Ag掺杂优化g-C3N4结构及提升可见光降解性能的研究

石墨相氮化碳的改性已经成为光催化领域,特别是光催化材料领域的研究热点。本文以硝酸银和尿素为原料制备一系列不同Ag含量的Ag/g-C₃N₄光催化剂,并以罗丹明B水溶液模拟废水,在可见光下考察Ag/g-C₃N₄催化剂的光催化降解性能,最终获取最佳Ag掺杂量。通过XRD、SEM、FTIR、UV-Vis、PL等对光催化剂进行分析,发现Ag的掺杂有助于g-C₃N₄的剥离,改变了g-C₃N₄的电子结构,降低了其带隙能,使其在可见光区的吸收增强,抑制了光生电子-空穴对的复合。研究表明,当Ag掺杂量为2%时,Ag/g-C₃N₄光催化剂的效果最佳,300 min内降解率高达95.8%。     

载银g-C3N4(Ⅰ)/g-C3N4(Ⅱ)同素异质结催化剂的制备及光催化固氮产氨性能

Ag作为助催化剂能够促进光电子的迁移,在光催化分解水制氢气、CO₂还原、重金属离子还原等反应中应用颇多,然而,到目前为止未见将Ag单质作为助催化剂用于光催化固氮产氨反应的报道。本工作制备了负载单质Ag的g-C₃N₄(Ⅰ)/g-C₃N₄(Ⅱ)同素异质结催化剂,并考察了其光催化固氮产氨的性能。采用X射线衍射(XRD)、透射电镜(TEM)、紫外可见光谱(UV-Vis)、X射线光电子能谱(XPS)、拉曼光谱(Raman)、荧光光谱(PL)、电化学阻抗谱(EIS)、光电流分析等手段对制备的催化剂进行了表征。结果表明,Ag以单质态存在于催化剂表面。所担载的Ag的等离子体效应一方面促进了催化剂对可见光的吸收,使反应体系能产生更多的光生电子-空穴对;另一方面使得光生电子能够在g-C₃N₄与Ag单质间迁移,提高了催化剂的电子-空穴分离效率。负载Ag后g-C₃N₄(Ⅰ)/g-C₃N₄(Ⅱ)同素异质结催化剂的铵离子产生速率为1.36 mg·L-1·h-1·g-1_cat,相比未负载Ag时(0.59 mg·L-1·h-1·g-1_cat)大幅提高,与Pt负载催化剂相当,并且是由单纯三聚氰胺和尿素制备的g-C₃N₄的4.9倍和3.4倍。除固氮反应外,制备的载银g-C₃N₄(Ⅰ)/g-C₃N₄(Ⅱ)同素异质结催化剂在光催化还原氧气制取双氧水的反应中也表现出优良的催化性能。     

过硫酸氢盐催化材料(Co3O4/ACF)的制备及应用

通过改变溶剂热法和水热法中材料的配比和温度制备了18种四氧化三钴/活性炭纤维(Co₃O₄/ACF)复合材料,并将这些复合材料用于催化过一硫酸盐(PMS)降解染料橙黄Ⅱ。考察了制备材料的配比(Co²⁺和ACF)和温度对制得的Co₃O₄/ACF复合材料催化降解橙黄Ⅱ效率的影响,并采用X射线衍射仪、扫描电镜等对复合材料的元素组成和形貌进行了表征。结果表明:水热法制得的复合材料催化性能好,3 min内可完全降解100 mg/L橙黄Ⅱ。从表征结果可见,水热法能更有效地使Co₃O₄颗粒以纳米尺寸分散负载在ACF上。材料的配比对产品的催化降解效率无显著影响,温度对水热法制得的产品的催化降解效率影响不大。水热法在320 ℃条件下煅烧制得的复合材料催化性能好且ACF能基本保持结构完整,Co负载量约为17.2 mg/g。水热法制备的Co₃O₄/ACF复合材料循环利用性能优于溶剂热法制得的材料,在循环使用四次后,28 min内橙黄Ⅱ降解效率仍能达到99%。其高效降解与Co₃O₄/ACF和溶解态Co²⁺的催化作用均有关。正交试验表明,降解过程中时间对降解效果的影响最大,其次是PMS的浓度,催化材料的加入量对降解效率无明显影响。因此,在复合材料应用中,应保证充足的降解时间,并适当提高PMS的浓度。     

ICVI法制备Si3N4P/ Si3N4 复合材料致密化行为数值模拟

根据Si₃N₄ 颗粒增强体的结构特点及等温化学气相法( ICVI) 的工艺特点, 对Si₃N₄ 颗粒增强Si₃N₄ 复合材料的致密化过程进行了数值模拟。用球形孔隙模型表征Si₃N₄ 颗粒增强体的结构特征, 用传质连续方程表征先驱体在预制体中的浓度分布。为了检验模型的准确性和适用性, 进行了相应的实验验证。模拟结果与实验结果具有相似的致密化规律, 预测的渗透时间和孔隙率与实验结果均十分接近, 表明本文中建立的数学模型可以较好地表征Si₃N₄P / Si₃N₄ 复合材料的ICVI 过程。     

氧化石墨烯/H2O2可见光催化性能影响因素

为了研究氧化石墨烯/H₂O₂可见光催化处理含难降解有机物废水影响因素,用改进的Hummers法制备了氧化石墨烯(GO),通过扫描电镜(SEM)、电子能谱(EDS)、拉曼光谱对GO的微观形貌、成分及结构进行了表征.以甲基橙(MO)为难降解有机物代表,通过改变光照、pH值以及GO的量探究了不同条件对GO/H₂O₂复合试剂降解甲基橙的光催化效果.研究表明：GO/H₂O₂复合试剂可以通过光催化产生羟基自由基降解污染物,通过改变光照、pH值及GO的量增加自由基含量可提升催化效果; 采用GO/H₂O₂复合试剂比单独使用H₂O₂在48 h内对甲基橙的降解率可提高79.09%(pH=2).用改良的Hummers法制备GO成本较低,采用GO/H₂O₂复合试剂光催化降解甲基橙时,GO用量较少,且不产生危险废弃物,为实际应用中处理难降解有机物污水提供了一个绿色环保、节能高效的思路.     

超临界流体干燥法制备TiO2/ Fe2O3 和TiO2/ Fe2O3/ SiO2 复合纳米粒子及光催化性能

以TiCl₄ 、Fe (NO₃ )₃·9H₂O 和Na₂SiO₃19H₂O 为原料, 采用溶胶凝胶法结合超临界流体干燥法(SCFD)制备了纳米级TiO₂/ Fe₂O₃ 和TiO₂/ Fe₂O₃/ SiO₂ 复合光催化剂。以光催化降解苯酚对所得催化剂的催化活性进行了评价。结果表明, 纳米TiO₂/ Fe₂O₃ 复合粒子与单组分TiO₂ 比较, 复合粒子光催化活性高于单组分的TiO₂, 6h 苯酚降解率高达95.9 %。SiO₂ 的加入可以抑制纳米粒子粒径的长大和晶相的转变, 增强TiO₂ 纳米粒子的热稳定性。复合光催化剂中Fe₂O₃ 最佳掺入量为0.06 %, SiO₂ 最佳掺入量为10 %(摩尔分数) 。并用XRD、TEM 和FTIR 等手段进行了表征。TiO₂ 以锐钛矿型形式存在, SiO₂ 以无定性形式存在。比较了不同制备方法制得的TiO₂/ Fe₂O₃ 复合光催化剂, 得出超临界干燥法制备的光催化剂具有粒径小、比表面积大、分散性好、光催化活性高等特点。采用超临界流体干燥可直接得锐钛型纳米复合光催化剂。     

NiCo2O4/氧化石墨烯复合材料制备与电化学性能研究

为了研究NiCo₂O₄/氧化石墨烯(NiCo₂O₄/GO)复合材料的电化学性能,本文通过先水热合成前驱体再煅烧的方法制备了一系列NiCo₂O₄/GO复合材料.利用X射线衍射(XRD)、扫描电子显微镜(SEM)和电化学方法对其进行物理表征,其中以GO质量浓度为1 mg/mL悬浊液制备出的NiCo₂O₄ /GO-3复合材料呈类海胆状结构.在1 M KOH水溶液中使用循环伏安法、恒电流充/放电法和交流阻抗法研究了NiCo₂O₄/GO复合材料电化学性能.研究表明,与纯NiCo₂O₄相比,制备的NiCo₂O₄ /GO复合材料的比容量和赝电容性能均有明显提高,这主要是由于NiCo₂O₄ /GO复合材料中NiCo₂O₄与GO纳米片的相互作用形成的高孔隙率复合结构;NiCo₂O₄ /GO-3复合材料在电流密度为0.5~3.0 A/g时,比电容超过650 F/g,具有良好的倍率性能和高比容量.采用本文方法合成的NiCo₂O₄/GO复合材料,既提高了其倍率性能又保证了高比容量,是一种良好的超级电容器电极材料.     

等离子体电解氧化法制备多孔TiO2/V2O5复合物膜层及其增强光催化产氢活性

较差的光催化产氢效率极大地阻碍了TiO₂光催化剂的工业化应用。为此,本文在含有NH₄VO₃的磷酸盐溶液中,采用等离子体电解氧化(PEO)法制备了多孔TiO₂/V₂O₅复合膜光催化剂,通过扫描电子显微镜(SEM)、能谱仪(EDS)、X射线衍射(XRD)、X射线光电子谱(XPS)和紫外可见漫反射光谱(UV-Vis DRS)对其组成、结构及光吸收性质进行了表征,并采用气相色谱评价了薄膜催化剂的光催化产氢性能,研究了电解液中NH₄VO₃含量对膜的结构、组成和光催化产氢性能的影响。结果表明:复合膜催化剂主要由锐钛矿和金红石型TiO₂组成,具有微孔结构,V₂O₅主要以无定形形式存在于膜中,与TiO₂有很强的相互作用,影响TiO₂的晶面间距。研究发现,元素V抑制了TiO₂的结晶和金红石型TiO₂的形成,扩大了薄膜的光学吸收范围。针对Na₂S+ Na₂SO₃溶液中的光催化产氢性能的研究显示,在质量浓度为1 g/L NH₄VO₃的电解液中制备的TiO₂/V₂O₅薄膜的光催化活性最高,优于近年来报道的其他光催化剂。光催化重复实验表明,该复合膜催化剂具有较高的稳定性和较为恒定的光催化活性。     

一维TiO2纳米材料的制备及其光催化性能研究

采用水热法,通过改变水热温度成功制备出一系列一维TiO₂纳米管、纳米线和纳米带。运用X射线衍射、透射电子显微镜、N₂吸附-脱附和紫外-可见光谱等手段表征了材料的结构和性质,并考察了一维TiO₂样品光催化降解气相苯的活性。结果表明,一维TiO₂纳米材料具有较高的比表面积,光吸收出现明显的“蓝移”,光催化活性较P25有所提高,其中140 ℃水热温度下制备出的TiO₂纳米管的光催化活性最佳,80 min内对气相苯的去除率为77%,终产物CO₂的浓度为625 mg/m³。     

铝酸钙基稀土荧光粉CaAl4O7∶Eu3+的制备及热稳定性研究

在目前商用白光LED的实际应用中,存在发光色温高、显色指数低及热稳定性差等问题。为了改进白光LED存在的不足,使其更适用于人类生活的需求,本文通过共沉淀法合成了一系列CaAl₄O₇∶Eu^{3+高温红光荧光粉,采用扫描电子显微镜、X射线衍射仪、能谱仪分别对样品的形态、结构、组成元素及分布进行表征,并通过荧光光谱仪对CaAl₄O₇∶Eu3+的荧光特性及热稳定性进行了研究。实验结果表明,最佳样品为CaAl₄O₇∶0.02Eu3+}。其激发光谱中,在 393及464 nm处有两个强光激发峰,分别属于⁷F₀→⁵L₆及⁷F₀→⁵D₂跃迁；在发射光谱中,最强发射峰位于612 nm,为⁵D₀→⁷F₂跃迁的窄带红光发射；最佳样品的发光具有负的热猝灭效应,其在90 ℃时发射光强度最大,此时积分荧光发射强度为30 ℃时初始值的114.5%。当测试温度升高至150 ℃时,积分荧光发射强度仍为初始值的108%；在CaAl₄O₇∶0.02Eu^{3+的原型红光LED的电致发光测试中,发射红光比随着驱动电流的增大而增大。CaAl₄O₇∶0.02Eu3+}荧光粉具有优异的高温荧光特性,满足LED对荧光粉的发光热稳定性的要求,表明其在WLEDs领域具有潜在的应用前景。     

Synthesis of Co3O4 nanoparticles via the CTAB-assisted method

Cobalt oxide (Co₃O₄) nanoparticles were successfully synthesized by the cetyltrimethylammonium bromide (CTAB)-assisted method at normal pressure for the first time. The structure and morphology of the as-prepared Co₃O₄ nanoparticles were characterized by powder X-ray diffracton (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and N₂-sorption analysis. XRD studies indicated that the as-prepared product was well-crystallized cubic phase of Co₃O₄ with a cell constant of α = 8.0722 Å. The EM images showed that the obtained Co₃O₄ sample consisted of dispersive quasi-spherical particles with the size ranged from 15 to 25 nm.     

Fabrication of Co3O4 cubic nanoframes: Facet-preferential chemical etching of Fe ions to Co3O4 nanocubes

The novel Co₃O₄ cubic nanoframes, sized in ca. 30 nm, were firstly fabricated via a facile solvothermal route. Based on the transmission electron microscopy and the powder X-ray diffraction analyses of the time-dependent products, a mechanism of facet-preferential chemical etching of Fe³⁺ ions to the pre-synthesized Co₃O₄ nanocubes is proposed for the formation of Co₃O₄ cubic nanoframes. This synthetic strategy can probably be extended to fabricate nanoframes of some other binary metal oxides, by designing similar chemical etching process.     

g-C3N4/g-C3N4 isotype heterojunction as an efficient platform for direct photodegradation of antibiotic

A visible-light-driven g-C₃N₄/g-C₃N₄ isotype heterojunction photocatalyst was synthesized by one-step thermal treatment using urea and thiourea as the precursor. The photocatalytic activity of as-prepared photocatalyst was evaluated through the degradation of rhodamine B (RhB) and tetracycline hydrochloride (TC) under the visible light irradiation. The hybrid showed enhanced photocatalytic activity in photodegradating the applied pollutants as compared with single g-C₃N₄. When the ratio of urea to thiourea was 2:1, the prepared isotype heterojunction exhibited the highest photocatalytic activity and the photodegradation rates for RhB and TC were 99.8% and 95.1% after being visible light irradiated for 1 h and 4 h respectively. The enhanced photocatalytic performance of the isotype heterojunction is ascribed to the enhanced charge separation efficiency. After being reused for 5 times, the hybrid still showed excellent recyclability and chemical stability. Furthermore, NaI, BQ and IPA were used as the sacrificial agents for studying the surface reactions in the photocatalytic process. The method used in this work provides a new pathway to achieve more efficient degradation of antibiotics and to stimulate further studies in this important field.     

Crystallinity, magnetic and electrochemical studies of PVDF/Co3O4 polymer electrolyte

Organic-inorganic nanocomposites are gaining importance in the recent times as polymer electrolyte membranes. In the present work, composites were prepared by combining nano sized Co₃O₄ and poly(vinyledene fluoride) (PVDF), using spin coating technique. The surface of the PVDF/Co₃O₄ system characterized through field emission scanning electron microscopy (FESEM) revealed a porous structure of the films. The nanoparticles tend to aggregate on the surface and inside the pores, leading to a decrease in the porosity with an increase in Co₃O₄ content. Co₃O₄ nanoparticles prohibit crystallization of the polymer. Differential scanning calorimetry (DSC) studies revealed a decrease in crystallinity of PVDF/Co₃O₄ system with an increase in the oxide content. Magnetic property studies of the composite films revealed that with an increase in Co₃O₄ content, the saturation magnetization values of the nanocomposites increased linearly, showing successful incorporation of the nanoparticles in the polymer matrix. Further, ionic conductivity of the composite films was evaluated from electrochemical impedance spectroscopy. Addition of Co₃O₄ nanoparticles enhanced the conductivity of PVDF/Co₃O₄ system.     

Novel ternary g-C3N4/Fe3O4/MnWO4 nanocomposites: Synthesis,characterization, and visible-light photocatalytic performance for environmental purposes

The g-C₃N₄/Fe₃O₄/MnWO₄ nanocomposites were prepared by a refluxing-calcination procedure. Visible-light-induced photocatalytic experiments showed that the g-C₃N₄/Fe₃O₄/MnWO₄ (10%) nanocomposite has excellent ability to degrade a range of contaminants including rhodamine B, methylene blue, methyl orange, and fuchsine, which is about 7, 10, 25, and 31 times of the g-C₃N₄ photocatalyst, respectively. Reactive species trapping experiments revealed that superoxide anion radicals play major role in the photodegradation reaction of rhodamine B (RhB). After the treatment process, the utilized photocatalyst was magnetically recovered and reused with negligible loss in the photocatalytic activity, which is vital in the photocatalytic processes. Finally, a mechanism was proposed for the enhanced interfacial carrier separation and transfer and the improved photocatalytic performance.     

Synthesis of sphere-like Co3O4 nanocrystals via a simple polyol route

A simple polyol method was developed to synthesize uniform sphere-like Co₃O₄ nanocrystals in ethylene glycol. Powder X-ray diffraction (XRD) and electron diffraction (ED) showed that the as-prepared sample was indexed as the cubic spinel structure. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) indicated that the Co₃O₄ nanocrystals were spherical with the crystallite size in the range of 90-110 nm. Infrared spectra and Raman spectra confirmed the formation of the Co₃O₄ nanocrystals. The magnetic properties of the Co₃O₄ nanocrystals were measured by using a superconducting quantum interference device (SQUID) magnetometer, which showed that the as-prepared sample exhibited a tiny hysteresis loop with the magnetization value of 2.4 emu/g and the coercivity of 110 Oe.     

Synthesis and characterization of Co3O4 hollow spheres

Co₃O₄ hollow spheres were hydrothermally prepared at 130 °C for 16 h in the presence of Poly-vinylpyrrolidone (PVP). The as-prepared products were characterized by powder X-ray diffraction (XRD), field-emission scanning electron microscope (FE-SEM), transmission electron microscopy (TEM), infrared spectrum (IR), X-ray photoelectron spectrum (XPS), and optical absorption spectrum. PVP surfactant plays important roles in the formation of Co₃O₄ hollow spheres. These Co₃O₄ hollow spheres have average diameters of ca. 350 nm, and the wall thickness around the shell is about 42 nm. The possible formation mechanism of hollow Co₃O₄ spherical structures has simply been proposed.     

Synthesis and characterization of Co3O4/RuO2 composite nanofibers fabricated by an electrospinning method

Co₃O₄-RuO₂ composite nanofibers (NFs) were synthesized by an electrospinning method and were calcinated at 400°C for 1 hr in air. Scanning electron microscopy and high-resolution transmission electron microscopy (HRTEM) examinations show that all the synthesized NFs have uniform surface morphology and their diameters are in the range of ~ 30-~70 nm. X-ray diffraction (XRD) results show that crystalline Co₃O₄ phase and RuO₂ phase coexist in the composite NF matrix which is confirmed by X-ray photoemission spectroscopy. In addition, the HRTEM energy-dispersive X-ray spectroscopy mapping results show that the Co₃O₄ and RuO₂ phases are uniformly distributed across the NF matrix.     

Preparation and characterization of new visible-light-driven BaCo0.5Nb0.5O3 photocatalyst

A new type of visible-light-driven photocatalyst BaCo_0.5Nb_0.5O₃ was successfully synthesized via a sol-gel process in this study. After heating the precursors at 1000 °C, a pure perovskite phase was obtained. The particle size and crystallinity of BaCo_0.5Nb_0.5O₃ powders markedly increased with a rise in the calcination temperature. The band gap of BaCo_0.5Nb_0.5O₃ calculated from the UV-visible spectra was found to be less than that of titania. BaCo_0.5Nb_0.5O₃ was demonstrated to have photocatalytic activity under visible light irradiation and this activity significantly depended on the synthesis temperature. The sol-gel derived powders were found to have better photocatalytic activity than the solid-state derived powders because of the reduced particle size and increased surface area.     

Synthesis and characterization of Ca3Co4O9 thin films prepared by sol-gel spin-coating technique on Al2O3(001)

Ca₃Co₄O₉ thin films are deposited on Al₂O₃(001) substrates using a sol-gel spin-coating process. X-ray diffraction shows that the film exhibits a single phase of Ca₃Co₄O₉ with the (00l) planes parallel to the film surface. The temperature dependence of magnetic susceptibility showed as expected the existence of two magnetic transitions similar to those observed in bulk samples: a ferrimagnetic and a spin-state transition around 19 and 375 K, respectively. At 5 K the magnetization curves along the c-axis of the Al₂O₃(001) show that the remanent magnetization and coercive field are close to those obtained for films grown by pulsed laser deposition, which evidences the interest to use such an easy technique to grow complex thin films oxides.