水热法制备Bi2O3纳米片及其电化学性能的研究

以Bi(NO₃)₃和氨水为原料、水溶性淀粉为分散剂, 采用水热法制备了Bi₂O₃纳米片, 用X射线衍射(XRD)、扫描电子显微技术(SEM)和氮气吸附-脱附等对材料进行了表征. 结果表明Bi₂O₃纳米片厚度分布比较窄, 比表面积达到9.26 m²/g. 同时, 采用循环伏安法和充放电仪测试了Bi₂O₃纳米片的电化学性能, 结果显示其具有一定的电化学活性.     

沉淀法制备Bi2O3的晶相转变过程及其光催化性能

以硝酸铋为原料,氨水为沉淀剂,通过液相沉淀法制得前驱体Bi(OH)₃,并将Bi(OH)₃分别在不同温度和时间下焙烧。利用X射线衍射(XRD)、拉曼光谱、热重(TG)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)及紫外-可见漫反射光谱(UV-Vis DRS)详细研究了Bi(OH)₃转变为Bi₂O₃的过程及相变过程中粒子形貌、大小、光吸收性质等。结果表明,前驱体Bi(OH)₃经过焙烧之后,发生了如下的转变过程:Bi(OH)₃→Bi₅O₇NO₃→β-Bi₂O₃/Bi₅O₇NO₃→β-Bi₂O₃/Bi₅O₇NO₃/α-Bi₂O₃→α-Bi₂O₃,而且转变过程伴随着粒子长大。在上述转变过程中,与Bi₅O₇NO₃向β-Bi₂O₃转变的过程相比,从β-Bi₂O₃到α-Bi₂O₃相变过程更为迅速。此外,以光催化降解罗丹明B(RhB)为模型反应,考察了不同晶相的Bi₂O₃光催化活性,结果表明Bi₅O₇NO₃和β-Bi₂O₃材料具有优异的光催化性能,而α-Bi₂O₃具有较低的光催化活性。     

富含光诱导氧空位Bi12O17Br2的制备及其高效光催化固氮性能

采用一步水热法制备了Bi₁₂O₁₇Br₂光催化剂,其平均微片尺寸为1.2μm,比表面积约为29 m²·g^-1。Bi₁₂O₁₇Br₂的禁带宽度为2.42 eV,能够响应可见光。值得注意的是,在光照条件下Bi₁₂O₁₇Br₂表面能够产生氧空位;光诱导氧空位不仅能促进氮气在催化剂表面的吸附,而且对吸附的氮气分子的活化起到至关重要的作用。实验结果表明在可见光照射下,Bi₁₂O₁₇Br₂光催化剂上的氨生成速率为337.6μmol·g^-1·h^-1。在可见光的驱动下,Bi₁₂O₁₇Br₂光催化剂能够实现氮气与水反应生成氨的过程。     

Bi2Ti2O7/TiO2/Bi4Ti3O12多异质结的构筑及其增强的可见光催化性能

以静电纺丝技术制备的TiO₂纳米纤维为基质,硝酸铋为铋源,KOH为矿化剂,成功制备了多异质结Bi₂Ti₂O₇/TiO₂/Bi₄Ti₃O₁₂复合纳米纤维光催化剂。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外可见漫反射光谱(UV-Vis DRS)等一系列表征,对其物相组成、微观形貌和光学性质等进行分析。结果表明：TiO₂纳米纤维的介入,将Ⅰ型异质结Bi₂Ti₂O₇/Bi₄Ti₃O₁₂分离为2个Ⅱ型异质结Bi₂Ti₂O₇/TiO₂和Bi₄Ti₃O₁₂/TiO₂。Bi₂     

光还原法合成Pt/Fe2O3/氮掺杂还原氧化石墨烯催化剂及其抗烧结性能

采用静电纺丝法获得的多孔Fe₂O₃纳米棒与氮掺杂还原氧化石墨烯(N?RGO)的复合材料作为载体,通过光还原法成功制备清洁、高活性的Pt/Fe₂O₃/N?RGO催化剂,并进一步研究其中的光还原反应机理和催化剂的抗烧结性能。研究结果表明,在可见光照射下,Fe₂O₃对光的强吸收作用促使光生电子和空穴的产生,N?RGO有效延长光生载流子的寿命,使得电子从O^2-转移到Fe³⁺。Fe₂O₃/N?RGO中部分还原的Fe²⁺具有较强的还原能力,可使PtCl₆^2-在Fe₂O₃表面还原并迅速成核,生长为粒径约2.13 nm的Pt纳米颗粒。此外,甲醇作为空穴清除剂可以快速有效地消耗掉扩散到载体表面的光生空穴,使导带中积累的电子与PtCl₆^2-发生还原反应,从而提高Pt纳米颗粒的光还原速率。电纺Fe₂O₃纳米棒独特的粗糙表面为Pt纳米颗粒异相成核提供了大量活性位点。富含点缺陷的N?RGO片层能缩短Fe₂O₃的光生载流子扩散路径,提高光沉积的效率;同时,其特征褶皱结构可以作为物理屏障,防止Pt纳米颗粒聚集。得益于金属与载体间的强相互作用,在500℃高温老化后,Pt纳米颗粒仍能维持较小的尺寸(2.67 nm),表现出优良的抗烧结性能。在对硝基苯酚加氢反应中,Pt/Fe₂O₃/N?RGO在400℃老化后仍具有高达22.2 L·g^-1·s^-1的反应速率常数,约为老化前的1.6倍。     

Y2O3/TiO2 "核-壳"结构在染料敏化太阳电池中的应用

在纳米TiO₂多孔薄膜表面包覆超薄绝缘体,形成"核-壳"结构的势垒层,是目前染料敏化太阳电池（DSC）光阳极改性的研究热点之一.本文选取氧化钇（Y₂O₃）作为包覆层材料,采用浸渍法对纳米TiO₂多孔薄膜进行修饰,研究Y₂O₃包覆处理对TiO₂薄膜微观结构及能带结构的影响;将浸渍法制备得到的Y₂O₃/TiO₂"核-壳"结构光阳极应用于DSC中,研究了饣覆层对电子传输复合以及DSC光电转换性能的影响.结果表明,Y₂O₃包覆处理后,薄膜的平带电势负移,且电子复合得到有效抑制,电子寿命增大,电池的开路电压明显提高.研究表明,适量引入Y₂O₃可以达改善电池性能的目的.     

PO43-掺杂Bi2O2CO3/Bi0的制备及其可见光催化性能

构建氧空位以及附着金属单质Bi(Bi⁰)是增强半导体材料光吸收性能、促进半导体光生载流子分离的有效方法。通过简单的共沉淀法及氢气热还原成功制备了PO₄^3-掺杂Bi₂O₂CO₃附着Bi⁰(Bi-P-BOC)的可见光催化剂,并对其在可见光下催化降解氧氟沙星(OFX)的性能及机理进行了研究。材料表征结果表明BOC随着PO₄^3-的均匀掺杂,可见光吸收能力增强,表面缺陷增多,比表面积增大。而随着氢气热还原,BOC表面形成Bi⁰的同时也原位构建了大量的氧空位。可见光催化性能测试表明,Bi-P-BOC可以在180 min内降解约85%的OFX,降解速率为0.013 0 min^-1,是BOC降解速率的8倍。Bi-P-BOC光催化降解机理表明其具有更好的可见光吸收能力,Bi⁰以及氧空位的存在促进了光生载流子的分离,h⁺是其...     

CuWO4-x/Bi12O17Cl2梯型异质结增强PMS活化性能用于高效抗生素去除(英文)

利用光催化剂中产生的光生电荷活化过一硫酸盐(PMS)用于抗生素等污染物的去除,由于结合了光催化反应和PMS活化的独特优势,近年来引起了广泛的关注。然而,对于单一光催化剂,严重的光生电子空穴对的复合限制了其活化PMS的效率。于此,本文构建了CuWO_4-x/Bi₁₂O₁₇Cl₂光催化剂,通过梯型异质结促进电荷分离,实现高效PMS活化。通过X射线衍射仪技术(XRD)、高分辨透射电子显微镜(TEM)、傅里叶变换红外光谱(FTIR)和紫外-可见漫反射光谱(UVVis)等分析手段对所制备催化剂的形貌和结构进行了详细的表征。另外,通过在可见光照射下降解四环素(TC),系统地研究了CuWO_4-x/Bi₁₂O₁₇Cl₂的催化活性。结果发现,与CuWO_4-x和Bi₁₂O₁₇Cl₂相比,CuWO_4-x/Bi₁₂     

Cu、Mn、Ce改性V2O5-WO3/TiO2/堇青石催化剂Urea-SCR脱除NO

采用硅胶为黏结剂,在堇青石蜂窝陶瓷上以涂覆法依次负载Cu、Mn、Ce改性的纳米TiO₂粉末、W改性的V₂O₅粉末得到复合催化剂,在120～550 ℃用尿素选择性催化还原(Urea-SCR)氮氧化物时显示良好活性。与商业催化剂V₂O₅-WO₃/TiO₂相比,添加Cu、Mn、Ce后,催化剂脱硝活性显著提高,活性温度窗口明显拓宽。结果表明,催化剂的高活性与催化剂表面适度的酸碱性、高比值的V⁴⁺/V⁵⁺以及良好的氧化还原性能和锐钛矿相的TiO₂、丰富的表面裂纹的存在等因素有关。     

TiO2/石墨烯复合材料的光生电荷分离调控与光催化产氢性能研究

半导体光生电荷分离是光催化过程中的关键步骤之一,其效率极大地影响了最终光催化性能.将TiO₂纳米片与石墨烯复合,能够促进TiO₂中光生电子和空穴的分离,从而提高其光催化活性.为了研究光生电荷的分离对TiO₂/石墨烯复合材料光催化性能的影响,通过调控TiO₂纳米片的尺寸来调节TiO₂/石墨烯复合材料中光生电荷分离的能力,然后研究其对TiO₂/石墨烯复合材料光催化性能的影响.合成了一系列不同厚度的TiO₂纳米片,将其与石墨烯复合,并通过光沉积负载Pt纳米颗粒作为助催化剂,用于光催化产氢.实验结果显示,随着TiO₂纳米片厚度减小,其与石墨烯形成的复合结构的光催化性能显著提高.这主要是由于TiO₂纳米片厚度减小时,光生电子沿厚度方向穿过TiO₂纳米片迁移到石墨烯的距离缩短,从而减少了光生电子在迁移过程中与空穴的复合;同时TiO₂纳米片厚度减小使其比表面积增大,使得TiO₂/石墨烯界面面积增大,从而使石墨烯更好地分离出TiO₂中的光生电子,有更多的光生电子到达石墨烯参与催化反应,提高TiO₂/石墨烯复合材料的光催化性能.此研究表明通过控制TiO₂纳米片的尺寸来调控TiO₂/石墨烯复合材料中光生电子和空穴的分离,是显著提高其光催化性能的有效途径.     

高催化活性2D/2D Ti3C2/Bi4O5Br2纳米片异质结的构建及其可见光催化去除NO

This study concentrated on the production of a two-dimensional and two-dimensional (2D/2D) Ti₃C₂/Bi₄O₅Br₂ heterojunction with a large interface that applied as one of the novel visible-light-induced photocatalyst via the hydrothermal method. The obtained photocatalysts enhanced the photocatalytic efficiency of the NO removal. The crystal structure and chemical state of the composites were characterized using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results showed that Ti₃C₂, Bi₄O₅Br₂, and Ti₃C₂/Bi₄O₅Br₂ were successfully synthesized. The experimental results of scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that the prepared samples had a 2D/2D nanosheet structure and large contact area. This structure facilitated the transfer of electrons and holes. The solar light absorptions of the samples were evaluated using the UV-Vis diffuse reflectance spectra (UV-Vis DRS). It was found that the absorption band of Ti₃C₂/Bi₄O₅Br₂ was wider than that of Bi₄O₅Br₂. This represents the electrons in the Ti₃C₂/Bi₄O₅Br₂ nanosheet composites were more likely to be excited. The photocatalytic experiments showed that the 2D/2D Ti₃C₂/Bi₄O₅Br₂ composite with high photocatalytic activity and stability. The photocatalytic efficiency of pure Bi₄O₅Br₂ for the NO removal was 30.5%, while for the 15%Ti₃C₂/Bi₄O₅Br₂ it was 57.6%. Moreover, the catalytic reaction happened in a short period. The concentration of NO decreased exponentially in the first 5 min, which approximately reached the final value. Furthermore, the stability of 15%Ti₃C₂/Bi₄O₅Br₂ was favorable: the catalytic rate was approximately 50.0% after five cycles of cyclic catalysis. Finally, the scavenger experiments, electron spin resonance spectroscopy (ESR), transient photocurrent response, and surface photovoltage spectrum (SPS) were applied to analyze the photocatalytic mechanism of the composite. The results indicated that the 2D/2D heterojunction Ti₃C₂/Bi₄O₅Br₂ improved the separation rate of the electrons and holes, thus enhancing the photocatalytic efficiency. In the photocatalytic reactions, the photogenerated electrons (e⁻) and superoxide radical (·O₂⁻) were critical active groups that had a significant role in the oxidative removal of NO. The in situ Fourier-transform infrared spectroscopy (in situ FTIR) showed that the photo-oxidation products were mainly NO₂⁻ and NO₃⁻. Based on the above experimental results, a possible photocatalytic mechanism was proposed. The electrons in Bi₄O₅Br₂ were excited by visible light. They jumped from the valence band (VB) of Bi₄O₅Br₂ to the conduction band (CB). Then, the photoelectrons transferred from the CB of Bi₄O₅Br₂ to the Ti₃C₂ surface, which significantly promoted the separation of the electron-hole pairs. Therefore, the photocatalytic efficiency of Ti₃C₂/Bi₄O₅Br₂ on NO was significantly improved. This study provided an effective method for preparing 2D/2D Ti₃C₂/Bi₄O₅Br₂ nanocomposites for the photocatalytic degradation of environmental pollutants, which has great potential in solving energy stress and environmental pollution.     

微波液相法一步合成H3PW12O40/Bi2WO6光催化剂及其脱氮性能

采用微波液相法一步合成了固载型H₃PW₁₂O₄₀/Bi₂WO₆光催化剂. 通过紫外-可见漫反射光谱(UV-Vis)、 场发射扫描电子显微镜(SEM)、 表面积及孔隙度(BET)测定、 氨气程序升温脱附(NH₃-TPD)、 吡啶吸附红外光谱(Py-FTIR)和X射线衍射(XRD)对所合成催化剂的结构和性质进行了考察, 并以吡啶浓度为15 mg/g的模拟油对光催化剂的脱氮效果进行评价. 结果表明, 与传统浸渍固载法相比, 微波液相一步法不仅能高效合成H₃PW₁₂O₄₀/Bi₂WO₆光催化剂, 且所合成的催化剂能被低能量的光激发. 固载H₃PW₁₂O₄₀不但能提高Bi₂WO₆纳米颗粒的表面酸量, 还能通过改变Bi₂WO₆前驱液的酸强度来调控催化剂形貌. 在H₃PW₁₂O₄₀固载量为15%(质量分数), 微波功率为800 W, 反应时间为90 min条件下得到的H₃PW₁₂O₄₀/Bi₂WO₆的光催化脱氮活性最高, 在催化剂与模拟油质量比为1/300, 500 W氙灯光照60 min的最佳光催化反应条件下, 模拟油脱氮率达到92.63%.     

Synthesis and study of Bi2Ti2O7/TiO2 composites as efficient visible-light-active photocatalysts in the reduction of aqueous Cr(VI)

In this work, Bi_2Ti_2O_7/TiO_2 composites were synthesized and studied as potential visible-light-activated photocatalysts in the reduction of aqueous Cr(VI). Bi_2Ti_2O_7/TiO_2 composites with tunable compositions were synthesized via a solvothermal-calcination two-step method, simply by changing the molar ratios of Bi(NO_3)_3·5H_2O to tetrabutyl titanate in the reactants. The compositions, structures and optical properties of the as-synthesized Bi_2Ti_2O_7/TiO_2 composites were characterized by X-ray diffraction, field emission scanning electron microscopy and UV–vis diffuse reflectance spectra. The photocatalytic activity of the as-synthesized Bi_2Ti_2O_7/TiO_2 composites was tested in the reduction of aqueous Cr(VI)under visible-light(λ420 nm) irradiation, and compared with that of TiO_2 nanoparticles. It was observed that the as-synthesized Bi_2Ti_2O_7/TiO_2 composites exhibited much higher photocatalytic activity than TiO_2 nanoparticles, and the most efficient composite(300 mg) can achieve the complete reduction of Cr(VI) in 300 mL of 50 mg/L K_2Cr_2O_7 aqueous solution under visible-light(λ420 nm)irradiation in 90 min.     

Tunable Synthesis of Core-shell α-Fe2O3/TiO2 Composite Nanoparticles and Their Visible-light Photocatalytic Activity

Uniform α-Fe₂O₃/amorphous TiO₂ core-shell nanocomposites were prepared via a hydrolysis method and α-Fe₂O₃/anatase TiO₂ core-shell nanocomposites were obtained via a post-calcination process. The structure and morphology of the products were characterized by powder X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and scanning electron microscopy. Amorphous TiO₂ nanoparticles with diameters of ten to several tens nanometer were formed on the surface of α-Fe₂O₃ nanoparticles and the coverage density of the secondary TiO₂ nanoparticles in the composite can be controlled by varying the concentration of Ti(BuO)₄ in the ethanol solution. The visible-light photocatalytic properties of different products towards Rhodamine B(RhB) were investigated. The results show that the α-Fe₂O₃/amorphous TiO₂ exhibits a good photocatalytic property owing to the extension of the light response range to visible light and the efficient separation of photogenerated electrons and holes between α-Fe₂O₃ and amorphous TiO₂.     

超临界水热极速合成异质结构H4SiW12O40/Bi2WO6光催化剂及其脱氮性能

采用超临界水热合成方式极速合成一种H_4SiW_(12)O_(40)/Bi_2WO_6光催化剂,通过X射线衍射(XRD)、场发射扫描电子显微镜(SEM)、透射电子显微镜(TEM)、比表面积及孔隙度(BET)测定对所合成催化剂的结构和性质进行了考察,并以吡啶含量为15 mg/g的模拟油对光催化剂的脱氮效果进行评价。结果表明,该光催化剂为二维纳米片自组装成的三维球状结构,其中,H_4SiW_(12)O_(40)与Bi_2WO_6不是简单的固载关系而是在超临界水热条件下生成一种新的晶相,正是由于这种晶相的存在,使得H_4SiW_(12)O_(40)牢固固载在Bi_2WO_6光催化剂本体上的同时,对光生载流子进行了有效疏导,提升了H_4SiW_(12)O_(40)/Bi_2WO_6光催化剂的使用寿命和光催化活性。本研究针对光催化剂制备周期与晶形发育的矛盾,将超临界水热技术与光催化剂模板导向合成技术有机结合,在获得良好晶形异质结构H_4SiW_(12)O_(40)/Bi_2WO_6光催化剂的同时明显缩短了光催化剂的制备周期,从而降低了催化剂的制备成本,攻克了光催化剂工业化应用的主要矛盾,所制备的H_4SiW_(12)O_(40)/Bi_2WO_6光催化剂轻质油脱氮效率达97%以上。     

光催化氧气还原制备H2O2

H₂O₂广泛应用于化工和环保领域,其分解的唯一产物是水,有利于生产与自然生态系统的协调可持续发展。工业上H₂O₂的合成主要是通过蒽醌法间接合成,该方法能耗大,污染环境。而直接由H₂与O₂混合制备H₂O₂,具有极大的安全风险,且需要消耗大量H₂。通过光催化技术将O₂和H₂O转化成H₂O₂的方法,避免了H₂与O₂的直接混合,同时采用取之不尽的太阳能作为能量来源,近年来备受关注。本文总结了光催化还原O₂制备H₂O₂的研究进展,对比分析了不同催化体系,如g-C₃N₄、TiO₂以及其他光催化剂的反应性能及调控措施,介绍了光催化制备H₂O₂的机理,并对该领域的发展进行了展望。     

Au/TiO_2/MoS_2等离子体复合光催化剂的制备及其增强光催化产氢活性

采用尿素沉积法制备了Au/Ti O_2/Mo S_2等离子体复合光催化剂。通过光催化产氢实验,在10%(φ,体积分数)甘油水溶液为牺牲剂条件下,研究了不同Mo S_2含量、Au固载2%(w,质量分数)时,Au/Ti O_2/Mo S_2(ATM)复合样品的光催化产氢活性。结果表明,当Mo S_2含量为0.1%(w)时,复合样品ATM0.1显示出最高的光催化产氢活性,其产氢速率达到708.85μmol·h~(-1),是Ti O_2/Mo S_2(TM)两相复合样品中光催化活性最高样品TM6.0产氢速率的11倍。三相复合样品显示增强光催化产氢活性主要是由于吸附在Ti O_2/Mo S_2层状复合材料上的Au纳米颗粒具有表面等离子共振效应,能强烈吸收波长范围550–560 nm的可见光,诱导产生光生电子,金纳米颗粒上的电子受到激发后转移到Ti O_2导带上,Ti O_2导带上的电子传递给片状Mo S_2,最终在Mo S_2上催化氢气产生。     

羧基功能化石墨烯增强TiO2光催化产氢性能

The use of semiconductor photocatalysts (CdS, g-C₃N₄, TiO₂, etc.) to generate hydrogen (H₂) is a prospective strategy that can convert solar energy into hydrogen energy, thereby meeting future energy demands. Among the numerous photocatalysts, TiO₂ has attracted significant attention because of its suitable reduction potential and excellent chemical stability. However, the photoexcited electrons and holes of TiO₂ are easily quenched, leading to limited photocatalytic performance. Furthermore, graphene has been used as an effective electron cocatalyst in the accelerated transport of photoinduced electrons to enhance the H₂-production performance of TiO₂, owing to its excellent conductivity and high charge carrier mobility. For an efficient graphene-based photocatalyst, the rapid transfer of photogenerated electrons is extremely important along with an effectual interfacial H₂-production reaction on the graphene surface. Therefore, it is necessary to further optimize the graphene microstructures (functionalized graphene) to improve the H₂-production performance of graphene-based TiO₂ photocatalysts. The introduction of H₂-evolution active sites onto the graphene surface is an effective strategy for the functionalization of graphene. Compared with the noncovalent functionalization of graphene (such as loading Pt, MoS_x, and CoS_x on the graphene surface), its covalent functionalization can provide a strong interaction between graphene and organic molecules in the form of H₂-evolution active sites that are produced by chemical reactions. In this study, carboxyl-functionalized graphene (rGO-COOH) was successfully modified via ring-opening and esterification reactions on the TiO₂ surface by using an ultrasound-assisted self-assembly method to prepare a high-activity TiO₂/rGO-COOH photocatalyst. The Fourier transform infrared (FTIR) spectra, X-ray photoelectron spectroscopy (XPS), and thermogravimetric (TG) curves revealed the successful covalent functionalization of GO to rGO-COOH by significantly enhanced ―COOH groups in FTIR and increased peak area of carboxyl groups in XPS. A series of characterizations, including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), XPS, and UV-Vis adsorption spectra, were performed to demonstrate the successful synthesis of TiO₂/rGO-COOH photocatalysts. The experimental data for the hydrogen-evolution rate showed that the TiO₂/rGO-COOH displayed an extremely high hydrogen-generation activity (254.2 μmol∙h⁻¹∙g⁻¹), which was 2.06- and 4.48-fold higher than those of TiO₂/GO and TiO₂, respectively. The enhanced photocatalytic activity of TiO₂/rGO-COOH is ascribed to the carboxyl groups of carboxyl-functionalized graphene, which act as effective hydrogen-generation active sites and enrich hydrogen ions owing to their excellent nucleophilicity that facilitates the interfacial hydrogen production reaction of TiO₂. This study provides novel insights into the development of high-activity graphene-supported photocatalysts in the hydrogen-generation field.