表现出较高催化活性的原因之一。

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.

CaF_2-doped ZrO_2:A base catalyst for synthesis of dimethyl carbonate

The effect of CaF2-doped ZrO2 catalyst for the synthesis of dimethyl carbonate （DMC） was studied by X-ray diffraction （XRD）, CO2-temperature programmed desorption （TPD）, Raman spectra, and X-ray photoelectron spectroscopy （XPS）. Catalytic performance was evaluated in the bath and distillation reactors. Results showed that the CaF2/ZrO2 catalysts had activity and stability for DMC synthesis.

Structural,optical,and electrical properties of Cu-doped ZrO_2 films prepared by magnetron co-sputtering

Copper （Cu）-doped ZrO2 （CZO） films with different Cu content （0 at.%- 8.07 at.%） are successfully deposited on Si （100） substrates by direct current （DC） and radio frequency （RF） magnetron co-sputtering. The influences of Cu content on structural, morphological, optical and electrical properties of CZO films are discussed in detail. The CZO films exhibit ZrO2 monocline （1^-11） preferred orientation, which indicates that Cu atoms are doped in ZrO2 host lattice. The crystallite size estimated form x-ray diffraction （XRD） increases by Cu doping, which accords with the result observed from the scanning electron microscope （SEM）. The electrical resistivity decreases from 2.63 Ω·cm to 1.48 Ω·cm with Cu doping content increasing, which indicates that the conductivity of CZO film is improved. However, the visible light transmittances decrease slightly by Cu doping and the optical band gap values decrease from 4.64 eV to 4.48 eV for CZO fihns.

ZrO_(2)/InP和ZrO_(2)/InAs堆栈的元素扩散研究

Ⅲ-Ⅴ族化合物半导体有望在5 nm以下节点替代Si作为场效应管的沟道材料,其与高k栅介质界面质量对器件性能极为关键。本文分别在InAs和InP衬底上通过H_(2)^(18)O蒸汽预处理表面,再利用原子层沉积技术原位制备了ZrO_(2)薄膜,通过角分辨X射线光电子能谱和飞行时间二次离子质谱技术系统性地研究了退火前后界面处衬底元素原子和氧原子扩散行为,并讨论了物理机制。本工作将加深Ⅲ-Ⅴ/高k栅介质界面在材料学上的理解。

Preparation and photocatalytic activity of Cu^(2+)-doped TiO_2/SiO_2

Cu^2＋-doped nanostructured TiO2-coated SiO2 （TiO2/SiO2） particles were prepared by the layer-by-layer assembly technique and their photocatalytic property was studied. TiO2 colloids were synthesized by the sol-gel method using TiOSO4 as a precursor. The experimental results showed that TiO2 nanopowders on the surface of SiO2 particles were well distributed and compact. The amount of TiO2 increased with the increase in coating layers. The shell structure appeared to be composed of anatase titania nanocrystals at 550℃. The 2-layer coated TiO2 particles on the surface showed a higher degradation rate compared with all the different-layer samples. The photocatalytic activity of Cu^2＋-doped TiO2/SiO2 was higher than that ofundoped TiO2/SiO2. The optimum dopant content was about 0.10wt%.

Novel Electro-Optical Modulator Utilizing GeO_2-Doped Silica Waveguide

In order to achieve a modulator with broad bandwidth and perfect impedance match,a novel electro-optical modulator based on GeO2-doped silica waveguides on silicon substrate is designed.The finite element model of the whole electro-optical modulator is established by means of ANSYS.With the finite element method analysis,the performance of the novel modulator is predicted.The simulation reveals that the designed modulator operates with a product of 3 dB optical bandwidth and modulating length of 226.59 GHz·cm,and a characteristic impedance of 51.6 Ω at 1 550 nm wavelength.Moreover,the calculated electrical reflected power of coplanar waveguide electrode is below-20 dB in the frequency ranging from 45 MHz to 65 GHz.Therefore,the designed modulator has wide modulation bandwidth and perfect impedance match.

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.

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.

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.

Interfacial Structure of Nanocrystalline SnO_2 and SiO_2-doped SnO_2

The study of nanocrystalline SnO2 (n-SnO2) and SiO2-doped SnO2 (n-Si-SnO2) samples pre-pared by the sol-gel process showed that SiO2 doping can effectively restrained the growth of nanocrystalline SnO2 grains, thus improving thermal stability of the materials.

Study on the Synthesis of La(3)-doped Nano-TiO_2 and Photocatalytic Degradation of Methyl Orange

In this paper,La（3）-doped Nano-TiO2（La（3）-TiO2） was synthesized via hydrothermal process.Structure and optical properties of the synthesized samples were characterized via XRD,FT-IR,DRS,etc.The results showed that the phase transformation of TiO2 from anatase to rutile was effectively prevented by La（3）-doping,which improved the thermal stability of anatase,and also suppressed particle aggregation and grain growth of TiO2.The formation of Ti-O-La bond promoted UV absorption intensity of TiO2,and provoked red shift of absorbed light.And the spectra response range of TiO2 was extended significantly to visible light by La（3）-doping,then photocatalytic performance was improved effectively.Compared with pure nano-TiO2,the performance of La（3）-TiO2 which photocatalyticly degraded methyl orange was increased significantly.

Zero-field splitting parameters and local structures for tetragonal Cr^(2+) centers in Cr^(2+)-doped ZnSe semiconductors

The inter-relation between zero-field splitting （ZFS） parameters and local lattice structures of the （CrSe4）6 clusters in ZnSe semiconductors has been established by using the complete diagonalization （of the energy matrix） method. On the basis of this, the local lattice distortions, the ZFS parameters D, a, F and the optical spectrum for Cr2＋ ions doped into ZnSe are theoretically investigated, and the contributions of the spin singlets have been taken into account. The calculated ZFS parameters are in good agreement with the experimental values. From our calculations, the tetragonal distortion parameters AR = 0.091A and Aθ = 4.28° of Cr2＋ in ZnSe are acquired, and the results suggest that there exists a tetragonal expansion distortion for the local lattice structure of （CrSe4）6- clusters in ZnSe crystals. The influence of the spin singlets on ZFS parameters is also discussed, indicating that the contributions to ZFS parameters a and F cannot be ignored.

Crystallization and Luminescence Properties of Sm3＋-Doped SrO-Al2O3-SiO2 Glass-Ceramics

The Sm^（3＋）-doped SrO-Al2O3-SiO2（SAS） glass-ceramics with excellent luminescence properties were prepared by batch melting and heat treatment. The crystallization behavior and luminescent properties of the glass-ceramics were investigated by DTA, XRD, SEM and luminescence spectroscopy. The results indicate that the crystal phase precipitated in this system is monocelsian（SrAl2Si2O） and with the increase of nucleation/crystallization temperature, the crystallite increases from 66 % to 79 %. The Sm（3＋）-doped SAS glass-ceramics emit green, orange and red lights centered at 565, 605, 650 and 715 nm under the excitation of 475 nm blue light which can be assigned to the 4 G5/2→6 Hj/2（j=5, 7, 9, 11） transitions ofSm^（3＋）, respectively. Besides, by increasing the crystallization temperature or the concentration ofSm^（3＋）, the emission lights of the samples located at 565, 605 and 650 nm are intensified significantly. The present results demonstrate that theSm^（3＋）-doped SAS glassceramics are promising luminescence materials for white LED devices by fine controlling and combining of these three green, orange and red lights in appropriate proportion.

Emission property of Y_2O_3-doped Mo secondary emitter

Y2O3-doped Mo secondary emitters were prepared by liquid-liquid doping and solid-solid doping,respectively.The back-scattered scanning observation result indicates that the emitter prepared by liquid-liquid doping has fine microstructure whereas that prepared by solid-solid doping has large grain size.Y2O3-doped Mo emitter with small grain size prepared by liquid-liquid doping exhibits high emission property,i.e.,the secondary electron yield can get to 5.24,about 1.7 times that prepared by solid-solid doping.Moreover,Y2O3-doped Mo emitter exhibits the best emission performance among La2O3-doped Mo,Y2O3-doped Mo, Gd2O3-doped Mo and Ce2O3-doped Mo emitters due to the largest penetration depth of primary electrons and escape depth of secondary electrons in this emitter.The secondary emission of the emitter with small grain size can be explained by reflection emission model and transmission emission model,whereas only transmission emission exists in the emitter with large grain size.

MCM-41负载SO_4^(2-)/ZrO_2超强酸的性能研究

采用浸渍 -焙烧法制备了 MCM-4 1负载 SO2 - 4 /Zr O2 ( SZ)超强酸催化剂 ,并考察了其织构性质及酸性的变化规律 .结果发现 ,过高的 SZ负载量会引起 MCM-4 1介孔结构的破坏 ,而负载量过低则不能产生超强酸性 .适宜的负载量为 4 0 %左右 .样品的超强酸性随其 Zr O2 含量的增加而递增 .SZ的引入同时也增加了样品的中强酸酸性和弱酸酸性 ,样品酸性可通过改变

非晶和纳米ZrO_2,ZrO_2∶Y发光研究

利用共沉淀法制备了非晶和纳米ZrO2 和ZrO2 ∶Y(7% )。通过X射线衍射对其晶化过程的结构变化进行了表征 ,并在不同温度和气氛下进行处理 ,研究了对其发光性质的影响。结果表明发射谱由一个Gaus sian带 (峰值 2 6 9eV)和一个非对称带 (峰值 3 12eV)构成 ,它们对应的发光中心分别为F+ 心和 (F F) + 心。非晶样品的发光强度比纳米晶样品强 ,发光强度主要受氧空位的浓度和晶粒尺寸的影响 ,随着处理温度的升高 。

S_2O_8^(2-)/ZrO_2-Al_2O_3固体超强酸催化剂的研制与应用

A S 2O 2- 8/ZrO 2 Al 2O 3 type solid superacid catalyst was prepared from ZrOCl 2·8H 2O, AlCl 3· 6H 2O and (NH 4) 2S 2O 8 by coprecipitation, maceration and calcination processes. Their crystal structures and acidities were determined by XRD and Hammett method, respectively. The activity of the catalyst was studied as function of Al 2O 3 content, calcination temperature and time in the esterification of acetic acid with butanol, and a conversion of 96 5% was obtained. The catalyst gave also higher yields in syntheses of ketals and acetals: cyclohexanone ethylene ketal(86 2%), acetophenone ethylene ketal(78 5%), acetylacetic ester ketal(88 5%), benzaldehyde glycol acetal(76 3%). The chemical structures of the products were confirmed by IR spectra.