Facile synthesis of Au/ZnO nanoparticles and their enhanced photocatalytic activity for hydroxylation of benzene

Au/ZnO nanocomposites have been prepared by a simple chemical method. For the first time, the nanocomposites were directly used as photocatalysts for hydroxylation of aromatic hydrocarbons under UV and visible light irradiation. The results show that the as-prepared photocatalysts display high photocatalytic activity for UV and visible catalytic hydroxylation of benzene. Without the assistance of any solvent or additive, high selectivity and high conversion efficiency were still obtained. Different photocatalytic mechanisms were proposed depending on whether excitation happens on ZnO semiconductor or on the surface plasmon band of Au. The former is Au nanoparticles act as electron buffer due to irradiation by UV light and ZnO nanoparticles as reactive sites for hydroxylation of benzene, the latter is that Au nanoparticles act as light harvesters and inject electrons into ZnO conduction band and as photocatalytic sites under visible light irradiation.     

From UV to Near‐Infrared Light‐Responsive Metal–Organic Framework Composites: Plasmon and Upconversion Enhanced Photocatalysis

The exploitation of photocatalysts that harvest solar spectrum as broad as possible remains a high‐priority target yet grand challenge. In this work, for the first time, metal–organic framework (MOF) composites are rationally fabricated to achieve broadband spectral response from UV to near‐infrared (NIR) region. In the core–shell structured upconversion nanoparticles (UCNPs)‐Pt@MOF/Au composites, the MOF is responsive to UV and a bit visible light, the plasmonic Au nanoparticles (NPs) accept visible light, whereas the UCNPs absorb NIR light to emit UV and visible light that are harvested by the MOF and Au once again. Moreover, the MOF not only facilitates the generation of “bare and clean” Au NPs on its surface and realizes the spatial separation for the Au and Pt NPs, but also provides necessary access for catalytic substrates/products to Pt active sites. As a result, the optimized composite exhibits excellent photocatalytic hydrogen production activity (280 µmol g^?1 h^?1) under simulated solar light, and the involved mechanism of photocatalytic H₂ production under UV, visible, and NIR irradiation is elucidated. Reportedly, this is an extremely rare study on photocatalytic H₂ production by light harvesting in all UV, visible, and NIR regions.     

Photodegradation pathway of rhodamine B with novel Au nanorods @ ZnO microspheres driven by visible light irradiation

A series of Au–ZnO photocatalysts were successfully synthesized from ZnO microspheres impregnated with Au nanorods by the seed-mediated method, and their photocatalytic activity of degradation of rhodamine B (RhB) was investigated. The nanocomposite catalyst exhibited high photocatalytic activity and degraded 92% of RhB solution under visible light irradiation in 330 min. The enhancement of photocatalytic effects was mainly ascribed to the surface plasmon resonance effect of Au nanorods; therefore, Au–ZnO spheres can absorb resonant photons and transfer the electron to the conduction band (CB) of ZnO leading to the separation of electrons and holes under visible light. Meanwhile, the photocatalytic performance was beneficial from the flower-like porous structure of ZnO, which enhances adsorption of the dye molecules and dissolved oxygen on the catalyst surface and facilitates the electron/hole transfer. Furthermore, the degradation pathway was proposed on the basis of the intermediates during the photodegradation process using liquid chromatography analysis coupled with mass spectroscopy (LC–MS). The degradation mechanism of pollutant is ascribed to the superoxide radicals (^·O^2?), which is the main oxidative species for the N-deethylated degradation of RhB. Moreover, the Au–ZnO photocatalysts demonstrated excellent photostability after five cycles. This work provides a facile and effective approach for removal of organic dyes under visible light and thus can be potentially used in the environmental purification.     

Au修饰ZnO纳米带及其光催化性质研究

采用离子溅射方法在ZnO纳米带表面蒸镀Au层,经过500℃退火,在样品表面形成Au纳米颗粒,通过SEM、XRD对退火后样品进行结构表征,结果表明,随着蒸镀Au量的增加,在500℃退火后的Au颗粒尺寸逐渐减小,且分布均匀。Au颗粒与ZnO纳米带接触可以形成肖特基结,肖特基结能够有效地使电子与空穴分离并且快速导出电子,所以能够有效提高光催化活性。将以上产物作为光催化剂,在紫外光照射下降解甲基橙（Methyl Orange）,研究其光催化性能,与纯zn0相比,金修饰ZnO纳米带的光催化性能有明显的提高,且不同Au颗粒尺寸降解能力不同。     

Synthesis and characterization of plasmonic visible active Ag/ZnO photocatalyst

Ag deposited ZnO nanoparticles (NPs) have been synthesized by simple sol–gel method for visible light active photocatalytic application. X-ray diffraction (XRD), TEM, UV–DRS and PL studies have been used to characterize the photocatalyst. The results show that Ag/ZnO NPs are wurtzite phase (WZ) of ZnO with Ag NPs in the surface region forming a hetero-interface of Ag–WZ (ZnO). Visible light activity of the material has been studied using photocatalytic degradation kinetics of methylene blue as a probe pollutant. Ag/ZnO NPs exhibit five times higher visible-light driven photocatalytic activity than pristine ZnO and four times than the reference Degussa P-25, under identical conditions. The high visible activity of Ag/ZnO may be attributed to the surface plasmon effect complemented sensitization in the presence of metallic Ag and effective charge separation through Ag–WZ hetero-interfaces.     

Enhanced photocatalytic activity of ZnO/CuO nanocomposite for the degradation of textile dye on visible light illumination

The photocatalytic degradation of organic dyes such as methylene blue and methyl orange in the presence of various percentages of composite catalyst under visible light irradiation was carried out. The catalyst ZnO nanorods and ZnO/CuO nanocomposites of different weight ratios were prepared by new thermal decomposition method, which is simple and cost effective. The prepared catalysts were characterized by different techniques such as X-ray diffraction, transmission electron microscopy, field emission scanning electron microscopy, Fourier transform infrared spectroscopy and UV–visible absorption spectroscopy. Further, the most photocatalytically active composite material was used for degradation of real textile waste water under visible light illumination. The irradiated samples were analysed by total organic carbon and chemical oxygen demand. The efficiency of the catalyst and their photocatalytic mechanism has been discussed in detail.     

RGO/ZnO纳米棒复合材料的合成及光催化性能

采用水热合成法制备ZnO纳米棒及RGO/ZnO纳米棒复合材料。研究不同含量的RGO对RGO/ZnO纳米棒复合材料光催化活性的影响。采用X射线衍射仪(XRD)、场发射电子显微镜(FESEM)、光电子能谱仪(XPS)及漫反射紫外-可见吸收光谱(UV-Vis)检测手段对RGO/ZnO进行表征。结果显示:RGO与ZnO纳米棒成功复合。加入GO的含量不同,获得的RGO/ZnO样品在可见光区域的吸光度值不同。以甲基橙作为模拟污染物的光催化结果表明,RGO/ZnO复合材料具有高的紫外-可见光光降解效率,加入GO与ZnO的质量比为3%时,样品紫外-可见光光催化性能最佳,120min内甲基橙基本可以完全降解;且在波长大于400nm可见光照射下,RGO/ZnO具有一定的可见光活性,180min内其降解甲基橙效率最大可达26.2%。同时,RGO/ZnO具有较好的光稳定性。     

Extension of optical properties of ZnO/SiO2 materials induced by incorporation of Au or NiO nanoparticles

Incorporating noble metal nanoparticles (NPs) and oxides has been proved to be an effective method to tune the optical properties of silica based materials. In this paper the optical and photocatalytic properties have been studied for ZnO/SiO₂ modified with Au or NiO nanoparticles. Changes in the optical properties of semiconductor ZnO particles have been observed due to the deposition of coloured Au and NiO nanoparticles by reducing the band gap energy and thus extending light absorption to visible domain. The excellent surface characteristics of NiO/ZnO/SiO₂ and Au/ZnO/SiO₂ favour the adsorption behaviour of these materials and limit the recombination of electron–holes pairs. Crystal Violet degradation under VIS light proved to have higher efficiency in the presence of Au/ZnO/SiO₂ (97%) than for NiO/ZnO/SiO₂ (60%).     

Doping effects of Co(2+) ions on ZnO nanorods and their photocatalytic properties

A series of Zn(1-x)Co(x)O nanorods with dopant content ranging from x = 0.00 to 0.10 was prepared by a wet chemical method. All Zn(1-x)Co(x)O samples were investigated by x-ray diffraction, transmission electron microscopy, energy-dispersion x-ray line mapping analysis, and UV-visible absorption spectroscopy. It was found that Co(2+) ions were homogeneously substituted for Zn(2+) ions in ZnO nanorods. Rhodamine B degradation was used as a probe reaction to evaluate the effect of Co(2+) doping on ZnO nanorods and photocatalytic performance under UV light and visible light irradiation. Co(2+) ions acted as the trapping or recombination centers for electrons and holes, leading to a reduction in photodegradation efficiency under UV light illumination. Alternatively, Co(2+) ions enhanced the optical absorption and produced the photoinduced carriers under visible illumination in terms of two charge transfer transitions involving Co(2+) ions. Consequently, Co(2+) ions substituted in the lattice of ZnO nanorods significantly improved the visible light photocatalytic activity.     

Enhancing stability and photocatalytic activity of ZnO nanoparticles by surface modification of graphene oxide

This work reports a simple method for the preparation of high-quality GO-ZnO nanocomposite materials. Transmission electron microscopy (TEM) revealed that the ZnO nanoparticles are uniformly distributed on the GO sheets and the diameter of the ZnO nanoparticles falls in 5-8 nm. Further experimental results imply that involving GO sheets into the system could remarkably prevent the aggregation of ZnO nanoparticles compared to pure ZnO. The photocatalytic activity and stability of the prepared GO-ZnO composite for the degradation of Acid Orange 7 (AO 7) under UV light irradiation is significantly enhanced in comparison to the as-synthesized pristine ZnO nanoparticles. Considering the high photocatalytic acitivity and relative stability, this high-quality GO-ZnO nanocomposite is beneficial for the applications in environmental engineering and other fields.     

Calcium germanate nanowires by vanadium doping with improved photocatalytic activity

Vanadium-doped calcium germanate nanowires were prepared by a simple hydrothermal method. The samples were analysed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and solid UV–Vis diffuse reflectance spectrum. The photocatalytic activity of the vanadium-doped calcium germanate nanowires was investigated by the degradation of methylene blue (MB) under solar light irradiation. The results show that the vanadium-doped calcium germanate nanowires are composed of rhombohedral Ca₃GeO₅ and orthorhombic CaV₃O₇ phases. The nanowires have the diameter and length of 50–200 nm and several dozens of micrometres, respectively. The band gap of the vanadium-doped calcium germanate nanowires strongly depends on the vanadium doping mass percentage. The absorption spectrum can be broadened to visible light region. The photocatalytic activity of the vanadium-doped calcium germanate nanowires is remarkably improved. Vanadium-doped calcium germanate nanowires with the vanadium doping mass percentage of 10% have the highest photocatalytic activity for MB degradation under solar light irradiation.     

纳米ZnO可见光催化活性的改善及其降解性能

由于半导体ZnO禁带宽度较宽,因而其可见光催化活性较差.本文分别采用N掺杂、碳包覆、贵金属修饰以及半导体复合等方式来改善纳米ZnO的可见光催化活性,并以罗丹明B为降解污染物,对比了不同材料可见光催化降解有机污染物的效率.研究结果显示以氨水为氮源,通过水热法制备的氮掺杂N-ZnO光催化剂,相比于纯ZnO,对可见光吸收增强...     

A novel poly(triazine imide) hollow tube/ZnO heterojunction for tetracycline hydrochloride degradation under visible light irradiation

A novel poly(triazine imide) hollow tube (PTI)/ZnO heterojunction was prepared by a molten salts method. The photocatalyst was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV–vis diffuse reflectance spectroscopy (DRS) and photoluminescence (PL) spectroscopy, respectively. The results showed the ZnO nanoparticles were successfully coupled into the PTI hollow tube to form PTI/ZnO heterojunction. The degradation of tetracycline hydrochloride (TC) under visible light irradiation was used to evaluate the activity of photocatalyst. The PTI/ZnO-6?wt% heterojunction exhibits the highest photocatalytic activity, which can degrade almost all TC within 90?min. The kinetic constant of degradation reaction with PTI/ZnO-6?wt% heterojunction (0.034?min^?1) is about 5 times as high as that of the PTI (0.0070?min^?1). A possible photocatalytic mechanism for heterojunction according to the energy-band theory was proposed.     

Synthesis,characterisation and antimicrobial activity of manganese- and iron-doped zinc oxide nanoparticles

The present work reports study on antimicrobial activity of pure and doped ZnO nanocomposites. Polyvinyl pyrrolidone capped Mn- and Fe-doped ZnO nanocomposites were synthesised using simple chemical co-precipitation technique. The synthesised materials were characterised using transmission electron microscope (TEM), X-ray powder diffraction (XRD), energy dispersive X-ray fluorescence (EDXRF), Fourier transform infrared (FTIR) spectroscopy and ultraviolet (UV) visible spectroscopy. The XRD and TEM studies reveal that the synthesised ZnO nanocrystals have a hexagonal wurtzite structure with average crystalline size ～7–14 nm. EDXRF and FTIR study confirmed the doping and the incorporation of impurity in ZnO nanostructure. The antimicrobial activities of nanoparticles (NPs) were studied against fungi, gram-positive and gram-negative bacteria using the standard disc diffusion method. The photocatalytic activities of prepared NPs were evaluated by degradation of methylene blue dye in aqueous solution under UV light irradiation. Experimental results demonstrated that ZnO NPs doped with 10% of Mn and Fe ions showed maximum antimicrobial and photodegradation efficiency in contrast with that of the 1% loading. The enhancement in antimicrobial effect and photocatalytic degradation is attributed to the generation of reactive oxygen species due to the synergistic effects of Mn and Fe loading.     

Microwave-assisted silica coating and photocatalytic activities of ZnO nanoparticles

A new and rapid method for silica coating of ZnO nanoparticles by the simple microwave irradiation technique is reported. Silica-coated ZnO nanoparticles were characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), high-resolution transmission electron microscopy (HR-TEM), CHN elemental analysis and zeta potential measurements. The FT-IR spectra and XPS clearly confirmed the silica coating on ZnO nanoparticles. The results of XPS analysis showed that the elements in the coating at the surface of the ZnO nanoparticles were Zn, O and Si. HR-TEM micrographs revealed a continuous and uniform dense silica coating layer of about 3 nm in thickness on the surface of ZnO nanoparticles. In addition, the silica coating on the ZnO nanoparticles was confirmed by the agreement in the zeta potential of the silica-coated ZnO nanoparticles with that of SiO₂. The results of the photocatalytic degradation of methylene blue (MB) in aqueous solution showed that silica coating effectively reduced the photocatalytic activity of ZnO nanoparticles. Silica-coated ZnO nanoparticles showed excellent UV shielding ability and visible light transparency.     

Pd纳米粒子对BiOBr的光吸收和光催化性能的影响

首先合成高结晶度的BiOBr纳米片,然后利用光化学气相沉积（PCVD）法将不同含量的Pd纳米粒子沉积在BiOBr纳米片上．运用N,一物理吸附．脱附、x射线粉末衍射（XRD）、透射电镜（TEM）、x射线光电子能谱（xIX3）、光致发光（PL）谱、紫外可见漫反射吸收光谱（uV-VisDRS）技术对合成的Pd／BiOBr进行了表征．考察了Pd含量对BiOBr光吸收性能和紫外光（A=254am）、可见光下对染料酸性橙Ⅱ的光催化降解性能的影响．结果表明,沉积Pd对样品的比表面积影响不大,Pd纳米粒子能在一定程度上增强催化剂对可见光的吸收能力,并显著抑制光生电子和空穴的复合．紫外光下,当Pd的质量分数为0．5％时,BiOBr催化降解染料的活性提高到1．6倍,而在可见光下含4％的Pd能使BiOBr表现出最高的催化活性,为纯BiOBr的1．5倍．     

高可见光活性磁性催化剂ZnO/ZnFe_2O_4/石墨烯的制备与表征

以硝酸锌和硫酸亚铁为原料,采用水热法一步合成了ZnO/ZnFe_2O_4纳米颗粒,再通过水合肼还原氧化石墨烯合成了ZnO/ZnFe_2O_4/石墨烯磁性催化剂。采用X射线衍射(XRD),场发射扫描电子显微镜(FESEM),透射电子显微镜(TEM),傅立叶变换红外光谱仪(FT-IR)等仪器对催化剂的结构进行了表征。以亚甲基蓝作为目标降解物,考察了不同石墨烯掺量的磁性催化剂在可见光照射下的光催化性能。结果表明,当石墨烯掺量为3%时,磁性催化剂的活性最优,可见光照射60min后亚甲基蓝溶液的降解率高达98%。磁性催化剂稳定性良好,且由于ZnFe_2O_4的存在,磁性催化剂可通过外部磁场进行回收。     

Photocatalytic Properties of Porous Silicon Nanowires

Porous silicon nanowires are synthesized through metal assisted wet-chemical etch of highly-doped silicon wafer. The resulted porous silicon nanowires exhibit a large surface area of 337 m(2)·g(-1) and a wide spectrum absorption across the entire ultraviolet, visible and near infrared regime. We further demonstrate that platinum nanoparticles can be loaded onto the surface of the porous silicon nanowires with controlled density. These combined advancements make the porous silicon nanowires an interesting material for photocatalytic applications. We show that the porous silicon nanowires and platinum nanoparticle loaded porous silicon nanowires can be used as effective photocatalysts for photocatalytic degradation of organic dyes and toxic pollutants under visible irradiation, and thus are of significant interest for organic waste treatment and environmental remediation.     

Tailoring the photoluminescence of ZnO nanowires using Au nanoparticles

Rational design of hybrid nanostructures through attaching nanowires with nanoparticles is an effective route to enhance the existing functionalities or to explore new ones. We carry out a systematic investigation on the photoluminescence of ZnO nanowire-Au nanoparticle hybrid nanostructures synthesized by attaching Au nanoparticles onto ZnO nanowires. Citrate-stabilized 40?nm Au nanoparticles effectively quench the green emission and enhance the UV emission of the ZnO nanowires, which is consistent with the wavelength-dependent generation of surface plasmon. The UV/green emission intensity ratio could be reversibly and reproducibly tailored by attaching/detaching Au nanoparticles. This enhancement of UV emission diminishes if the Au nanoparticles are coated with a polymer layer. We also find that the orange-red emission of the ZnO nanowires is related to the excess oxygen on the ZnO surface, and it is also tunable via annealing and surface modifications.     

Hierarchical Metal/Semiconductor Nanostructure for Efficient Water Splitting

A hierarchically patterned metal/semiconductor (gold nanoparticles/ZnO nanowires) nanostructure with maximized photon trapping effects is fabricated via interference lithography (IL) for plasmon enhanced photo‐electrochemical water splitting in the visible region of light. Compared with unpatterned (plain) gold nanoparticles‐coated ZnO NWs (Au NPs/ZnO NWs), the hierarchically patterned Au NPs/ZnO NWs hybrid structures demonstrate higher and wider absorption bands of light leading to increased surface enhanced Raman scattering due to the light trapping effects achieved by the combination of two different nanostructure dimensions; furthermore, pronounced plasmonic enhancement of water splitting is verified in the hierarchically patterned Au NPs/ZnO NWs structures in the visible region. The excellent performance of the hierarchically patterned Au NPs/ZnO NWs indicates that the combination of pre‐determined two different dimensions has great potential for application in solar energy conversion, light emitting diodes, as well as SERS substrates and photoelectrodes for water splitting.