AgBr/ZnO复合材料光催化剂及其光催化性能

通过一步水热法制备了AgBr/ZnO复合光催化剂,并采用扫描电子显微镜、透射电子显微镜、X射线衍射仪、X射线光电子能谱仪、紫外–可见光漫反射光谱仪和光致发光光谱仪对样品进行表征,分析了AgBr/ZnO体系的合成对材料光催化性能的影响。以罗丹明B溶液为目标污染物,研究复合催化剂的光催化活性。结果表明:在制备的复合样品中,Ag Br与ZnO摩尔比为1:5时(AgBr/ZnO-2)光催化活性最好,在可见光照射下,60 min对罗丹明B的降解率可达98.98%,相比于ZnO光催化活性明显提升,降解速率常数提升了11.08倍;与商用TiO2(P25)相比,降解速率常数提升了10.14倍,这主要归因于Ag Br/ZnO拥有比ZnO更低的电子空穴复合概率,且复合催化剂的光学吸收带边发生红移,从而增强了对可见光的吸收。     

Ag/AgBr/BiOBr hollow hierarchical microspheres with enhanced activity and stability for RhB degradation under visible light irradiation

Ag/AgBr/BiOBr hollow hierarchical microspheres were synthesized through a one-pot solvothermal process. The phase structure, morphology and optical property of the samples were characterized by XRD, SEM, XPS and DRS. Ag/AgBr/BiOBr hollow microspheres exhibited higher photocatalytic activity and improved stability than AgBr/BiOBr nanoplates for rhodamine B degradation under visible light irradiation. The enhanced activities of Ag/AgBr/BiOBr could be attributed to the hollow structure and Ag deposition, which is favorable for adsorption of reactants, enhancement of photoadsorption and transfer of photogenerated carriers. Ag deposition also prevented the decomposition of AgBr under light illumination and contributed to an improved stability.     

Designing effective and stable S-scheme RGO/AgVO3/AgBr hybrid with enhanced photocatalytic performance

The low separation of photogenerated electron-hole pairs and cycle stability has been the main bottleneck which restricts the development of photocatalytic technology for water purification. Here, RGO/AgVO₃ composites were fabricated by photo-ultrasonic assisted reduction method, and AgBr nanoparticles were assembled on the surface of RGO/AgVO₃ via an in situ ion exchange method. A series of characterization and experimental results indicated that the introduction of RGO influenced the growth of crystal phase for AgVO₃ nanorods, resulting that AgVO₃ nanorods became thicker and shorter with the increase in RGO content. Moreover, RGO could also work as a bridge to promote the migration of electrons, leading different improvement for photocatalytic activity. Furthermore, in situ growth of AgBr on the surface of AgVO₃ nanorods could prevent its agglomeration and exfoliation, thus improving the photocatalytic activity and cycle stability of composites. RGO_1%/AgVO₃/AgBr_30% exhibited excellent photocatalytic activity and stability for methylene blue (MB) degradation due to its unique structure, and its removal ratio reached at 96.2% within 50 min. Meanwhile, the separation of photogenerated electron-hole pairs of AgVO₃ was markedly improved due to the introduction of RGO and AgBr. Based on the trapping experiments and theoretical calculation of band gap, a possible S-scheme photocatalytic mechanism for improved photocatalytic activity was proposed.     

新型三元复合可见光催化剂Au/Bi_2WO_6/RGO的制备及其性能

采用溶剂热法制备钨酸铋/石墨烯(Bi_2WO_6/RGO)光催化剂,然后利用光还原法将Au纳米颗粒沉积于该二元光催化剂表面,制备出Au/Bi_2WO_6/RGO三元复合可见光催化剂。运用X射线衍射(XRD)、紫外可见漫反射吸收光谱(UV-Vis DRS)和透射电镜(TEM)对催化剂的晶体结构、光吸收性能、形貌性能进行了分析表征。以罗丹明B (Rh B)为模拟污染物,评价了该催化剂的可见光催化性能。结果表明,RGO和Au纳米颗粒的引入,增强了Bi_2WO_6可见光吸收,同时抑制了光生载流子的复合,从而提高Bi_2WO_6可见光催化降解RhB的性能。     

Dual Z-scheme heterojunction g-C3N4/Ag3PO4/AgBr photocatalyst with enhanced visible-light photocatalytic activity

Recently, there has been a significant interest in developing high-performance photocatalysts for removing organic pollutants from water environment. Herein, a ternary graphitic C₃N₄ (g-C₃N₄)/Ag₃PO₄/AgBr composite photocatalyst is synthesized using an in-situ precipitation-anion-exchange process and characterized by several spectroscopic and microscopic techniques. During the photocatalytic reaction, X-ray photoelectron spectroscopy clearly illustrated the formation of metallic Ag on the g-C₃N₄/Ag₃PO₄/AgBr composite surface. The ternary composite photocatalyst demonstrated an increased photoactivity under visible light (>420 nm), achieving a complete decolorization of methyl orange (MO) in 5 min. The ternary g-C₃N₄/Ag₃PO₄/AgBr hybrid was also applied to the 2-chlorophenol degradation under visible light, further confirming its excellent photocatalytic activity. In addition, quenching experiments revealed that holes (h⁺) and O₂^?– were the major attack species in the decolorization of MO. The enhanced photoactivity of g-C₃N₄/Ag₃PO₄/AgBr results from the efficient transfer/separation of photoinduced charges with the dual Z-scheme pathway and the charge recombination sites on the formed Ag particles.     

可见光驱动溴化银/溴氧化铋复合纳米 材料制备及活性评价*

室温沉淀法合成溴氧化铋（BiOBr）纳米片,然后通过离子交换法制备溴化银/溴氧化铋（AgBr/BiOBr）复合纳米材料,采用X射线衍射（XRD）、场发射扫描电子显微镜（FE-SEM）及紫外可见分光光度计（UV-Vis）对其进行表征,并进行了光催化降解实验。以节能、绿色的LED灯为可见光光源,AgBr/BiOBr复合材料光催化降解罗丹明B（RhB）和甲基橙（MO）的效率均高于BiOBr。AgBr/BiOBr降解RhB的活性强于MO。在AgBr/BiOBr光催化系统中,超氧自由基和空穴是主要的活性物种。不同pH条件下,AgBr/BiOBr对RhB均表现出理想的光催化降解效果,酸性条件下降解效率最佳;碱性环境下AgBr/BiOBr光催化降解MO的活性最高。经过循环利用,AgBr/BiOBr可见光催化活性呈现出一定程度的降低,归因于降解过程中产生了金属银。     

AgBr/TiO_2复合催化剂:双注法制备及其可见光催化性能

以TiO2为载体,采用双注法合成了AgBr/TiO2复合光催化剂.利用X射线衍射仪(XRD)、紫外可见分光光度计(UV-Vis)和扫描电子显微镜(SEM)对AgBr/TiO2的结构、光吸收、形貌进行了表征.研究了AgBr/TiO2在可见光下对甲基橙和丁基罗丹明B的光催化活性.结果表明,与TiO2相比,AgBr/TiO2的光吸收范围拓展到400—600nm波段,并且随着AgBr负载量的增加,AgBr/TiO2的可见光吸收强度增强;当AgBr与TiO2的摩尔比为0.25时,AgBr/TiO2具有最大催化活性;在相同条件下,AgBr/TiO2对丁基罗丹明B的降解效果优于甲基橙.     

Boron-Doped Graphene/ZnO Nanoflower Heterojunction Composite with Superior Photocatalytic Activity

The boron-doped graphene (BG) is synthesized successfully by one pot reduce-doping of graphene oxide (GO) with borane tetrahydrofuran (BH₃·THF) and the novel BG/ZnO p–n heterojunction composite between p-type BG and n-type ZnO is obtained via a simple hydrothermal method. The samples are characterized by scanning electron microscopy, the Raman spectroscopy and the UV–Vis diffuse spectroscopy. The results confirm the formation of p–n junction between BG and ZnO. The photodegradation of MB demonstrate that the BG/ZnO composite has superior photocatalytic activity under UV–Vis or visible irradiation. The photocatalytic activity k value of BG/ZnO p–n heterojunction composite is 3.1 and 4.5 times as that of r-GO/ZnO and pure ZnO under white light and is 1.8 and 3.9 times under visible light, respectively. The superior photocatalytic activity of the BG/ZnO composite is ascribed to the formation of p–n heterojunction. The p–n heterojunction can promote the separation of electron/hole pairs and inhibit the recombination of electrons in conduction band and holes in valence band by transferring holes from the valence band of n-type ZnO to the valence band of p-type BG.     

Ag nanoparticles loaded TiO2/MWCNT ternary nanocomposite: A visible-light-driven photocatalyst with enhanced photocatalytic performance and stability

A visible light active photocatalyst, Ag/TiO₂/MWCNT was synthesized by loading of Ag nanoparticles onto TiO₂/MWCNT nanocomposite. The photocatalytic activity of Ag/TiO₂/MWCNT ternary nanocomposite was evaluated for the degradation of methylene blue dye under UV and visible light irradiation. Ag/TiO₂/MWCNT ternary nanocomposite exhibits (~9 times) higher photocatalytic activity than TiO₂/MWCNT and (~2 times) higher than Ag/TiO₂ binary nanocomposites under visible light irradiation. The enhancement in the photocatalytic activity is attributed to the synergistic effect between Ag nanoparticles and MWCNT, which enhance the charge separation efficiency by Schottky barrier formation at Ag/TiO₂ interface and role of MWCNT as an electron reservoir. Effect of different scavengers on the degradation of methylene blue dye in the presence of catalyst has been investigated to find the role of photogenerated electrons and holes. Simultaneously, the Ag/TiO₂/MWCNT shows excellent photocatalytic stability. This work highlights the importance of Ag/TiO₂/MWCNT ternary nanocomposite as highly efficient and stable visible-light-driven photocatalyst for the degradation of organic dyes.     

AgBr@Ag/TiO2 core–shell composite with excellent visible light photocatalytic activity and hydrothermal stability

AgBr@Ag/TiO₂ core–shell photocatalysts were fabricated by a facile green route. TiO₂ was uniformly coated on the surface of cubic AgBr, making AgBr@Ag/TiO₂ core–shell photocatalyst show excellent hydrothermal stability. Beneficial from that Ag nanoparticles and AgBr can respond to visible light and core–shell structure can effectively separate the photogenerated electrons and holes, AgBr@Ag/TiO₂ core–shell composites exhibited outstanding visible light photocatalytic activity for the degradation of acid orange 7. The activity of AgBr@Ag/TiO₂ is related to the thickness of TiO₂ shell, and the optimal shell thickness for obtaining the highest activity is 10 nm.     

复合纳米棒状Ag3PO4/ZnO材料的光催化性能

以一维棒状ZnO为载体,采用原位生长法制备纳米棒状Ag_3PO_4/ZnO复合材料。通过XRD、SEM、TEM、XPS和UV-Vis-DRS等测试对纳米棒状Ag_3PO_4/ZnO复合材料进行了表征,并评价了样品在可见光下的光催化性能。结果显示,ZnO几乎无可见光活性,通过水热法制备的ZnO形貌发生了改变,为比表面积的增加做出了贡献,为Ag_3PO_4提供了更多的负载可能。在可见光照射下,纯ZnO和Ag_3PO_4对苯酚的降解率分别为20%和38%,复合材料Ag_3PO_4/ZnO对苯酚的降解率为91.24%,光催化降解性能明显高于纯ZnO和Ag_3PO_4。最后,光催化稳定性的研究证明,Ag_3PO_4/ZnO复合材料形成了有效的异质结结构,抑制了电子-空穴的复合,提高了Ag_3PO_4/ZnO复合材料的稳定性。     

Preparation of rare earth-doped ZnO hierarchical micro/nanospheres and their enhanced photocatalytic activity under visible light irradiation

Rare earth-doped ZnO hierarchical micro/nanospheres were prepared by a facile chemical precipitation method and characterized by X-ray diffraction, field-emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, UV-visible diffuse reflectance spectroscopy and photoluminescence spectroscopy. The results showed that the as-synthesized products were well-crystalline and accumulated by large amount of interleaving nanosheets. It was also observed that the rare earth doping increased the visible light absorption ability of the catalysts and red shift for rare earth-doped ZnO products appeared when compared to pure ZnO. The photocatalytic studies revealed that all the rare earth-doped ZnO products exhibited excellent photocatalytic degradation of phenol compared with the pure ZnO and commercial TiO₂ under visible light irradiation. Nd-doped ZnO had the highest photocatalytic activity among all of the rare earth-doped ZnO products studied. The optimal Nd content was 2.0 at% under visible light irradiation. The enhanced photocatalytic performance of rare earth-doped ZnO products can be attributed to the increase in the rate of separation of photogenerated electron–hole pairs and hydroxyl radicals generation ability as evidenced by photoluminescence spectra.     

Ionic liquid-assisted preparation of g-C3N4/RGO co-intercalated CuBi2O4 hierarchical nanoflower and enhancement of the photocatalytic activity

A new p-n type CBO/CN/RGO ternary heterojunction photocatalyst combining three-dimensional multi-stage rosette CuBi₂O₄ and two-dimensional g-C₃N₄ and RGO flakes was successfully prepared by ionic liquid-assisted hydrothermal method. The successful construction of p-n heterojunctions of CBO/CN/RGO composites was verified by means of UV–vis diffuse reflection, Mott Schottky curves and TEM, and construction the heterojunctions significantly improved that of the transfer and transport speed of photogenerated carriers. The photocatalytic degradation of MO by CBO/CN/RGO-6% reached 91.83% within 150 min, while the kinetic constants of degradation k were 9.7 and 7.9 times greater than those of single-phase CBO and g-C₃N₄, respectively. Three cycles of experiments demonstrated that the degradation efficiency of CBO/CN/RGO-6% composites remained above 88% for RhB, which fully proved that the CBO/CN/RGO-6% composites possessed good chemical stability. Based on its excellent photocatalytic performance and good stability, CBO/CN/RGO-6% is expected to be the preferred material for environmental wastewater treatment.     

g-C3N4基复合纳米材料光催化性能研究进展

g-C₃N₄可见光利用率高,具有非常好的光催化性能,是一种新型的无金属半导体光催化材料,然而电导率低,易团聚,光生载流子容易复合限制了其在实际生产中的应用。为进一步提高g-C₃N₄基复合材料的光催化性能,研究者做了大量修饰工作,并取得显著成果。本文主要从半导体材料耦合(细分为原子层沉积法和三元纳米材料复合)、贵金属修饰和量子点敏化三个方面概括了近年来对g-C₃N₄的修饰改性工作,探究了g-C₃N₄基复合材料在光催化降解有机污染物、光解水制氢、催化“记忆”效应和降解重金属等不同领域方面取得的成效。指出g-C₃N₄基复合材料发展面临的问题,最后对g-C₃N₄基复合材料未来的发展提出了展望。     

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。     

ZIF-8制备原位碳掺杂氧化锌及其光催化性能研究

以ZIF-8为前驱体,采用热解法制备碳掺杂氧化锌。分别研究ZIF-8在350、400、450 ℃下煅烧以及陈化10 min、3 h、24 h对制备原位碳掺杂氧化锌的影响。通过热重（TG）、X射线衍射（XRD）和扫描电镜（SEM）研究样品的形貌和结构;紫外可见漫反射光谱（UV-vis）和光致发光光谱（PL）证明原位碳掺杂氧化锌具有可见光吸收能力和更低的光生载流子复合率;DFT模拟计算表明氧化锌晶格中掺入碳元素能有效减小带隙值。原位碳掺杂氧化锌较纯氧化锌在可见光和紫外光照射下的光催化性能分别提高1.5倍和3.0倍。空穴和羟基自由基是原位碳掺杂氧化锌光催化降解体系的主要活性基团,并由此提出了碳掺杂氧化锌的光催化机理。     

Facile synthesis of Ag/AgBr/RGO nanocomposite as a highly efficient sunlight plasmonic photocatalyst

Well-dispersed Ag/AgBr colloidal spheres and the corresponding reduced graphene oxide (RGO) hybridized nanocomposite, Ag/AgBr/RGO, were synthesized by a simple one-step polyolthermal method. By rational tuning the synthesis conditions such as the content of polyvinylpyrrolidone (PVP), hexadecyltrimethyl ammonium bromide (CTAB), and the initial reaction temperature, the morphology, size and dispersity of the Ag/AgBr products can be easily controlled. The formation mechanism of as-prepared Ag/AgBr colloidal spheres was further proposed. The hybridization of Ag/AgBr spheres with RGO enhanced the composite catalytic performance, and the Ag/AgBr/RGO hybrid exhibited excellent catalytic activity and stability towards decomposition of Rhodamine B (RhB) under sunlight irradiation.     

Photocatalytic hydrogen generation of ZnO rod–CdS/reduced graphene oxide heterostructure prepared by Pt-induced oxidation and light irradiation-assisted methods

A synthesis method including Pt-induced oxidation and light irradiation-assisted routes has been developed to prepare a ZnO rod–CdS/reduced graphene oxide (RGO) heterostructure. Here, graphene oxide nanosheets are reduced and loaded onto the surface of Zn spheres using a redox process. ZnO rods are generated from Zn spheres by a Pt-induced oxidation method, and CdS nanoparticles are then loaded onto the surface of RGO via a light irradiation-assisted method. The ZnO rod–CdS/RGO heterostructure exhibits 3.8 times higher photocatalytic hydrogen generation rate from an aqueous solution containing Na₂S/Na₂SO₃ than the reference ZnO rod–CdS heterostructure under simulated solar light irradiation. The optimal contents of RGO nanosheets and CdS nanoparticles are 2 wt% and 20 at.%, respectively.     

新型g-C3N4/CuS复合材料的制备及光催化研究

一步水热法合成CuS修饰的石墨相氮化碳(g-C3N4/CuS)复合光催化剂,通过FE-SEM、XRD、FTIR、UV-Vis-DRS等手段对其进行了表征,利用Cr(VI)溶液考察了g-C3N4/CuS在可见光下的光催化还原性能.实验结果表明,g-C3N4/CuS复合光催化剂的光催化活性明显优于单一的g-C3N4和CuS.可见光照射下,180 min内Cr(VI)的去除率可达70％以上.CuS的引入不仅扩宽了g-C3N4的可见光吸收范围,而且降低了g-C3N4光生电子和空穴的复合率,从而显著提高g-C3N4的光催化活性.该复合材料的催化活性受溶液的pH值影响较大,酸性条件下更有利于光催化反应的进行;共存低浓度腐殖酸对Cr(VI)的去除没有显著影响.g-C3N4/CuS具有良好的可见光催化活性,可用于废水中Cr(VI)的光催化还原去除.     

Reduced graphene oxide as co-catalyst for enhanced visible light photocatalytic activity of BiOBr

BiOBr-reduced graphene oxide (RGO) composites were successfully synthesized via a simple hydrothermal method. Their morphology, structure and photocatalytic activity in the degradation of nitrobenzene were characterized by scanning electron microscopy, X-ray diffraction, nitrogen adsorption-desorption, UV–vis absorption spectroscopy, photoluminescence spectra, electrochemical impedance spectra and total organic carbon, respectively. The results showed that the introduction of RGO could enhance the visible light photocatalytic activity of BiOBr. The BiOBr-RGO composite with 0.6 wt% RGO exhibited an optimal photocatalytic activity, and the maximum degradation rate of nitrobenzene was about 2.16 times that of pure BiOBr due to the increased light absorption and the reduced electron-hole pair recombination in BiOBr with the introduction of RGO.