不同形貌TiO2薄膜的可控制备及其光电化学性能研究

采用水热法在FTO(fluorine-doped tin oxide)基底上制备不同形貌的锐钛矿结构TiO₂薄膜。通过不断增大反应前驱物中盐酸浓度,TiO₂薄膜由球状颗粒薄膜逐渐演变生长成大面积高能(001)面裸露的TiO₂纳米片阵列薄膜。通过对形貌演化规律及X射线衍射图谱变化规律进行分析,提出了不同形貌TiO₂薄膜的生长演化机制,并对盐酸在其中的作用进行了说明。为了进一步改善TiO₂薄膜的性能,采用连续离子层吸附反应法对不同形貌的TiO₂薄膜进行CdS量子点敏化。采用紫外可见吸收光谱分析法和三电极体系对复合薄膜的光吸收性能和光电化学(PEC)性能进行了研究,实验数据显示CdS/TiO₂复合薄膜的光电化学性能皆明显优于单纯TiO₂薄膜,而且纳米片阵列薄膜的性能明显优于其他形貌薄膜,说明了大面积高能(001)面裸露的TiO₂纳米片阵列薄膜的性能优越性。     

TiO2/Ni3[Ge2O5](OH)4复合材料的制备及光催化性能

以Ni₃[Ge₂O₅](OH)₄为载体,氟钛酸铵为原料,采用水热辅助液相沉积法制备了纳米TiO₂/ Ni₃[Ge₂O₅](OH)₄复合材料。通过X射线衍射(XRD)、拉曼光谱分析(RM)、场发射扫描电子显微镜(FE-SEM)、高分辨透射电镜(HTEM)、紫外-可见吸收光谱(UV-Vis)等表征手段对样品的物相组成、结构特性及微观形貌做了检测分析,并且探究了不同二氧化钛负载量对纳米TiO₂/Ni₃[Ge₂O₅](OH)₄复合材料光降解亚甲基蓝能力的影响规律。结果表明,实验实现了纳米TiO₂与Ni₃[Ge₂O₅](OH)₄的紧密复合与有效分散,TiO₂为锐钛矿型结构,平均粒径20 nm。该复合材料能够有效抑制光生载流子的复合,改善材料的吸附性能,提高材料的光催化效率。当复合材料中TiO₂与Ni₃[Ge₂O₅](OH)₄的摩尔比为3.1∶1时,材料对亚甲基蓝的光催化效率最高,90 min亚甲基蓝的光降解率为99.81％。     

SiW12、CsPbI3协同提高TiO2纳米管光电转换效率的研究

为克服TiO₂纳米管在光电转换时电子-空穴复合率高和吸收光谱范围窄的缺陷,利用多酸H₄SiW₁₂O₄₀(SiW₁₂)和CsPbI₃量子点对其协同修饰,采用电沉积法将SiW₁₂沉积在TiO₂纳米管上,制备了SiW₁₂/TiO₂纳米管复合薄膜;使用高温热注射法合成出CsPbI₃量子点,再通过化学浴沉积法沉积CsPbI₃量子点到复合薄膜上,得到SiW₁₂/CsPbI₃/TiO₂纳米管复合薄膜,探究SiW₁₂沉积时间、CsPbI₃沉积次数对TiO₂纳米管光电性能的影响。利用扫描电子显微镜(SEM)、能谱仪(EDS)、透射电子显微镜(TEM)、X射线衍射(XRD)仪、红外分光光度计(FT-IR)、紫外-可见分光光度计(UV-Vis)对薄膜进行表征,使用电化学工作站测试薄膜的光电化学性能。结果表明:TiO₂纳米管沉积多酸SiW₁₂和CsPbI₃量子点后,光吸收范围扩大、电荷转移电阻降低,光电转换效率得到显著提升,最高达到0.52%。说明SiW₁₂和CsPbI₃的协同作用很好地抑制了TiO₂纳米管电子-空穴的复合,并拓宽了吸收光谱范围,提高了TiO₂纳米管的光电转换效率。     

H2SO4-H2O中硝酸铜对脱硫石膏晶须生长的影响

以处理后的脱硫石膏为原料,在H₂SO₄-H₂O体系中以Cu(NO₃)₂为晶形控制剂采用水热法制备脱硫石膏晶须,探讨了Cu(NO₃)₂对脱硫石膏晶须生长的影响机理。结果表明:Cu(NO₃)₂对脱硫石膏有明显促溶作用,其中Cu²⁺可减小溶液中各离子的活度系数,使溶液中的Ca²⁺浓度增大。NO^-₃通过静电作用在Ca²⁺周围聚集并对SO^2-₄产生屏蔽作用,导致脱硫石膏继续溶解并使Ca²⁺和SO^2-₄的浓度处于相对稳定状态,有利于半水脱硫石膏晶体的形核与生长。此外,Cu²⁺还可在晶须的生长过程中选择性吸附在晶须表面,生成CuSO₄,促进了脱硫石膏的结晶生长,最终在Cu(NO₃)₂用量为2.0%(质量分数)时制备的脱硫石膏晶须长径比约为73。     

还原氧化石墨烯增强碳化硼陶瓷的制备与表征

采用球磨混合、雾化造粒方法制备了氧化石墨烯/碳化硼(GO/B₄C)复合粉体,并将其在2 100 ℃和30 MPa压力下真空热压,得到了还原氧化石墨烯/碳化硼(rGO/B₄C)复合材料,使用扫描电镜(SEM)、热重分析(TG)和X射线衍射(XRD)等表征方法和三点弯曲法以及排水法等测试方法对复合材料进行表面相分析和力学性能表征,研究了GO添加量对rGO/B₄C复合材料的弯曲强度和断裂韧性等力学性能的影响。结果表明,将稳定分散的GO/水悬浮液逐步加入到球磨中的B₄C浆料中,可以得到混合均匀的GO/B₄C复合粉体。在粉末浆料中加入质量分数为1.5%的GO, rGO/B₄C复合材料的弯曲强度和断裂韧性分别为535 MPa和5.2 MPa·m^1/2,分别比B₄C陶瓷提高了72.6%和136%,有利于碳化硼陶瓷在军事防护领域的应用。并从石墨烯拔出、裂纹偏转和桥接等方面解释了rGO/B₄C复合材料的增韧机理。     

稀上元素(镧、铈)掺杂TiO2复合材料的制备及其光催化性和抑菌性的研究

以钛酸丁酯(C₁₆H₃₆O₄Ti)、蒸馏水、无水乙醇、冰乙酸、氧化镧(La₂O₃)和氧化铈(CeO₂)为原料,采用溶胶-凝胶法制备了纳米TiO₂和稀土元素掺杂的TiO₂复合材料.利用X射线衍射仪、扫描电子显微镜、ICP-OES等离子体发射光谱元素分析、紫外-可见光谱仪和培养基扩散法对样品进行了表征和性能研究.实验结果表明:本实验成功制备了锐钛矿晶型的TiO₂粉末和镧掺杂的二氧化钛粉末(La/TiO₂),因氧化铈微溶于酸,没有溶解到溶液中,Ce基本没有掺入到二氧化钛中,所制备的粉末主要是锐钛矿型二氧化钛和氧化铈的混合物,对TiO₂的性能基本没有影响.La/TiO₂粉末中La元素的含量为8.24;,在300 min内La/TiO₂光催化罗丹明B溶液的脱色率提高达到91.2;,对金黄色葡萄球菌有良好的抑制作用.     

TiO2烧结助剂对纳米η-Al2 O3制备Al2 O3-Cr2 O3固溶体的影响研究

以纳米η-Al₂O₃粉和工业铬绿为原料,以摩尔比1:1配比制备Al₂O₃-Cr₂O₃固溶体,以TiO₂为烧结助剂,在还原气氛下经1400 ℃、1500 ℃和1600 ℃固相烧结.研究了TiO₂的加入对纳米η-Al₂O₃制备Al₂O₃-Cr₂O₃固溶体的致密度、线收缩率、相组成、晶胞参数、互扩散程度和微观结构的影响.结果表明:TiO₂的加入能促进Al₂O₃-Cr₂O₃固溶体的致密化;当温度为1600 ℃,TiO₂的添加量为2wt;时,试样的体积密度最大为4.57 g·cm^-3,线收缩率为19.8;;TiO₂的加入能使Al₂O₃-Cr₂O₃固溶体中Al³⁺和Cr³⁺的互扩散程度增加;微观结构表明,TiO₂的加入能使Al₂O₃-Cr₂O₃固溶体晶粒之间结合更紧密,实验温度范围内,随着TiO₂添加量的增加晶粒从沿晶断裂向穿晶断裂转变,只在晶间和晶内存在极少量气孔,当温度为1600 ℃,TiO₂的添加量为2wt;时,晶粒大小较均匀,平均晶粒尺寸约10μm.     

射频磁控溅射氧气流量对制备的Ga2O3∶Cr薄膜光致发光性能的影响

在不同氧气流量下,采用双靶射频磁控共溅射的方法在蓝宝石(α-Al₂O₃)基底上制备得到系列掺Cr的Ga₂O₃(Ga₂O₃∶Cr)薄膜,详细研究了薄膜在900 ℃退火前后的结构和光学性能。结果表明,未退火的Ga₂O₃∶Cr薄膜为非晶结构,其发光主要位于蓝绿波段。经900 ℃退火后,薄膜的结构由非晶变为多晶,且在近红外波段观测到了来源于Cr³⁺掺杂的发光。退火后的薄膜结晶质量和近红外发光均与氧气流量密切相关,而其光学带隙不受氧气流量的影响。在所研究的氧气流量范围,4 mL/min氧气流量下薄膜的近红外发光强度最强,这与此条件下薄膜结晶质量较好以及Cr³⁺替代Ga³⁺的数量较多有关。以上研究成果可为制备高质量Ga₂O₃∶Cr薄膜提供参考。     

SnO2/氮掺杂石墨烯纳米复合材料的制备及其电化学性能研究

采用温和的水热法在氧化石墨烯(GO)片层上原位生长纳米SnO2颗粒, 通过氨水调节体系pH值并对石墨烯进行掺氮,成功制备出了SnO2/氮掺杂石墨烯(N-rGO)和SnO2/石墨烯(rGO)纳米复合材料,并对它的电池和电催化性能进行研究.XRD和SEM等分析结果表明,SnO2颗粒均匀地分布在N-rGO和rGO表面,粒径分别为50 nm和100 nm左右.进一步的TEM结果表明,SnO2颗粒是由更细小的粒径为5~7 nm SnO2颗粒所组成的二次团聚体.半电池性能测试结果表明:在100 mA/g电流密度下,SnO2/N-rGO和SnO2/rGO的可逆容量分别为901 mAh/g、756 mAh/g,比同等条件下纯的纳米SnO2高6.0和4.9倍;在2 A/g的高电流密度放电情况下, SnO2/N-rGO和SnO2/rGO的放电比容量分别可以达到619 mAh/g和511 mAh/g,表现出优异的倍率性能.电催化性能测试表明:SnO2/N-rGO的催化活性要高于SnO2/rGO,催化氧还原反应(ORR)主要按照四电子转移过程进行,为非铂催化剂的研究提供了一个新的思路.     

静电纺丝法制备CeO2微纳米纤维及其除氟性能

以聚丙烯腈(PAN)为载体,六水合硝酸铈[Ce(NO₃)₃·6H₂O]为原料,采用静电纺丝法制备了Ce(NO₃)₃/PAN纤维,在空气中热处理得到CeO₂微纳米纤维,通过XRD、BET和SEM对CeO₂微纳米纤维进行表征。采用静态吸附实验探讨了CeO₂微纳米纤维去除水溶液中氟离子的性能,考察了溶液pH值、初始氟离子浓度及共存阴离子等对吸附性能的影响。结果表明,pH=3时,CeO₂微纳米纤维对F^-的吸附性能最佳,CeO₂吸附量随着F^-浓度的增大呈上升趋势。CeO₂微纳米纤维对F^-的吸附等温线遵循Langmuir模型,二级动力学模型能很好地描述CeO₂微纳米纤维对F^-的吸附过程。CeO₂微纳米纤维的除氟性能优良,可为其实际应用提供理论参考。     

Migration of Cu ions in Cu2O---Al2O3---SiO2 glasses on heating in air

The behavior of copper ions in the Cu₂O·Al₂O₃·4SiO₂ (in moles) glass on heating in air at temperatures up to 500°C was studied. When the glass, in which about 90% of Cu was present as Cu⁺ ions, was heated in air above 300°C, a CuO layer was formed on the surface. The amount of CuO was increased with heating temperature and time, corresponding to the decrease in weight of the glass. Furthermore, the fraction of Cu²⁺ ions in the glass increased. These observations suggest that oxygens do not diffuse into the glass, but Cu⁺ ions migrate to the surface from the interior to balance the surplus positive charge produced by the oxidation of Cu⁺ to Cu²⁺ ions inside the glass. The following reaction scheme for the formation of the CuO layer was proposed; 2Cu⁺(interior) + ₂¹O₂(surface) → Cu²⁺(interior) + CuO(surface).     

The effect of oxygen pressure on the microstructures of Co-doped rutile TiO2 thin films grown by pulsed laser deposition

Comprehensive microstructures of 7% cobalt-doped rutile TiO₂ thin films grown on c-plane sapphire by pulsed laser deposition were characterized using transmission electron microscopy (TEM). The effects of oxygen pressure during growth on the Co distribution inside the films were investigated, and the detailed growth mechanism of both TiO₂ and TiO₂+Co was discussed. The similar oxygen sublattices and low mismatch between (1 0 0) rutile and c-plane sapphire favors the rutile phase. However, the three-fold symmetry of the substrate surface resulted in three rutile domain orientation variants, and they grow adjacent to each other. Cobalt was found to precipitate out as nanocrystals inside the TiO₂ matrix as the growth pressure of oxygen was decreased. At 0.05 mTorr oxygen pressure, almost all of the Co segregates into crystallographically aligned nanocrystals with a particle size of 4.4±0.15 nm. All the samples have magnetic coercivity at room temperature. The magnetic moment per Co atom increased with decreased oxygen pressure, suggesting that the Co that replaced the Ti²⁺ in the TiO₂ lattice does not have a large magnetic moment.     

CrO2 (1 0 0) and TiO2 (1 0 0) film heteroepitaxy on a BaF2 (1 1 1)/Si (1 0 0) substrate

Multi-domained heteroepitaxial rutile-phase TiO₂ (1 0 0)-oriented films were grown on Si (1 0 0) substrates by using a 30-nm-thick BaF₂ (1 1 1) buffer layer at the TiO₂–Si interface. The 50 nm TiO₂ films were grown by electron cyclotron resonance oxygen plasma-assisted electron beam evaporation of a titanium source, and the growth temperature was varied from 300 to 600 °C. At an optimal temperature of 500 °C, X-ray diffraction measurements show that rutile phase TiO₂ films are produced. Pole figure analysis indicates that the TiO₂ layer follows the symmetry of the BaF₂ surface mesh, and consists of six (1 0 0)-oriented domains separated by 30° in-plane rotations about the TiO₂ [1 0 0] axis. The in-plane alignment between the TiO₂ and BaF₂ films is oriented as [0 0 1] TiO₂ || BaF₂ or [0 0 1] TiO₂ || BaF₂ . Rocking curve and STM analyses suggest that the TiO₂ films are more finely grained than the BaF₂ film. STM imaging also reveals that the TiO₂ surface has morphological features consistent with the BaF₂ surface mesh symmetry. One of the optimally grown TiO₂ (1 0 0) films was used to template a CrO₂ (1 0 0) film which was grown via chemical vapor deposition. Point contact Andreev reflection measurements indicate that the CrO₂ film was approximately 70% spin polarized.     

制备方法对Al2O3-CeO2物化性质及CO2加氢制甲醇催化性能的影响

复合氧化物界面性质与CO₂加氢制甲醇反应的催化性能有着重要的关系。本文对比考察了物理共混法、浸渍法、传统共沉淀法和微流控连续共沉淀法对Al₂O₃-CeO₂复合氧化物界面性质和催化性能的影响。浸渍作用尽管使Al₂O₃/CeO₂界面产生了一定的结构性质调变,但贫瘠的氧空位缺陷导致催化反应效率低。共沉淀样品中固溶结构的存在增强了Al₂O₃/CeO₂界面的相互作用,增大了电子结合能,形成的大量氧空位缺陷有利于CO₂活化转化。而微流控连续共沉淀法合成样品因具有更小的晶粒尺寸、均匀的复合相结构和丰富的氧空位缺陷,表现出更为优异的催化性能。在原料气配比为V(H₂)∶V(CO₂)∶V(N₂)=72∶24∶4,反应温度为320 ℃,反应压力为3 MPa,体积空速为9 000 mL·g^-1·h^-1的条件下,Al₂O₃-CeO₂复合氧化物的CO₂转化率、甲醇选择性及甲醇时空产率分别达到15.3%,86.4%和0.076 g·mL^-1·h^-1。     

Surface modification of a TiO2 film electrode prepared by the sol-gel method and its effect on photoelectrochemical behavior

The surface of a TiO₂ film electrode, about 1 μm thick, prepared by the sol-gel method, was modified by being additionally coated with about 0.1 μm thick TiO₂---SiO₂, TiO₂---ZrO₂ or TiO₂---Al₂O₃ films. The effect of the additional coating on the photoelectrochemical properties of a TiO₂ film electrode was investigated in detail. On addition of the second additive to TiO₂, the flat band potential was shifted toward negative potential for SiO₂ and positive potential for ZrO₂ and Al₂O₃, which is attributed to the change in the point of zero zeta potential (pzzp), not in the electron affinity (EA). However, enhancement in photocurrent was not observed for all the cases.