铑掺杂钛酸锶的第一性原理计算研究

基于密度泛函第一性原理研究了研究了铑(Rh)(掺杂量分别为:5.5%,8.3%,12.5%,25.0%)掺杂钛酸锶(SrTiO_3)的电子结构及光学性质。研究结果表明:铑元素的掺入使得钛酸锶整体的价带发生移动,禁带宽度逐渐缩小,当铑的掺入量达到25%时价带能级穿越费米能级,同时可以发现随着铑掺入量的增加,钛酸锶对于可见光的吸收逐渐增加,掺入量达到12.5%以上时对于紫外可见光(波长:200～800 nm)的吸收明显大幅提升。     

共沉淀法制备Mo/N共掺杂TiO_2可见光光催化剂

采用共沉淀法制备了Mo/N共掺杂TiO2光催化剂(Mo-N-TiO2)。结果表明,所得光催化剂为锐钛矿晶型,Mo/N共掺杂使样品对可见光吸收增强,吸收带边明显红移。在Mo∶N∶Ti摩尔比为0.012 5∶0.02∶1,煅烧温度为500℃的最优制备条件下,样品在白炽灯下照射2 h对亚甲基蓝溶液脱色率达55.7%。Mo以+6价的形式存在,并取代Ti4+进入TiO2晶格中,导致TiO2表面的Lew is酸性增强,有利于其导带中光生电子向表面迁移,促进了光生电子-空穴对的分离,同时与共掺杂引起的带边红移和较完整的锐钛矿相的协同作用有效提高了TiO2的可见光催化活性。     

基于第一性原理的锐钛矿相EuxTi1-xO2-xNx电子结构及吸收光谱研究

基于第一性原理,采用密度泛函理论平面波超软赝势方法,建立了Eu单掺杂及Eu-N共掺杂的锐钛矿TiO2模型,对各模型的能带分布,态密度及吸收光谱进行计算.结果表明Eu-N共掺杂的锐钛矿TiO2在稳定性、光催化性能、吸收光谱红移等方面均优于Eu单掺杂的锐钛矿TiO2.     

Na:O共掺杂AlN晶体的第一性原理研究

基于密度泛函理论的第一性原理全势线性缀加平面波法,分别研究了Al N在Na单掺杂和Na:O共掺杂情况下的晶格结构、电子态密度及能带结构。计算结果表明:Na单掺杂Al N和Na:O共掺杂Al N均为直接带隙半导体材料,且表现出p型掺杂特性;相比于本征Al N晶体,两者的晶格结构均膨胀,而Na:O共掺杂相对Na单掺杂Al N晶格膨胀较小;Na单掺杂Al N的价带顶态密度具有较强的局域化特性,不利于掺杂浓度的提高;与Na单掺杂Al N相反,Na:O共掺杂Al N的价带顶态密度局域化特性明显减弱,受主能级变浅,有利于Al N的p型掺杂。     

N、S共掺杂改性TiO_2的制备及其光催化活性

采用焙烧法制备了具有可见光催化活性的光催化剂SxTi1-xN2-yOy.光电子能谱结果表明SxTi1-xN2-yOy中S是以 6价阳离子的形式存在,其掺杂方式是置换了晶格金属离子Ti4 形成阳离子S6 的掺杂;且由于S6 阳离子的存在,导致N1s出现宽化移动现象,N在掺杂过程中形成了N-C、N-S、N-O及Ti-N键.紫外-可见漫反射及表面光电压谱研究结果表明,SxTi1-xN2-yOy吸收带边为528 nm,对应的带-带跃迁能量为2.3 eV,具有明显的可见光催化活性,SxTi1-xN2-yOy仍为n型半导体.模拟太阳光下的光催化降解苯甲酸试验表明,SxTi1-xN2-yOy在可见光下具有很好的光催化活性,是未改性TiO2的2.8倍.     

碳硅共掺杂AlN晶体的电子结构分析

采用基于密度泛函理论的全势线性缀加平面波法,研究了C∶Si共掺杂纤锌矿AlN晶体的32原子超胞体系,得到了该体系的能带结构、电子态密度等性质,在此基础上分析了C∶Si共掺杂实现AlN晶体p型掺杂的机理.在AlN晶体的掺杂体系中,当C、Si的浓度相等时,会形成C-Si复合物,但施主和受主杂质相互补偿致使自由载流子浓度较低;当提高C的掺杂浓度时,会形成C2-Si,C3-Si等复合物,这些复合物的生成能够提高受主杂质的固溶度,降低受主激活能,有效提高空穴浓度.分析表明:C∶Si共掺杂有利于获得p型AlN晶体.     

N、La共掺杂纳米TiO_2的制备及其光催化性能

以钛酸丁酯、尿素、硝酸镧为原料,采用超声辅助溶胶-凝胶法制备了N、La共掺杂纳米TiO_2光催化材料。用XRD、DSC-TG、UV-Vis DRS、FT-IR、SEM、EDS对材料结构和性能进行了表征。以苯酚为目标污染物,考察材料的光催化性能。结果表明:N、La共掺杂协同作用使晶粒细化,材料的光催化活性显著提高;当N掺杂摩尔分数为5%、La掺杂摩尔分数为1%、催化剂用量为1.5 g/L、焙烧温度为500℃时,光催化降解5 mg/L苯酚的效果最佳。     

Al-S共掺杂SnO2电子结构的第一性原理研究

本文采用第一性原理方法,研究了Al-S、Al-2S共掺SnO2的能带结构、态密度以及Mulliken布局.研究结果表明,Al-S共掺时,态密度向低能区方向移动,费米面附近出现深杂质能级,起复合中心的作用,主要由S的3p态贡献;Al-2S共掺时,态密度向低能方向移动程度更高,费米能级附近形成浅施主能级,能级距离导带底更近,S的3p态贡献更大.Al-S共掺会打破SnO2电子平衡状态,导致电荷密度重新分布.     

N、Bi共掺杂的TiO_2可见光光催化剂的制备及其光催化性能

采用溶胶-凝胶法制备系列BixTi1-xO_2光催化剂以及N和Bi共掺杂Ti O_2光催化剂,采用XRD、UV-Vis、N2-物理吸附和TEM等对催化剂进行微观结构表征,以普通节能灯为光源,考察催化剂光催化氧化室内甲醛的性能。结果表明,在Bi掺杂的Ti O_2光催化剂体系中,Bi0.15Ti0.85O_2光催化剂催化降解甲醛效果最佳,400℃焙烧2.5 h,节能灯光照48 h,可将(1.05±0.05)mg·m-3甲醛降解至0.08 mg·m-3,甲醛转化率92.8%,达到室内空气质量标准。当N与Bi共掺杂时,节能灯光照24 h,Bi0.15Ti0.85O_2-N(0.2)光催化剂表现出最佳的光催化氧化降解甲醛性能,即可将甲醛由(1.05±0.05)mg·m-3降解至0.082 mg·m-3,甲醛转化率达92.0%,较Bi0.15Ti0.85O_2催化剂光催化效率提高50%。     

N、Bi共掺杂TiO_2光催化剂的制备及对靛红降解性能研究

以硫脲为氮源,硝酸铋为铋源,钛酸四正丁酯为原料,利用溶胶-凝胶法制备了纯TiO2和不同比例N、Bi共掺杂的TiO2光催化剂样品。用紫外-可见分光光度仪对制备的催化剂样品进行了表征。结果表明,制备的N、Bi共掺杂TiO2纳米粉体在可见光区吸收红移,表现出优异的光催化性能;当N与Bi的物质的量比为8∶1、反应温度为25℃,底物的质量浓度为20 mg/L、pH值为5.0时,该光催化体系对靛红溶液的脱色效果最好,脱色率最高为23%。     

氮掺杂对金红石二氧化钛光电特性影响的理论研究

运用第一性原理LDA+U方法,计算不同浓度氮元素掺杂金红石相二氧化钛的能带结构、态密度和光学性质,研究显示氮元素的掺入使TiO_2-x N _x 体系带隙变窄。而O-2p与N-2p轨道杂化耦合在费米能级附近出现了杂质能级,促使载流子跃迁变容易,从而拓展了TiO_2-x N _x 体系对可见光的响应范围。此外,杂质能级对电子-空穴对的复合有抑制作用,对光催化活性的提升具有积极作用。研究结果表明,当氮元素掺杂量（x）为0.062 5时,TiO_2-x N _x 体系光吸收性能与光电响应较好。     

The electronic structure and optical properties of Mn and B,C, N co-doped MoS2 monolayers

The electronic structure and optical properties of Mn and B, C, N co-doped molybdenum disulfide (MoS₂) monolayers have been investigated through first-principles calculations. It is shown that the MoS₂ monolayer reflects magnetism with a magnetic moment of 0.87 μB when co-doped with Mn-C. However, the systems co-doped with Mn-B and Mn-N atoms exhibit semiconducting behavior and their energy bandgaps are 1.03 and 0.81 eV, respectively. The bandgaps of the co-doped systems are smaller than those of the corresponding pristine forms, due to effective charge compensation between Mn and B (N) atoms. The optical properties of Mn-B (C, N) co-doped systems all reflect the redshift phenomenon. The absorption edge of the pure molybdenum disulfide monolayer is 0.8 eV, while the absorption edges of the Mn-B, Mn-C, and Mn-N co-doped systems become 0.45, 0.5, and 0 eV, respectively. As a potential material, MoS₂ is widely used in many fields such as the production of optoelectronic devices, military devices, and civil devices.     

Study on the interfacial properties of active Ti element/ZrO2 by using first principle calculation

Ti element is an important active element in brazing Zirconia ceramic (ZrO₂) ceramic. Therefore, the interface bonding mechanism of Ti and ZrO₂ was studied by using first principles calculation. Two kinds of interfaces with different termination and stacking sequence were established, and the interfacial bonding mechanism was studied using work of adhesion (W_ad), electronic behavior and interface energy. The results show that in the O-terminated interface, Ti and O form a strong ion-covalent bond at the interface, and the W_ad can reach 13.61 J/m². In the Zr-terminated interface, Ti and Zr form a metal-covalent bond, and the W_ad is 5.56 J/m². At a temperature of 1123K, when the lnP_O2 is larger than e⁻¹⁷, the O-rich interface is more stable in thermodynamics. Therefore, under the experimental condition, the interface tends to form Ti-O compounds when ZrO₂ is brazed using Ag(Ti) filler metal.     

The mechanical properties and electronic structures of V,Cr, Mn,Fe, Ni atoms doped MoCoB by first-principles calculation

MoCoB-based cermets have been regarded as the potential substitution of WC cermets with high hardness, high melting point and high oxidation resistance. Ternary borides-based cermets are widely used in extreme environment, such as high-pressure environment. Therefore, it is significant to explore the mechanical properties and electronic structures of transition elements X (X = V, Mn, Fe, Ni) atoms doped MoCoB under high pressure, which are performed by first-principles calculations to provide guidance for industry applications. The analysis of cohesive energy and formation enthalpy indicates high pressure leads to unstable states with lower lattice constants and crystal volumes. The deviation of cohesive energy and formation enthalpy indicate Mo₄Co₃FeB₄ and Mo₄Co₃NiB₄ have similar stability. The shear modulus, Young's modulus and bulk modulus increase under high pressure, which consists with the increasing of covalence. The variation of ductility and anisotropy indicate similar upward trend, which is verified by Poisson's ratio, B/G ratio and anisotropy index A^U. The analysis of overlap population indicates high pressure leads to the increasing of covalence of B-Co covalent bonds and the decreasing of the covalence of B-Mo covalent bonds. The analysis of electronic structures indicates the high pressure leads to higher hybridization and lower density of states of metallic bonds. The analysis of charge density difference consists with the variation of mechanical properties, implying shorter bond length and higher bonds strength under high pressure.     

N、Mn共掺杂TiO_2的制备、表征及光催化性能研究

应用溶胶凝胶法,以尿素、氯化锰和钛酸丁酯为原料制备了纯Ti O2、N掺杂、Mn掺杂及N、Mn共掺杂的Ti O2纳米粉体。采用XRD、SEM、EDS、UV-VIS等分析手段对样品的物相、形貌、成分和吸光性能进行了表征,并且以亚甲基蓝溶液为模拟污染物在阳光下进行了光催化实验。结果表明,样品主要为锐钛矿相二氧化钛及少量的金红石型二氧化钛;样品呈颗粒状,有一定程度的团聚;N掺杂、Mn掺杂及N、Mn共掺杂样品的吸收光谱分别红移至470、440、490 nm;光催化实验表明,在可见光照射下的光催化能力由强到弱依次为N、Mn共掺杂N掺杂Mn掺杂纯Ti O2。     

N，N，N-三（2-甲基苯并咪唑）胺氧钒配合物的合成、表征及光谱性质研究

本文用微波法合成了配体N,N,N-三（2-甲基苯并咪唑）胺,并以无水甲醇为溶剂,在常温条件下合成了配体与硫酸氧钒的配合物。通过红外光谱和元素分析对其结构进行了表征,并对其紫外吸收峰随pH值的变化及荧光性质进行了研究,结果表明配体在紫外光区吸收峰的强度随pH值的增大而降低,而配合物吸收峰的强度随pH值的增大先降低后增高,二者均发生红移;氧钒配位后使配体发生荧光猝灭。     

Improvement of microstructure,mechanical properties and cutting performance of Ti(C,N)-based cermets by ultrafine La2O3 additions

Ti(C,N)-WC-Mo₂C-TaC-Co-Ni cermets with various content of La₂O₃ were prepared by gas-pressure sintering at 1450 °C. The effects of ultrafine La₂O₃ additions (0, 0.05, 0.1 and 0.2 wt%) on the microstructure, mechanical properties, wear resistance and cutting performance of cermets were explored. In the microstructure of cermets, the La₂O₃ particles and dissolved La element in binder phases were observed, which could inhibit the dissolution-precipitation process of ceramics phases during liquid-sintering. Furthermore, the La₂O₃ could absorb and react with the impurity Al element with low melting point from raw powders, avoiding the appearance of liquid phase at the low temperature and partial overheating during sintering process. These mechanisms could inhibit the abnormal growth of Ti(C,N) core-(Ti,W,Mo,Ta)(C,N) rim structures effectively, leading to the thinning of brittle rim phases and coarsening of wear-proof Ti(C,N) particles. The decrease of proportion of brittle rim phase and ultrafine Ti(C,N) particles promoted the fracture toughness. The increase of proportion and grain size of Ti(C,N) improved the hardness, wear resistance and cutting performance significantly. However, the excessive addition of La₂O₃ would result in the agglomeration of La₂O₃, causing the sharp decline of mechanical properties and cutting performance. The cermet with 0.1 wt% La₂O₃ addition possessed the optimal mechanical properties with Vickers hardness, transverse rupture strength and fracture toughness of 1710 (HV30) Kgf/mm², 2480 MPa and 11.7 MPa m^1/2, respectively.     

Microstructure and mechanical properties of Ti(C,N)-based cermets fabricated by in situ carbothermal reduction of TiO2 and subsequent liquid phase sintering

Ti(C,N)-based cermets were prepared by in situ carbothermal reduction of TiO₂ and subsequent liquid phase sintering in one single process in vacuum. The densification behavior, phase transformation, and microstructure evolution of the cermets were investigated by DSC, XRD, SEM, and EDX. The results showed that the carbothermal reduction of TiO₂ was completed below 1250 °C, and Ti(C,N)-based cermets with refined grains were obtained after sintered at 1400 °C for 1 h by this method. The hard phase of the cermets mainly exhibited white core/gray rim structure, in great contrast to the typical black core/gray rim structure of hard phase in traditional cermets. Ti(C,N)-based cermets prepared by this novel method showed excellent mechanical properties with a transverse rupture strength of 2516±55 MPa, a Rockwell hardness of 88.6±0.1 HRA, and a fracture toughness of 18.4±0.7 MPa m^1/2, respectively.