Effect of Zr–Al Co-Doping on Structure and Photocatalytic Performance of ZnO Photocatalyst

利用水热处理结合焙烧的方法分别制备了Zr、Al掺杂及Zr–Al共掺的ZnO光催化剂。研究了制备的光催化剂样品的相结构和光谱性能;以紫外光（λ=254nm）为光源,酸性橙Ⅱ为降解对象,进行光催化活性测试;考察了Zr、Al掺杂对ZnO光催化剂反应活性的影响。研究表明,制备的产物均为六方晶系纤锌矿结构的ZnO;Zr、Al掺杂及Zr–Al共掺的ZnO样品的光催化活性相对于纯ZnO均有较大程度的提高,而且Zr–Al共掺的ZnO的光催化性能明显优于单一掺杂的。Zr–Al共掺可以明显改善ZnO表面状态,使ZnO具有更丰富的表面羟基,同时可以抑制光生电子–空穴对的复合,从而有利于光催化活性和稳定性的提高。     

掺杂金属离子对纳米ZnO光催化活性的影响

采用沉淀法制备纳米ZnO催化剂,并通过掺杂金属离子的方法对其进行改性。以紫外光照下降解甲基橙溶液为探针反应评价其光催化活性。结果表明,掺杂5%的铝明显提高了ZnO光催化剂的活性,比商业生产的TiO2的光催化活性高很多。结合X射线粉末衍射(XRD)和扫描电子显微镜(SEM)表征结果,发现离子掺杂的ZnO光催化剂的催化性能与ZnO晶粒大小和掺杂离子的分散性有密切关系,即ZnO晶粒尺寸越小和掺杂离子的分散性越好,所制备的离子掺杂ZnO的光催化性能越高。     

稀土掺杂对ZnO材料结构及光催化性能的影响研究

为提高ZnO光催化性能采用超声波辅助微波水热法分别制备了ZnO、Nd/ZnO及Dy/ZnO光催化材料,利用XRD、SEM、FESEM、XPS及亚甲基蓝降解实验对样品的结构与性能进行了表征.研究表明:掺杂Nd及Dy有助于促进六方纤锌矿结构ZnO晶体的生长.与纯ZnO相比,掺杂Nd及Dy促进了样品表面羟基化及氧的吸附,从而提高了ZnO的光催化活性.采用超声波辅助微波水热法制备的样品光催化性能优异,紫外光辐照4h后,ZnO、Nd/ZnO、Dy/ZnO样品对亚甲基蓝的降解率分别为89.69％,91.01％,91.13％.     

Fe3+、Si4+共掺杂TiO2光催化性能研究

采用溶胶-凝胶法制备了Fe/Ti/Si复合光催化剂,通过对甲基橙的降解来研究其光催化活性.结果表明,Fe的掺杂提高了光催化剂的光响应范围,可以充分地利用太阳光,Fe最佳掺量为3.5×10-6mol/g;适量掺杂SiO2增强了光催化剂的热稳定性,其最佳掺量为15%;Fe、Si共掺杂TiO2在脱色过程中产生了协同作用,提高了催化剂的光催化活性.     

铝掺杂纳米ZnO颗粒光催化降解活性艳蓝X-BR

以乙酸锌[Zn(CH3COO)2·2H2O]、氢氧化锂(LiOH·H2O)和氯化铝(AlCl3·6H2O)为原料,采用溶胶-凝胶法制备了纯纳米ZnO和掺铝ZnO,并用X射线衍射光谱、傅立叶红外光谱、紫外-可见吸收光谱、X射线光电子能谱和高分辨率透射电子显微镜对其进行了表征. 用紫外灯作为光源,活性艳蓝XB-R溶液为光催化反应模型降解物,研究了ZnO及掺铝ZnO的光催化性能,并考察了前驱体焙烧温度、光催化温度、光照时间、底物浓度、光催化剂的暗吸附性能、铝掺杂量以及催化剂的加入量等因素对降解率的影响. 结果表明,焙烧温度300℃时,晶粒结晶良好,粒径小;掺杂铝离子提高了ZnO的光催化活性,掺杂铝离子浓度为5%(摩尔比)的ZnO的光催化性能最好;掺杂后的样品粒度分布更均匀,且明显变小;在30℃下,加入催化剂浓度为0.1 g/L、降解时间为45 min时,对活性艳蓝XB-R溶液的降解率达到95%.     

ZnO磁性纳米材料的制备以及光催化性能的研究

用一个简单的方法将Fe与ZnO掺杂,并研究了它的光催化性能。通过球磨机制备出高效率降解甲基橙的光催化剂,一部分归因于ZnO掺杂了Fe,一部分则是由于在高速研磨下样品颗粒尺寸变小,氧化锌纳米颗粒的反应速度约为普通氧化锌颗粒100~1000倍,尺寸越小光催化效果越明显[1]。而且通过球磨机掺杂制备的光催化剂可以循环使用。     

La-N共掺杂改性TiO_2光催化性能研究

用溶胶-凝胶法制备了La、N共掺杂的TiO2光催化剂,以甲基橙为模拟污染物,考察了其光催化活性。结果表明,La-N共掺杂TiO2光催化剂与单掺N的TiO2以及纯TiO2相比,光催化活性有明显提高,当煅烧温度为600℃,添加La的摩尔分数为0.10%时,光催化活性最佳。     

V、La共掺杂对纳米TiO2光催化降解甲基橙的研究

采用Sol-gel法制备了V-La共掺杂纳米TiO2光催化剂,XRD结果表明,制备的催化剂为锐钛矿型.以甲基橙水溶液为模拟对象,分别从光照时间、催化剂用量、酸度大小三个方面考察了复合光催化剂的光催化活性,结果表明,V-La共掺杂纳米TiO2光催化剂的光催化活性均高于单掺或不掺杂催化剂.     

稀土元素Pr掺杂对ZnO材料结构及光催化性能的影响

采用溶胶-凝胶法制备了稀土元素Pr掺杂的纳米ZnO光催化剂,利用XRD、SEM、EDS及亚甲基蓝降解实验对样品的结构与性能进行了表征和测试。研究表明,与纯ZnO相比,掺杂Pr能有效促进ZnO的晶粒细化,稀土元素Pr以Pr_2O_3化学态形式高度分散在ZnO表面,增加了催化剂表面氧空位,改变了ZnO的晶格缺陷和光吸收范围,明显提高了ZnO的光催化性能。在摩尔比n(Pr)∶n(ZnO)=0.03∶0.97时,制得样品Zn_(0.97)Pr_(0.03)O的光催化性能最好,紫外灯照射150 min后,对亚甲基蓝的降解率为94.5%,比纯ZnO的降解效率提高了32.5%,对苯酚溶液和间苯二酚溶液的降解效率分别为82.2%,91.5%。     

稀土元素Pr掺杂对ZnO材料结构及光催化性能的影响

采用溶胶-凝胶法制备了稀土元素Pr掺杂的纳米ZnO光催化剂,利用XRD、SEM、EDS及亚甲基蓝降解实验对样品的结构与性能进行了表征和测试。研究表明,与纯ZnO相比,掺杂Pr能有效促进ZnO的晶粒细化,稀土元素Pr以Pr_2O_3化学态形式高度分散在ZnO表面,增加了催化剂表面氧空位,改变了ZnO的晶格缺陷和光吸收范围,明显提高了ZnO的光催化性能。在摩尔比n(Pr)∶n(ZnO)=0.03∶0.97时,制得样品Zn_(0.97)Pr_(0.03)O的光催化性能最好,紫外灯照射150 min后,对亚甲基蓝的降解率为94.5%,比纯ZnO的降解效率提高了32.5%,对苯酚溶液和间苯二酚溶液的降解效率分别为82.2%,91.5%。     

Zr掺杂g-C3N4光催化降解有机污染物

以盐酸胍为前驱体，硝酸锆为锆源，通过热聚合法制备了Zr掺杂的Zr/g-C3N4光催化剂。运用XRD、SEM、UV-Vis DRS、PL、XPS、BET等手段对催化剂的结构、形貌、光学性能进行了表征分析。结果表明：Zr掺杂改性的Zr/g-C3N4光催化剂拓宽了可见光的吸收，增大了比表面积，且降低了光生电子-空穴的复合率，具有较好的光催化活性。可见光照射下，在60 min内，5Zr/g-C3N4对罗丹明B（RhB）的光催化降解率达99.29%，光催化降解过程符合一级动力学方程，其速率常数k= 0.08647 min-1，是纯g-C3N4的8.3倍。捕获剂实验发现降解RhB的主要活性物种为超氧自由基，并推测了可能的反应机理。     

Improved photocatalytic performance of Gd and Nd co-doped ZnO nanorods for the degradation of methylene blue

This paper reports the synthesis of pure ZnO, Gd and Nd co-doped ZnO nanorods based nanocomposites via simple hydrothermal method. Subsequently, the prepared photocatalysts were characterized using XRD, SEM/EDX, TEM, UV–visible and PL spectroscopy. The XRD results demonstrate that Gd and Nd ions were incorporated into ZnO lattice in the synthesized ZnO based nanocomposites and showed hexagonal wurtzite structure. The SEM and TEM results show that nanorods having nanoscale diameter and length were successfully synthesized by hydrothermal method. The UV–visible spectroscopy verified that the band gap of ZnO was reduced due to incorporation of Gd and Nd into ZnO photocatalyst. Similarly, Gd and Nd incorporation into ZnO was found effective to reduce the recombination of electrons and holes as confirmed by PL spectroscopy. Moreover, the prepared nanocomposites with various atomic ratios (0.5–2%) were tested for photocatalytic degradation of methylene blue (MB), under visible light irradiation. The highly efficient and optimized 1.5% Nd/ZnO nanocomposite demonstrated enhanced photocatalytic performance for the degradation of methylene blue compared to pure ZnO and other nanocomposites. Furthermore, the recycling results show that the 1.5% Nd/ZnO nanocomposites displayed good stability and long-term durability. These finding suggest that the ZnO based nanocomposite could be efficiently used in various energy and environmental applications.     

ZnO/碳纳米管复合光催化材料对抗生素的光催化降解

采用溶胶法合成了ZnO/碳纳米管复合光催化材料,采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、紫外-可见漫反射吸收光谱(UV-Vis)等手段对复合催化剂进行了表征。以氙灯(250～800 nm)为光源,盐酸四环素为降解对象,评价样品的光催化活性。比较ZnO/CNTs复合材料和纯ZnO对抗生素的降解能力,并考察光催化剂的重复利用能力。结果表明,通过溶胶法得到了在碳纳米管表面均匀、致密包覆ZnO颗粒的复合材料。由于ZnO/CNTs材料良好的吸附性能,其光催化活性高于纯ZnO,在300 W氙灯光源下反应2 h,对盐酸四环素的降解率达82.38%,同时复合材料显示了抑制ZnO光蚀的能力。     

S,Fe共掺杂纳米TiO_2的制备及其光催化性能

以水热法制得了S,Fe共掺杂的纳米TiO2光催化剂(TiO2-S-Fe),XRD分析表明,其为锐钛矿晶型,S,Fe掺杂能抑制TiO2粒径的生长;UV-vis漫反射表明,TiO2-S-Fe对可见光吸收增强,吸收带边明显红移;XPS显示S,Fe共掺杂,使得TiO2表面羟基氧含量提高,从而提高催化剂活性;可见光降解甲基橙溶液结果表明,共掺杂样品光催化效果优于单掺样品,S和Fe共掺杂对提高TiO2可见光活性具有协同效应。当Fe3+∶S∶Ti(摩尔比)=0.005∶1∶1,180℃下水热反应3 h时,制得的TiO2-S-Fe可见光催化活性比纯TiO2的活性提高了约10倍。     

Attachment of ZnO nanoparticles onto layered double hydroxides microspheres for high performance photocatalysis

In this study, ZnO nanoparticles were successfully deposited on the surface of ZnMgAl–CO₃–LDHs microspheres to form ZnO/ZnMgAl–CO₃–LDHs heterojunction photocatalysts by coprecipitation process. The samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and UV–vis diffuse reflectance spectroscopy. The results show that ZnO nanoparticles with diameters about 10–80 nm are tightly grown on the nanosheets of the ZnMgAl–CO₃–LDHs microspheres. Compared with the pristine ZnMgAl–CO₃–LDHs microspheres and pure ZnO, the photocatalytic activity of the heterojunction ZnO/ZnMgAl–CO₃–LDHs photocatalyst is significantly enhanced towards the degradation of phenol under UV light irradiation. The enhancement of the photocatalytic activity of the heterojunction catalysts can be ascribed to their improved light absorption property and the lower recombination rate of the photoexcited electrons and holes during the photocatalytic reaction. The optimal molar ratio of ZnO/ZnMgAl–CO₃–LDHs for the photocatalysis is 3. The heterojunction photocatalyst ZnO/ZnMgAl–CO₃–LDHs may be a promising photocatalyst for future application in water treatment due to its excellent performance in degradation of phenol.     

Structural,optical and photocatalytic properties of hafnium doped zinc oxide nanophotocatalyst

A series of novel hafnium (Hf) doped ZnO nanophotocatalyst were synthesized using a simple sol–gel method with a doping content of up to 6 mol%. The structure, morphology and optical characteristics of the photocatalysts were characterized by XRD, SEM, TEM, FTIR, XPS, DRS and PL spectroscopy. The successful synthesis and chemical composition of pure and doped ZnO photocatalysts were confirmed by XRD and XPS. DRS confirmed that the spectral responses of the photocatalysts were shifted towards the visible light region and showed a reduction in band gap energy from 3.26 to 3.17 eV. Fluorescence emission spectra indicated that doped ZnO samples possess better charge separation capability than pure ZnO. The photocatalytic activity of Hf-doped ZnO was evaluated by the methylene blue (MB) degradation in aqueous solution under sunlight irradiation. Parameters such as irradiation time and doping content were found effective on the photoactivity of pure ZnO and Hf-doped ZnO. The photocatalysis experiments demonstrated that 2 mol% Hf-ZnO exhibited higher photocatalytic activity as compared to ZnO, ZnO commercial and other hafnium doped ZnO photocatalysts and also revealed that MB was effectively degraded by more than 85% within 120 min. The enhanced photoactivity might be attributed to effective charge separation and enhanced visible light absorption. It was concluded that the presence of hafnium within ZnO lattice could enhance the photocatalytic oxidation over pure ZnO.     

阴极电沉积制备铝掺杂ZnO薄膜及其光催化性能

以不锈钢为基体,采用阴极电沉积法,从Zn(NO3)2和Zn(NO3)2+Al(NO3)3水溶液中制备了纯ZnO薄膜和铝掺杂ZnO薄膜.用X射线衍射、 扫描电镜和紫外-可见光漫反射光谱研究了铝掺杂对ZnO薄膜相变和光催化活性的影响.结果表明:在铝掺杂ZnO薄膜中,部分Al3+进入ZnO的晶 格,形成固溶体:铝掺杂使ZnO的吸收阈值蓝移大约50nm.和纯ZnO薄膜相比,铝掺杂ZnO薄膜在紫外光和可见光区均呈现出更高的催化活性, 反应60min后.甲基橙的降解率分别提高了45%和30%.探讨了铝掺杂ZnO薄膜光催化活性提高的原因.     

微波水热法制备稀土元素铒掺杂TiO_2光催化剂及光催化活性

采用微波水热法和溶胶-凝胶法制备稀土元素Er掺杂TiO_2光催化剂TiO_2-Er,以甲基橙溶液为模拟污染物,在微波辐射-紫外光照(MW-UV)和太阳光照条件下,考察TiO_2-Er光催化剂的光催化降解活性。分别用N_2吸附-脱附、ICP-AES和PL光谱分析对TiO_2-Er光催化剂进行结构测试和表征。结果表明,Er掺杂能显著提高TiO_2光催化剂光催化活性,微波水热法制备的TiO_2-Er光催化剂具有较高的光催化活性;微波水热法和溶胶-凝胶法制备的TiO_2-Er光催化剂微波辐射-紫外光照50 min,甲基橙降解率分别为100%和98.5%,太阳光照4 h,甲基橙降解率分别为99.0%和97.5%。微波水热法具有晶化时间短和元素掺杂均匀的优点,制备的TiO_2-Er光催化剂具有形貌均匀、孔径较大、孔分布均匀和比表面积较大等特点,且Er掺杂能抑制光生e~-/h~+复合,使光生e~-/h~+的分离效率得到提高,有利于光催化活性的提高。     

Sea urchin shaped ZnO coupled with MoS2 and polyaniline as highly efficient photocatalysts for organic pollutant decomposition and hydrogen evolution

In this work, an attempt has been made to fabricate multifunctional composite photocatalysts by coupling sea urchin shaped ZnO with MoS₂ and polyaniline (PANI) sheets, and a significant improvement in photocatalytic activity was perceived with composites in comparison to pristine components. It was found that the ternary ZnO–MoS₂-PANI photocatalyst showed excellent adsorptive decomposition of organic pollutants natural sunlight irradiation. In addition, enhanced photocatalytic hydrogen evolution was also evidenced, which revealed the multifunctional nature of the photocatalysts. In the case of organic pollutant decomposition, the presence of MoS₂ in ZnO–MoS₂-PANI offers abundant catalytic active sites which result in adsorption of the pollutants and boost the photocatalytic activity. While for the photocatalytic hydrogen evolution, the binary ZnO-PANI composite showed the utmost activity in comparison to the pristine components and ZnO–MoS₂-PANI, which is due to the fact that the higher loading of MoS₂ in the composite increases the number of S atoms on the basal planes, which are inactive for H₂ evolution, and hence results in decreased photocatalytic activity. The results discussed in this work may pave the approach for the design and development of ZnO based multifunctional materials for diverse photocatalytic applications.     

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%。