Plasmonic Ag/AgBr nanohybrid: synergistic effect of SPR with photographic sensitivity for enhanced photocatalytic activity and stability

A plasmonic Ag/AgBr nanohybrid has been synthesized by in situ thermal reduction of AgBr nanoparticles in polyols. This directly converted Ag/AgBr shows significant absorption over the full visible spectrum. The enhanced light absorption in the spectral region of 450 nm to 800 nm was due to the plasmonic nanosized Ag grown on the surface of AgBr nanoparticles with mixed morphologies and increased sizes. Under visible light irradiation, the plasmonic Ag/AgBr exhibits high activity and stability for the photodegradation of organic pollutants, e.g. methylene blue. The contribution of the SPR and its synergistic effect with the photosensitive AgBr in the photocatalytic activity were verified. Based on the plasmon-mediated charge injection and the band structure of the metal-semiconductor heterojunction, a mechanism of the plasmon synergistically enhanced photocatalytic process was proposed.     

Plasmonic enhancements of photocatalytic activity of Pt/n-Si/Ag photodiodes using Au/Ag core/shell nanorods

We report the plasmonic enhancement of the photocatalytic properties of Pt/n-Si/Ag photodiode photocatalysts using Au/Ag core/shell nanorods. We show that Au/Ag core/shell nanorods can be synthesized with tunable plasmon resonance frequencies and then conjugated onto Pt/n-Si/Ag photodiodes using well-defined chemistry. Photocatalytic studies showed that the conjugation with Au/Ag core/shell nanorods can significantly enhance the photocatalytic activity by more than a factor of 3. Spectral dependence studies further revealed that the photocatalytic enhancement is strongly correlated with the plasmonic absorption spectra of the Au/Ag core/shell nanorods, unambiguously demonstrating the plasmonic enhancement effect.     

New insight into daylight photocatalysis of AgBr@Ag: synergistic effect between semiconductor photocatalysis and plasmonic photocatalysis

Noble metal nanoparticles (NPs) are often used as electron scavengers in conventional semiconductor photocatalysis to suppress electron-hole (e(-)-h(+) ) recombination and promote interfacial charge transfer, and thus enhance photocatalytic activity of semiconductors. In this contribution, it is demonstrated that noble metal NPs such as Ag NPs function as visible-light harvesting and electron-generating centers during the daylight photocatalysis of AgBr@Ag. Novel Ag plasmonic photocatalysis could cooperate with the conventional AgBr semiconductor photocatalysis to enhance the overall daylight activity of AgBr@Ag greatly because of an interesting synergistic effect. After a systematic investigation of the daylight photocatalysis mechanism of AgBr@Ag, the synergistic effect was attributed to surface plasmon resonance induced local electric field enhancement on Ag, which can accelerate the generation of e(-)-h(+) pairs in AgBr, so that more electrons are produced in the conduction band of AgBr under daylight irradiation. This study provides new insight into the photocatalytic mechanism of noble metal/semiconductor systems as well as the design and fabrication of novel plasmonic photocatalysts.     

Polyhedral AgBr microcrystals with an increased percentage of exposed {111} facets as a highly efficient visible-light photocatalyst

Synthesis of inorganic single crystals with exposed high-reactivity facets is a desirable target in the catalytic chemistry field. Polyhedral AgBr microcrystals with an increased percentage of exposed high-reactivity {111} facets have been successfully prepared for the first time, and the photocatalytic performance of these microcrystals when used as an AgBr/Ag plasmonic photocatalyst was investigated. The results indicate that the as-prepared sample has high photocatalytic activity and, under the same measurement conditions, the photodegradation rate of methyl orange dye over these microcrystals is at least four times faster than with other shapes of AgBr/Ag microstructure, as well as 20?times faster than with the highly efficient Ag(3)PO(4) photocatalyst. DFT calculations suggest that the AgBr (111) surface is mainly composed of unsaturated Ag atoms and has a relatively high surface energy, both of which are favorable for enhancing the photocatalytic activity of the AgBr/Ag polyhedron photocatalyst. This work not only provides a highly efficient plasmonic photocatalyst of polyhedral AgBr/Ag microcrystals with an increased percentage of exposed high-reactivity AgBr {111} facets, but also demonstrates that the shape and crystalline quality of the exposed facets have an important influence on the photocatalytic activities.     

离子交换法制备AgBr/Ag2WO4复合催化剂及其可见光催化性能

以Ag₂WO₄为载体,采用离子交换法合成了新型的AgBr/Ag₂WO₄复合光催化剂.利用XRD、SEM和UV-Vis对AgBr/Ag₂WO₄催化剂进行了表征,在可见光条件下(500 W、λ>420 nm)、以甲基橙(MO)为染料模型研究了AgBr/Ag₂WO₄的光催化活性.结果表明,AgBr/Ag₂WO₄具有比单独的AgBr和Ag₂WO₄更佳的催化活性,其中30%-AgBr/Ag₂WO₄复合催化剂具有最大光催化活性.机理研究表明,在MO的降解过程中,·O₂^-起主要作用,h⁺次之而·OH可以忽略.AgBr和Ag₂WO₄之间构成的异质结有效分离了光生电子和空穴,提高了催化剂的活性.     

Polyhedral AgBr Microcrystals with an Increased Percentage of Exposed {111} Facets as a Highly Efficient Visible‐Light Photocatalyst

Synthesis of inorganic single crystals with exposed high‐reactivity facets is a desirable target in the catalytic chemistry field. Polyhedral AgBr microcrystals with an increased percentage of exposed high‐reactivity {111} facets have been successfully prepared for the first time, and the photocatalytic performance of these microcrystals when used as an AgBr/Ag plasmonic photocatalyst was investigated. The results indicate that the as‐prepared sample has high photocatalytic activity and, under the same measurement conditions, the photodegradation rate of methyl orange dye over these microcrystals is at least four times faster than with other shapes of AgBr/Ag microstructure, as well as 20 times faster than with the highly efficient Ag₃PO₄ photocatalyst. DFT calculations suggest that the AgBr (111) surface is mainly composed of unsaturated Ag atoms and has a relatively high surface energy, both of which are favorable for enhancing the photocatalytic activity of the AgBr/Ag polyhedron photocatalyst. This work not only provides a highly efficient plasmonic photocatalyst of polyhedral AgBr/Ag microcrystals with an increased percentage of exposed high‐reactivity AgBr {111} facets, but also demonstrates that the shape and crystalline quality of the exposed facets have an important influence on the photocatalytic activities.     

Ag/AgBr/Co–Ni–NO3 Layered Double Hydroxide Nanocomposites with Highly Adsorptive and Photocatalytic Properties

A facile anion‐exchange precipitation method was used to synthesize bifunctional Ag/AgBr/Co–Ni–NO₃ layered double hydroxide (LDH) nanocomposites by adding AgNO₃ solution to a suspension of Co–Ni–Br LDH. The Ag/AgBr nanoparticles were highly dispersed on the sheets of Co–Ni–NO₃ LDH. The prepared nanocomposites were used to adsorb and photocatalytically degrade organic pollutants from water. Without light illumination, the nanocomposites quickly adsorbed methyl orange, and the adsorptive capacity, which can reach 230 mg g^?1, is much higher than those of Co–Ni–Br LDH, Ag/AgBr, and activated carbon. The photocatalytic activities of the nanocomposites for the removal of dyes and phenol are higher than those of Co–Ni–Br LDH and Ag/AgBr. The proposed method can be applied to prepare other LDH/silver salt composites. The high absorptive capacity and good photocatalytic activity of such nanostructures could have wide applications in wastewater treatment.     

Synthesis of cubic Ag@AgCl and Ag@AgBr plasmonic photocatalysts and comparison of their photocatalytic activity for degradation of methyl orange and 2,4-dichlorophenol

Uniform cubic Ag@AgCl and Ag@AgBr plasmonic photocatalysts with side length of 0.7 µm were synthesized by a facile green route, in which a controllable double-jet precipitation technique was employed to fabricate homogeneous cubic AgCl and AgBr grains while a photoreduction process was used to produce Ag nanoparticles (NPs) on the surface of AgCl and AgBr grains. The synthesized samples were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) analysis, X-ray photoelectron spectroscopy (XPS), and ultraviolet–visible (UV–Vis) diffuse reflectance spectroscopy (DRS). The photocatalytic activities of Ag@AgCl and Ag@AgBr were compared using degradation of methyl orange (MO) dye and 2,4-dichlorophenol (2,4-DCP) under visible-light irradiation. Ag@AgBr showed higher photocatalytic activity for MO degradation but weaker activity for 2,4-DCP decomposition. Possible degradation mechanisms are proposed to interpret these contrary paradoxical experimental results.     

Nanoplasmonic zirconium nitride photocatalyst for direct overall water splitting

The ability of plasmonic nanostructures to efficiently harvest light energy and generate energetic hot carriers makes them promising materials for utilization in photocatalytic water spitting.Apart from the traditional Au and Ag based plasmonic photocatalysts,more recently the noble-metal-free alternative plasmonic materials have attracted ever-increasing interest.Here we report the first use of plasmonic zirconium nitride（ZrN） nanoparticles as a promising photocatalyst for water splitting.Highl...     

F‐doped Ag/AgBr with enhanced visible‐light photocatalytic activity and mechanism

Novel F‐doped Ag/AgBr photocatalysts containing various amounts of F^? were synthesized by an ion exchange method. The photocatalysts were characterized using X‐ray diffraction (XRD), scanning and transmission electron microscopies, X‐ray photoelectron, ultraviolet–visible absorption and photoluminescence spectroscopies and electron spin resonance (ESR). Powder XRD revealed that F^? was inserted into the crystal lattices of AgBr and partially replaced Br^?, resulting in the contraction of the AgBr lattices. Methyl orange photodegradation experiments showed that the photocatalytic activity of F‐doped Ag/AgBr was significantly dependent on the amount of F^?. Ag/AgBr doped with 0.02 M F^? achieved the highest activity of 91% after 8 min. ESR showed the main active species in methyl orange degradation was ^?OH. The main enhancement mechanism is that F^? inhibits the recombination of electron–hole pairs.     

Synthesis, characterization and photocatalytic property of AgBr/BiPO4 heterojunction photocatalyst

A novel heterojunction AgBr/BiPO(4) photocatalyst was synthesized with the hydrothermal method. The photocatalyst was characterized by X-Ray powder Diffraction (XRD), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectrometry (EDS), Transmission Electron Microscopy (TEM), X-ray Photoelectron Spectrscopy (XPS) and Diffuse Reflectance Spectroscopy (DRS). The XRD, SEM-EDS, TEM and XPS analyses indicated that the heterojunction structure formed during the process of hydrothermal treatment. The photocatalytic activity of the photocatalysts was evaluated by degradation of methylene blue dye (MB). The results indicated that the AgBr/BiPO(4) heterojunction exhibited a much higher photocatalytic activity than the pure BiPO(4). The mechanism of the enhancing AgBr/BiPO(4) heterojunction's photocatalytic activity was discussed. It was also found that the photocatalytic degradation of MB over AgBr/BiPO(4) heterojunction photocatalysts followed the pseudo-first-order reaction model.     

高效Ag@AgBr等离子体光催化剂的制备及可见光活性研究

采用水热法和光致还原法制备了具有等离子体共振效应的Ag@AgBr可见光催化剂,利用XRD,SEM,EDX,DRS和XPS等手段对产物的结构和性能进行表征,并研究了催化剂在可见光下对罗丹明B(RhB)的光催化降解性能,考察了催化剂的循环使用及捕获剂对Ag@AgBr光催化性能的影响.结果表明:贵金属Ag纳米粒子的表面等离子体共振效应可显著增强Ag@AgBr对可见光的吸收;催化剂对罗丹明B具有较高的可见光降解活性和稳定性,在可见光下照射90 min,对罗丹明B的降解率达95%以上,光催化剂循环使用5次仍具有良好的光催化降解活性;淬灭实验表明在Ag@AgBr降解罗丹明B过程中,吸附在催化剂表面的h+、·OH、O2·-是主要的活性物种.     

Method for Visible Light‐Induced Photocatalytic Degradation of Methylparaben in Water Using Nanostructured Ag/AgBr@m‐WO3

An efficient method of photocatalytic degradation of methylparaben in water using Ag nanoparticles (NPs) loaded AgBr‐mesoporous‐WO₃ composite photocatalyst (Ag/AgBr@m‐WO₃), under visible light is presented. In this process, quantification of methylparaben in water was carried out by high‐performance liquid chromatography (HPLC) and the HPLC results showed a significant reduction of methylparaben in water due to the enhanced of photocatalytic degradation efficiency of Ag/AgBr@m‐WO₃. For the material synthesis, highly ordered mesoporous‐WO₃ (m‐WO₃) was initially synthesized by sol–gel method and AgBr nanoparticles (NPs) were subsequently introduced in the pores of m‐WO₃, and finally, the Ag nanoparticles were introduced by light irradiation. The enhanced photocatalytic degradation of methylparaben in water is attributed to the formation of surface plasmonic resonance (SPR) due to the introduction of Ag NPs on the surface of the catalyst. Also, the formation of heterojunction between AgBr and mesoporous‐WO₃ in Ag/AgBr@m‐WO₃ significantly inhibited the recombination of light‐induced electron‐hole pairs in the semiconductor composite. The morphological and optical characterizations of the synthesized photocatalysts (Ag/AgBr@m‐WO₃) were carried out using SEM, TEM, XDR, N₂ adsorption–desorption, UV‐VIS diffuse reflectance spectroscopy (DRS). Also, the photocatalytic studies using radical scavengers were carried out and the results indicated that ${\text{O}}_2^{·-}$ is the main reactive species.     

g-C_3N_4/Ag/GO Composite Photocatalyst with Efficient Photocatalytic Performance: Synthesis,Characterization, Kinetic Studies,Toxicity Assessment and Degradation Mechanism

The g-C_3N_4/Ag/GO(CNAG) photocatalysts were synthesized by a facile two-step reaction route. The as-prepared CNAG samples were characterized by X-ray diffraction(XRD), Fourier transform-infrared spectroscopy(FTIR), X-ray photoelectron spectroscopy(XPS), photoluminescence spectroscopy(PL) and ultraviolet-visible diffuse reflectance spectroscopy techniques(UV-vis DRS). The photocatalytic activity was obtained by degrading rhodamine B(RhB) under simulated sunlight and the results showed that photocatalytic activity of CNAG was much higher than that of pure g-C_3N_4 and g-C_3N_4/Ag. When the mass ratio of GO was 6%, the as-prepared CNAG-6% sample possessed the highest photocatalytic activity and the kinetic constant of RhB degradation was 0.077 min~(-1), which was almost 4.3 times higher than that of pure g-C_3N_4(0.018 min~(-1)) and 2.5 times higher than that of the g-C_3N_4/Ag(0.031 min~(-1)) composite, respectively. The toxicity of CNAG samples was assessed via seed germination experiment and no significant inhibitory effect was observed. The enhanced photocatalytic activity could be attributed to the synergistic effect of partial surface plasma resonance(SPR) effect of Ag, strong visible light absorption and the high separation efficiency of photon-generated carrier. The CNAG-6% sample exhibited excellent stability during the cycle experiment. Finally, a possible photocatalytic mechanism was proposed.     

Effective photocatalytic degradation of an azo dye over nanosized Ag/AgBr-modified TiO<Subscript>2</Subscript> loaded on zeolite

Zeolite-based photocatalysts were prepared by the sol-gel and deposition methods. The photocatalysts were characterised by X-ray diffraction, nitrogen adsorption-desorption isotherms, FTIR spectroscopy, scanning electron microscopy and energy-dispersive X-ray spectrometry. The activity of the prepared photocatalysts was evaluated by the UV-induced degradation of acid blue 92, a textile dye in common use. The effect of various parameters, such as catalyst concentration, initial dye concentration, thiosulphate concentration and pH, on the rate and efficiency of the photocatalytic degradation of acid blue 92 was investigated. The results showed that each parameter influenced the degradation rate and efficiency in a particular way. It was also found that, under optimised conditions, Ag/AgBr/TiO₂/zeolite exhibited the highest photocatalytic performance. A comparison of catalytic activity when exposed to visible light under the same conditions showed that the photocatalysts containing AgBr had the highest activity.     

Nanosized Functional MOFs Loading Ag/AgBr with Throughout‐Visible‐Light Absorption for High‐Efficiency Photocatalysis

Porous metal‐organic frameworks (MOFs) loading metal nanoparticles to form a composite photocatalyst demonstrated unique advantages. Modification of the electron donating group on the aromatic linkers of MOFs could increase the absorption range of light, thereby increasing the photocatalytic activity. In this study, we prepared a composite photocatalyst using a stable NH₂‐functionalized MOF (UiO‐66‐NH₂) to load semiconductor Ag/AgBr nanoparticles, and the resultant composites have intense optical absorption throughout visible light range. The greatly enhanced optical absorption and the unique hetero‐junction between Ag/AgBr and UiO‐66‐NH₂ render efficient separation and utilization of photogenerated electron‐hole pairs. Therefore, Ag/AgBr@UiO‐66‐NH₂ showed much more excellent photocatalytic activity, compared with unmodified UiO‐66 loading Ag/AgBr (Ag/AgBr@UiO‐66) and reported AgX@MOF catalysts. Moreover, the composite photocatalysts showed excellent stability during cycling experiment.     

Plasmonic photocatalytic system using silver chloride/silver nanostructures under visible light

Plasmonic photocatalytic nanostructured system was investigated on silver chloride/silver nanoparticles under visible light. Silver chloride/silver nanoparticles were readily prepared using dispersing agent and light irradiation. The d-spacing analysis, high resolution-transmission electron microscopy, X-ray diffraction analysis and diffuse-reflectance spectroscopy demonstrated that silver nanoparticles were introduced on the surface of silver chloride nanoparticles and then silver chloride/silver nanostructured photocatalytic materials were successfully synthesized. The as-synthesized plasmonic photocatalysts exhibited the enhanced photocatalytic performance over nitrogen-doped titania nanomaterials. The improved catalytic activity was originated from the enhanced adsorption for visible light, electron–hole separation, and the formation of chloride atoms in silver chloride/silver nanostructured materials.     

Sunlight responsive photocatalysts: AgBr/ZnO hybrid nanomaterial

A novel high-effective sunlight-induced AgBr/ZnO hybrid nanophotocatalyst has been synthesized and it was characterized by different techniques such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and ultraviolet-visible spectrophotometry (UV-vis). The AgBr/ZnO hybrid nanophotocatalyst has excellent photocatalytic activity for photodegradation of methyl orange (MO) under sunlight irradiation. The MO degradation efficiency for AgBr/ZnO is about 98% after 1 hour under sunlight irradiation. These results suggested that AgBr/ZnO is a promising candidate for the development of highly efficient sunlight photocatalysts. In addition, the photocatalytic mechanism of AgBr/ZnO under sunlight irradiation is illustrated and discussed.     

Silicon‐grafted Ag/AgX/rGO nanomaterials (X = Cl or Br) as dip‐photocatalysts for highly efficient p‐nitrophenol reduction and paracetamol production

In this work, plasmonic Ag/AgX/rGO (X = Cl or Br) nano‐photocatalysts were grafted with silicon by adding trimethylsilyl chloride as silicon precursor. The synthesized Ag/AgX/rGO‐Si hybrids showed a large improvement of photocatalytic activity towards the synthesis of p‐aminophenol (PAP) as well as paracetamol (acetaminophen; APAP) through the photoreduction of p‐nitrophenol (PNP). The prepared catalysts Ag/AgX/rGO were characterized using SEM, XRD, FTIR and the reduction reaction of p‐nitrophenol was monitored by UV–Vis measurements, GC/MS and ¹HNMR data. From the results, it was demonstrated that the rate order of reduction process of the PNP to PAP and to APAP under visible light irradiation of the samples was as follows; Ag/AgBr/rGO‐Si > Ag/AgCl/rGO‐Si > Ag/AgBr/rGO > Ag/AgCl/rGO. The reaction mechanism had been postulated that was supported with the spectroscopic data. In addition, the catalysts were recovered from the reaction medium and re‐used in three cycles that indicated the reusability and stability of the catalysts. This study was featured by the following; i) fast reaction, ii) the reduction of p‐nitrophenol to paracetamol was performed in a facile one‐pot reaction compared to previous approaches that tends to reduce the production cost, and iii) investigations on the catalytic properties of Ag/AgX/rGO in organic transformations open the door to find a benefice of these catalysts in other organic reactions and in the development in the synthesis of pharmaceutical products.     

The Visible‐Light Photocatalytic Activity and Antibacterial Performance of Ag/AgBr/TiO2 Immobilized on Activated Carbon

Visible‐light‐driven Ag/AgBr/TiO₂/activated carbon (AC) composite was prepared by solgel method coupled with photoreduction method. For comparison, TiO₂, TiO₂/AC, and Ag/AgBr/TiO₂ were also synthesized. Their characteristics were analyzed by XRD, SEM‐EDS, TG‐DSC and UV–vis techniques. Photocatalytic activity and antibacterial performance under visible‐light irradiation were investigated by ICP‐AES, ATR‐FT‐IR and spectrophotometry methods using methylene blue and Escherichia coli as target systems, respectively. The results showed that Ag/AgBr was successfully deposited on anatase TiO₂/AC surface, and exhibited a distinct light absorption in the visible region. Ag/AgBr/TiO₂/AC displayed excellent antibacterial performance both in dark and under visible‐light illumination. The growth of E. coli cell was inhibited in the presence of Ag/AgBr/TiO₂/AC in dark. Moreover, upon visible‐light illumination, a significant damage of cell membrane was noticed. Ag/AgBr/TiO₂/AC was also shown higher photocatalytic efficiency for methylene blue degradation than those of TiO₂, TiO₂/AC, and Ag/AgBr/TiO₂. This is attributed to the synergetic effect between AC and Ag/AgBr/TiO₂, of which AC acts as the role of increasing reaction areas, continuous enriching, and transferring the adsorbed MB molecules to the surface of supported photocatalysts, and the Ag/AgBr/TiO₂ acts as a highly active photocatalyst for degrading MB molecules under visible‐light irradiation.