ZnIn2S4/TiO2/Ag复合光催化剂的制备及分解水制氢性能

首先采用溶剂热法将1D TiO_2纳米带均匀地穿插到片层结构组装而成的3D ZnIn_2S_4微球中,所形成的异质结构能有效抑制光生电子-空穴对。其次利用光沉积法将0D Ag纳米粒子负载在3D ZnIn_2S_4/1D TiO_2异质结构上。得益于0D Ag纳米粒子的等离子体效应及电子助催化剂作用,三元3D ZnIn_2S_4/1D TiO_2/0D Ag复合光催化剂在分解水制氢方面表现出优异的性能。在模拟太阳光照射下,ZnIn_2S_4/TiO_2/Ag复合光催化剂的产氢速率达到715μmol·g~(-1)·h~(-1),相对于ZnIn_2S_4/TiO_2、ZnIn_2S_4/P25、ZnIn_2S_4、TiO_2和P25分别提高了2.7倍、3.3倍、3.8倍、184倍和518倍。同时借助于X射线衍射、扫描电子和透射电子显微镜、X射线光电子能谱和紫外可见漫反射光谱等表征手段进一步论证了复合催化剂的优异性能。     

离子对UIO-66-2OH光催化性能的影响

实际废水中存在的离子会对有机污染物的光催化降解产生影响。以ZrCl₄和2,5-二羟基对苯二甲酸为原料,通过水热合成法成功制备了金属有机骨架材料UIO-66-2OH。通过红外（IR）、X射线粉末衍射（XRD）、X射线光电子能谱（XPS）和扫描电子显微镜（SEM）对UIO-66-2OH的结构进行表征。利用水中常见的金属阳离子和无机阴离子,探索UIO-66-2OH的光催化性能。研究发现,金属阳离子Fe³⁺和无机阴离子HCO₃^-、CO₃^2-可以加快光催化降解的速度。然而,金属离子Na⁺、K⁺、Ca²⁺、Mg²⁺、Cu²⁺和无机阴离子Cl^-、SO₄^2-、PO₄^3-会抑制光催化性能,且离子价态越高,抑制效果越明显。     

焙烧温度对Ni/CuO-ZrO2-CeO2-Al2O3催化剂在甲烷自热重整反应中积炭行为的影响

以Na₂CO₃为沉淀剂,在pH=9时,采用并流沉淀法制备了Ni/CuO-ZrO₂-CeO₂-Al₂O₃催化剂,催化剂中活性组分Ni的负载量(质量分数)为10%．采用TPO、SEM和XPS等方法研究了载体焙烧温度对催化剂积炭行为的影响．结果表明,载体焙烧温度为800 oC制备的Ni/CuO-ZrO₂-CeO₂-Al₂O₃催化剂不存在高温烧炭峰,可以避免由于积炭而降低反应的活性．反应40 h后,催化剂表面出现表面碳酸盐和非活性丝状积炭,这些物种可能会导致催化剂活性降低．     

Preparation of dendritic‐like CdS by hydrothermal method and its photocatalytic performance

In this article, dendritic‐like CdS has been prepared by a hydrothermal method using thiourea as the sulfur source, and the effects of experimental conditions on the morphologies of CdS have been investigated. The performances of CdS have been analyzed by X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and the fluorescence and photodegradation properties of CdS have also been investigated. The XRD result indicates that the dendritic‐like CdS are of hexagonal phase and they are highly crystallized. Also, the FESEM results show that the ratio of raw material affects the yield of CdS, the reaction time affects the morphology of CdS. The best morphology of CdS is dendritic structures and the length is about 6 μm. The fluorescence spectrum shows three peaks at 470 nm, 513 nm and 547 nm, which indicates that the dendritic‐like CdS mainly emits green and blue fluorescence. Moreover, the dendritic‐like CdS exhibits good photocatalytic activity and its photodegradation rate to methylene blue can reach 92%. The growth mechanism for the formation of CdS with dendritic structure is also described.     

Electrospinning synthesis and photocatalytic property of CaFe2O4/MgFe2O4 heterostructure for degradation of tetracycline

CaFe₂O₄/MgFe₂O₄ nanowires with heterostructure had been successfully synthesized by electrospinning method. The obtained samples were systematically characterized by scanning electron microscopy (SEM), X‐Ray diffraction (XRD), UV–Vis diffuse reflectance spectra (UV‐Vis DR) and Environment scanning electron microscopy (ESEM). The novel CaFe₂O₄/MgFe₂O₄ nanowires exhibit an enhanced photocatalytic activity for degrading of tetracycline (TC) under visible light. Compared with bare CaFe₂O₄ or MgFe₂O₄ samples, the prepared CaFe₂O₄/MgFe₂O₄ (Ca:Mg:Fe = 3:2:10) composited nanowires show the best photocatalytic performance with a degradation efficiency of 40% after 150 min reaction time. This enhancement is attributed to the heterostructure of CaFe₂O₄/MgFe₂O₄ nanowires, which effectively repress the recombination of photo‐generated electrons and holes. Based on heterostructure and energy band positions, the enhancement of mechanism under visible‐light enhances the photocatalytic activity.     

Noble Metals Can Have Different Effects on Photocatalysis Over Metal–Organic Frameworks (MOFs): A Case Study on M/NH2‐MIL‐125(Ti) (M=Pt and Au)

M‐doped NH₂‐MIL‐125(Ti) (M=Pt and Au) were prepared by using the wetness impregnation method followed by a treatment with H₂ flow. The resultant samples were characterized by powder X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), X‐ray absorption fine structure (XAFS) analyses, N₂‐sorption BET surface area, and UV/Vis diffuse reflectance spectroscopy (DRS). The photocatalytic reaction carried out in saturated CO₂ with triethanolamine (TEOA) as sacrificial agent under visible‐light irradiations showed that the noble metal‐doping on NH₂‐MIL‐125(Ti) promoted the photocatalytic hydrogen evolution. Unlike that over pure NH₂‐MIL‐125(Ti), in which only formate was produced, both hydrogen and formate were formed over Pt‐ and Au‐loaded NH₂‐MIL‐125(Ti). However, Pt and Au have different effects on the photocatalytic performance for formate production. Compared with pure NH₂‐MIL‐125(Ti), Pt/NH₂‐MIL‐125(Ti) showed an enhanced activity for photocatalytic formate formation, whereas Au has a negative effect on this reaction. To elucidate the origin of the different photocatalytic performance, electron spin resonance (ESR) analyses and density functional theory (DFT) calculations were carried out over M/NH₂‐MIL‐125(Ti).The photocatalytic mechanisms over M/NH₂‐MIL‐125(Ti) (M=Pt and Au) were proposed. For the first time, the hydrogen spillover from the noble metal Pt to the framework of NH₂‐MIL‐125(Ti) and its promoting effect on the photocatalytic CO₂ reduction is revealed. The elucidation of the mechanism on the photocatalysis over M/NH₂‐MIL‐125(Ti) can provide some guidance in the development of new photocatalysts based on MOF materials. This study also demonstrates the potential of using noble metal‐doped MOFs in photocatalytic reactions involving hydrogen as a reactant, like hydrogenation reactions.     

三维有序结构In掺杂TiO_2薄膜的可见光催化活性

采用自组装生长聚苯乙烯胶体模板和溶胶-凝胶法,制备出三维(3D)有序结构In掺杂TiO2(IO-TiO2-In)薄膜可见光催化剂.光催化实验证明,IO-TiO2-In薄膜降解甲醛的可见光活性是TiO2和三维有序结构TiO2(IOTiO2)薄膜的5倍.利用X射线电子衍射(XRD)谱、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)和紫外-可见(UV-Vis)漫反射吸收光谱确定了催化剂的晶相结构、表面微结构和能带结构.结果表明,IO-TiO2-In薄膜具有锐钛矿型三维有序结构,与TiO2相比,增加了比表面积,提高光的利用率;掺入的In离子在薄膜表面形成In2O3和O-In-Clx(x=1,2)物种,既增强可见光的吸收,又有效地促进了光生载流子的分离,提高了光生载流子在固/气界面参加光催化反应的利用率,使催化剂的可见光催化活性显著提高.     

光催化合成金属Ag纳米颗粒的生长机制——晶核密度控制的生长模式转换

利用AgNO3水溶液,通过严格控制TiO2薄膜的化学活性,系统研究了在TiO2表面光催化合成金属Ag纳米颗粒的生长行为。研究发现,光催化合成金属Ag纳米颗粒存在着两个完全不同的生长机制,分别对应着金属Ag纳米颗粒的各向同性和各向异性生长。当溶液浓度较低时,Ostwald熟化(OR)机制主导着金属Ag纳米颗粒的长大过程;当溶液浓度较高时,取向附生(OA)机制决定着金属Ag纳米颗粒长大成纳米片。原位消光光谱分析表明,OR机制和OA机制生长的前期具有相近消光特征,决定金属Ag纳米颗粒生长模式的关键是AgNO3溶液的浓度,更准确地说是金属Ag初级晶核的局域密度。在此基础上提出了有关光催化合成金属Ag纳米颗粒的生长模型。     

LiNbO_3不同晶面的光催化产氢性能

研究了LiNbO3(001)、(100)和(110)晶面的光催化产氢性能。(001)、(100)和(110)3个晶面光催化产氢性能之比为7.8∶1.3∶1.0。LiNbO3[001]晶向存在电偶极矩和自发极化,有利于增加光生电子和空穴的分离效率,减少光生电子和空穴的复合,提高LiNbO3(001)面的光催化活性。LiNbO3(001)面的空穴有效质量最小,有利于光生空穴的迁移,从而减少光生电子和空穴的复合,也有利于光催化性能的提高。     

Modelling of a tubular solid oxide fuel cell with different designs of indirect internal reformer

The cell performance and temperature gradient of a tubular solid oxide fuel cell with indirect internal reformer(IIR-SOFC) fuelled by natural gas, containing a typical catalytic packed-bed reformer, a catalytic coated wall reformer, a catalytic annular reformer, and a novel catalytic annular-coated wall reformer were investigated with an aim to determine the most efficient internal reformer system. Among the four reformer designs, IIR-SOFC containing an annular-coated wall reformer exhibited the highest performance in terms of cell power density(0.67 W cm-2)and electrical efficiency(68%) with an acceptable temperature gradient and a moderate pressure drop across the reformer(3.53×10-5kPa).IIR-SOFC with an annular-coated wall reformer was then studied over a range of operating conditions: inlet fuel temperature, operating pressure, steam to carbon(S : C) ratio, gas flow pattern(co-flow and counter-flow pattern), and natural gas compositions. The simulation results showed that the temperature gradient across the reformer could not be decreased using a lower fuel inlet temperature(1223 K–1173 K)and both the power density and electrical efficiency of the cell also decreased by lowering fuel inlet temperature. Operating in higher pressure mode(1-10 bar) improved the temperature gradient and cell performance. Increasing the S : C ratio from 2 : 1 to 4 : 1 could decrease the temperature drop across the reformer but also decrease the cell performance. The average temperature gradient was higher and smoother in IIR-SOFC under a co-flow pattern than that under a counter-flow pattern, leading to lower overpotential and higher cell performance. Natural gas compositions significantly affected the cell performance and temperature gradient. Natural gas containing lower methane content provided smoother temperature gradient in the system but showed lower power density and electrical efficiency.