Facile preparation of Ag/Ag2WO4/g‐C3N4 ternary plasmonic photocatalyst and its visible‐light photocatalytic activity

Introducing plasmonic metals into semiconductor materials has been proven to be an attractive strategy for enhancing photocatalytic activity in the visible region. In this work, a novel and efficient Ag/Ag₂WO₄/g‐C₃N₄ (AACN) ternary plasmonic photocatalyst was successfully synthesized using a facile one‐step in situ hydrothermal method. The composition, structure, morphology and optical absorption properties of AACN were investigated using X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and UV–visible diffuse reflectance spectroscopy, respectively. Photocatalytic performance of AACN was evaluated via rhodamine B and tetracycline degradation. The results indicated that AACN had excellent photocatalytic performance for rhodamine B degradation with a rate constant of 0.0125 min^?1, which was higher than those of Ag₂WO₄ and Ag/Ag₂WO₄. Characterization and photocatalytic tests showed that the strong coupling effect between the Ag/Ag₂WO₄ nanoparticles and the exfoliated ultrathin g‐C₃N₄ nanosheets was superior for visible‐light responsivity and reduced the recombination rate of photogenerated electrons and holes. A proposed mechanism is also discussed according to the band energy structure and the experimental results.     

Improved Photocatalytic Activity and Stability of Nano‐sized Ag/Ag2CO3 Plasmonic Photocatalyst by Surface Modification of Fe(III) Nanocluster

The surface modification of Ag/Ag₂CO₃ with Fe(III) ions has been achieved through simply photoreduction‐impregnation method. The obtained products were characterized by means of X‐ray diffraction (XRD), scanning electron microscopy (SEM), X‐ray photoelectron spectroscopy (XPS), and UV‐vis absorption spectroscopy. Under visible‐light irradiation (γ>420 nm), the Fe(III)/Ag/Ag₂CO₃ sample displays a higher photocatalytic activity and stability than pure Ag₂CO₃ and Ag/Ag₂CO₃ samples for the degradation of methyl orange (MO). The improved photocatalytic activity and stability of this ternary system could be ascribed to the synergetic effect between Ag nanoparticles and Fe(III) nanocluster. The metallic Ag nanoparticles cause an obviously enhanced visible‐light absorption to produce more photogenerated charges, while the Fe(III) works as an active site for the following oxygen reduction to reduce the recombination rate of photogenerated electrons and holes.     

Synthesis of V5+‐doped Ag/AgCl photocatalysts with enhanced visible light photocatalytic activity

V⁵⁺‐doped Ag/AgCl photocatalysts were prepared via the ion exchange method. The catalysts were characterized using X‐ray diffractometry, transmission electron microscopy, and energy‐dispersive X‐ray, X‐ray photoelectron, Fourier transform infrared and ultraviolet–visible spectroscopies. The V⁵⁺‐doped Ag/AgCl photocatalysts show much higher photocatalytic activities than Ag/AgCl under visible light irradiation for methyl orange (MO) decomposition. Especially, the 2.0 wt% V⁵⁺‐doped Ag/AgCl photocatalyst shows the highest photocatalytic activity and also high stability after five cycles. The MO degradation rate during each cycle is almost maintained at 97%. Electron spin resonance spectroscopy and radical trapping experiments reveal that holes play an important role in the photocatalytic process.     

还原氧化石墨烯-硒化银纳米复合材料的水热合成与表征及其活性氧物种产生(英文)

A visible-light photocatalyst containing Ag2Se and reduced graphene oxide(RGO) was synthesized by a facile sonochemical-assisted hydrothermal method. X-ray diffraction, scanning electron mi-croscopy with energy-dispersive X-ray analysis, and ultraviolet-visible diffuse reflectance spectros-copy results indicated that the RGO-Ag2Se nanocomposite contained small crystalline Ag2Se nano-particles dispersed over graphene nanosheets and absorbed visible light. The high crystallinity of the nanoparticles increased photocatalytic activity by facilitating charge transport. N2 adsorp-tion-desorption measurements revealed that the RGO-Ag2Se nanocomposite contained numerous pores with an average diameter of 9 nm, which should allow reactant molecules to readily access the Ag2Se nanoparticles. The RGO-Ag2Se nanocomposite exhibited higher photocatalytic activity than bulk Ag2Se nanoparticles to degrade organic pollutant rhodamine B and industrial dye Texbrite BA-L under visible-light irradiation(λ 420 nm). The generation of reactive oxygen spe-cies in RGO-Ag2Se was evaluated through its ability to oxidize 1,5-diphenylcarbazide to 1,5-diphenylcarbazone. The small size of the Ag2Se nanoparticles in RGO-Ag2Se was related to the use of ultrasonication during their formation, revealing that this approach is attractive to form po-rous RGO-Ag2Se materials with high photocatalytic activity under visible light.     

Microwave‐Hydrothermal Preparation and Visible‐Light Photoactivity of Plasmonic Photocatalyst Ag‐TiO2 Nanocomposite Hollow Spheres

Visible‐light‐driven plasmonic photocatalyst Ag‐TiO₂ nanocomposite hollow spheres are prepared by a template‐free chemically‐induced self‐transformation strategy under microwave‐hydrothermal conditions, followed by a photochemical reduction process under xenon lamp irradiation. The prepared samples are characterized by using scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, N₂ adsorption‐desorption isotherms, X‐ray photoelectron spectroscopy, UV/Vis and Raman spectroscopy. Production of ?OH radicals on the surface of visible‐light illuminated TiO₂ was detected by using a photoluminescence method with terephthalic acid as the probe molecule. The photocatalytic activity of as‐prepared samples was evaluated by photocatalytic decolorization of Rhodamine B (RhB) aqueous solution at ambient temperature under visible‐light irradiation. The results show that the surface plasmon absorption band of the silver nanoparticles supported on the TiO₂ hollow spheres was red shifted, and a strong surface enhanced Raman scattering effect for the Ag‐TiO₂ nanocomposite sample was observed. The prepared nanocomposite hollow spheres exhibits a highly visible‐light photocatalytic activity for photocatalytic degradation of RhB in water, and their photocatalytic activity is higher than that of pure TiO₂ and commercial Degussa P25 (P25) powders. Especially, the as‐prepared Ag‐TiO₂ nanocomposite hollow spheres at the nominal atomic ratio of silver to titanium ( R ) of 2 showed the highest photocatalytic activity, which exceeds that of P25 by a factor of more than 2.     

Facile Synthesis of Ag/Ag3PO4 Composites with Highly Efficient and Stable Photocatalytic Performance under Visible Light

The Ag/Ag₃PO₄ composites with various shapes (spheres, polyhedral, and microcubes) were synthesized by a facile precipitation method and a subsequent light‐reduction route at room temperature. The as‐prepared Ag/Ag₃PO₄ composites were characterized in detail by X‐ray diffraction, Fourier transform infrared spectra, X‐ray photoelectron spectroscopy, scanning electron microscopy, UV–vis diffuse reflection, and photoluminescence spectroscopy. The growth processes of different morphologies Ag/Ag₃PO₄ composites are also discussed. The decomposition test of rhodamine B (RhB) indicated that the Ag/Ag₃PO₄ composites enhanced the photocatalytic performance compared with pure Ag₃PO₄, which was attributed to the surface plasmon resonance (SPR) of Ag nanoparticles and the stability of the photocatalysts. Moreover, uniform cubes of Ag/Ag₃PO₄ showed the highest photocatalytic activity and could completely degrade RhB in 7 min, which could be primarily ascribed to the cubic structure of Ag/Ag₃PO₄ with strong visible‐light absorption and efficient separation of the photo‐generated electrons and holes. Furthermore, the possible photocatalytic mechanism is also discussed.     

Visible‐Light Photocatalytic Activity and Deactivation Mechanism of Ag3PO4 Spherical Particles

Ag₃PO₄ spherical particles were synthesized by a facile precipitation method using silver nitrate and Na₂HPO₄ as precursors. The as‐prepared samples had a high photocatalytic activity toward Rhodamine B (RhB) degradation under visible‐light illumination. With increasing recycling times the photocatalytic activity first increased and then decreased. Based on systematic characterization of particles by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), UV/Vis absorption spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM), a possible mechanism responsible for the improvement and subsequent decline of the photocatalytic performance of Ag₃PO₄ is proposed. Ag₃PO₄ spherical particles recycled for four times showed the highest photocatalytic activity because, according to our mechanism, Ag nanoparticles deposited on Ag₃PO₄ acted as electron trapping centers to prevent photogenerated electron‐hole pairs from recombination. A further increase in the recycle times decreases the photocatalytic activity owing to the shielding effect by Ag layers on the surface of Ag₃PO₄. The results presented herein shed new light on the photostability of Ag₃PO₄ spherical particles and are potentially applicable to other photocatalytically active composites.     

Preparation of high‐activity AgBr/Ag3PO4 photocatalyst based on hexadecyltrimethylammonium bromide and mechanism of photocatalytic enhancement

A high‐activity AgBr/Ag₃PO₄ heterojunction photocatalyst was synthesized based on hexadecyltrimethylammonium bromide. Its microspheres were characterized using X‐ray diffractometry, transmission electron microscopy and ultraviolet–visible diffuse reflectance spectroscopy. The new photocatalyst with high photocatalytic activity exceptionally outperforms pure Ag₃PO₄ and AgBr in methyl orange degradation. The enhancement of photocatalytic activity is attributed to the efficient separation of electron–hole pairs. In this photocatalytic reaction, h⁺ and ^?O^2? are the main reactive species that induce visible‐light‐driven degradation.     

Sonochemical Synthesis of Ag/AgCl Nanocubes and Their Efficient Visible‐Light‐Driven Photocatalytic Performance

A novel one‐step sonochemical approach to synthesize a plasmonic photocatalyst of AgCl nanocubes (ca. 115 nm in edge length) with a small amount of Ag metal species is presented. The nanoscale Ag/AgCl hybrid photocatalysts with cubic morphology are readily formed under ambient ultrasonic conditions and neither external heat treatment nor reducing agents are required. The size of the Ag/AgCl photocatalysts could be controlled by changing the concentrations of Ag⁺ ions and polyvinylpyrrolidone molecules in precursor solutions. The compositions, microstructures, influencing factors, and possible growth mechanism of the Ag/AgCl hybrid nanocubes were systematically investigated. The Ag/AgCl photocatalysts show excellent photocatalytic performance for degradation of various dye molecules under visible light.     

Synthesis of Highly Efficient Ag@AgCl Plasmonic Photocatalysts with Various Structures

By means of a simple ion‐exchange process (using different precursors) and a light‐induced chemical reduction reaction, highly efficient Ag@AgCl plasmonic photocatalysts with various self‐assembled structures—including microrods, irregular balls, and hollow spheres—have been fabricated. All the obtained Ag@AgCl catalysts were characterized by means of X‐ray diffraction, X‐ray photoelectron spectroscopy, scanning electron microscopy, and UV‐visible diffuse reflectance spectroscopy. The effect of the different morphologies on the properties of the photocatalysts was studied. The average content of elemental Ag in Ag@AgCl was found to be about 3.2 mol %. All the catalysts show strong absorption in the visible‐light region. The obtained Ag@AgCl samples exhibit enhanced photocatalytic activity for the degradation of organic contaminants under visible‐light irradiation. The stability of the plasmonic photocatalysts was also investigated in detail.     

Facile subsequently light-induced route to highly efficient and stable sunlight-driven Ag-AgBr plasmonic photocatalyst

In this paper, we successfully fabricate a stable and highly efficient direct sunlight plasmonic photocatalyst Ag-AgBr through a facile hydrothermal and subsequently sunlight-induced route. The diffuse reflectance spectra of Ag-AgBr indicate strong absorption in both UV and visible light region. The obtained photocatalyst shows excellent sunlight-driven photocatalytic performance. It can decompose organic dye within several minutes under direct sunlight irradiation and maintain a high level even though used five times. In addition, both the scanning electron microscopy images and X-ray photoelectron spectroscopy dates reveal the as-prepared photocatalyst to be very stable. Moreover, the mechanism suggests that the high photocatalytic activity and excellent stability result from the super sensitivity of AgBr to light, the surface plasmon resonance of Ag nanoparticles in the region of visible light, and the complexation between Ag(+) and nitrogen atom. Thus, the facile preparation and super performance of Ag-AgBr will make it available to utilize sunlight efficiently to remove organic pollutants, destroy bacteria, and so forth.     

Preparation of Antibacterial Waterborne Polyurethane/silver Nanocomposite

Stable aqueous dispersions of silver (Ag) nanoparticles were prepared by reducing silver nitrate solutions with sodium borohydride (NaBH₄) in the presence of waterborne polyurethane as a stabilizing agent. WPU/Ag nanocomposites were obtained after evaporating water. Transmission electron microscope (TEM) shows nanoscale Ag particles are well dispersed in WPU matrix at a lower concentration, while particles exhibit a little aggregation at a higher concentration. UV‐visible spectra, X‐ray powder diffraction, and energy dispersive X‐ray spectrometer (EDS) confirm the existence of Ag particle in WPU matrix. The WPU/Ag composite films show good antibiotic ability.     

Metallogels Derived from Silver Coordination Polymers of C3‐Symmetric Tris(pyridylamide) Tripodal Ligands: Synthesis of Ag Nanoparticles and Catalysis

By applying a recently developed crystal engineering rationale, four C₃ symmetric tris(pyridylamide) ligands namely 1,3,5‐tris(nicotinamidomethyl)‐2,4,6‐triethylbenzene, 1,3,5‐tris(isonicotinamidomethyl)‐2,4,6‐triethylbenzene, 1,3,5‐tris(nicotinamidomethyl)‐2,4,6‐trimethylbenzene, and 1,3,5‐tris(isonicotinamidomethyl)‐2,4,6‐trimethylbenzene, which contain potential hydrogen‐bonding sites, were designed and synthesized for generating Ag^I coordination polymers and coordination‐polymer‐based gels. The coordination polymers thus obtained were characterized by single‐crystal X‐ray diffraction. The silver metallogels were characterized by transmission electron microscopy (TEM) and dynamic rheology. Upon exposure to visible light, these silver metallogels produced silver nanoparticles (AgNPs), which were characterized by TEM, powder X‐ray diffraction, energy dispersive X‐ray and X‐ray photoelectron spectroscopy. These NPs were found to be effectively catalyzed the reduction of 4‐nitrophenolate to 4‐aminophenolate without the use of any exogenous reducing agent.     

Different Silver Nanoparticles in One Crystal: Ag210(iPrPhS)71(Ph3P)5Cl and Ag211(iPrPhS)71(Ph3P)6Cl

Two pure silver nanoparticles (Ag₂₁₀(ⁱPrPhS)₇₁(Ph₃P)₅Cl and Ag₂₁₁(ⁱPrPhS)₇₁(Ph₃P)₆Cl labeled as SD/Ag210 and SD/Ag211 (SD=SunDi), were found to co‐crystallize in forming compound 1 . Single‐crystal X‐ray diffraction (SCXRD) revealed that they differ by only one Ag(PPh₃). Their four‐shell nanoparticles consist of three pure Ag metal shells (Ag₁₉@Ag₅₂@Ag₄₅) shielded by a silver‐organic Ag₈₉(ⁱPrPhS)₇₁Cl[Ag(Ph₃P)]_n outermost shell. The number (n) of Ag(Ph₃P) is five for SD/Ag210 and six for SD/Ag211. The pseudo‐fivefold symmetric Ag nanoparticles exhibit surface plasmon absorption similar to a true metallic state but at the nanoscale. This work exemplifies the important effects of phosphine in stabilizing large silver nanoparticles; and offers a platform to investigate the origin of differences in nanoscale metal materials, even differing by only one metal atom; it also sheds light on the regioselective binding of auxiliary Ph₃P on the surface of silver nanoparticles.     

Visible-light-driven heterostructure Ag/Bi2WO6 nanocomposites synthesized by photodeposition method and used for photodegradation of rhodamine B dye

Visible-light-driven heterostructure Ag/Bi₂WO₆ nanocomposites were prepared by transforming Ag⁺ ions into metallic Ag⁰ nanoparticles loaded on top of Bi₂WO₆ nanoplates under visible light irradiation for 1 h. XRD, XPS, SEM and TEM analyses indicated that spherical metallic Ag nanoparticles were uniformly dispersed on top of orthorhombic Bi₂WO₆ thin nanoplates. Rhodamine B (RhB) was used as a dye model for investigation of photocatalytic performance of Bi₂WO₆ nanoplates with different weight contents of Ag nanoparticles illuminated by visible radiation. In this research, 10% Ag/Bi₂WO₆ nanocomposites have the highest photocatalytic activity in the degradation of RhB at 94.21% within 210 min because of the rapid diffusion of electronic charge through the Schottky barrier between metallic Ag nanoparticles and Bi₂WO₆ thin nanoplates, good electrical conductivity of metallic Ag nanoparticles, inhibited recombination of charge carriers and enhanced photocatalytic activity of Ag/Bi₂WO₆ nanocomposites. Main active species of the photocatalysis and stability of the photocatalyst were also evaluated.

     

Photocatalytic property of surface-modified TiO<Subscript>2</Subscript> nanobelts under visible light irradiation

A novel plasmonic photocatalyst, i.e., acid-etched TiO₂ nanobelts attached with Ag/AgI nanoparticles (NPs) was prepared by deposition–precipitation-photoreduction method. Such surface-modified nanobelts had larger area than the normal one. Ag NPs were formed from AgI by photo-reduction under Xenon lamp irradiation. X-ray diffraction, scanning electron microscopy analysis, UV–Vis diffuse reflectance spectra and fluorescence spectra were used to characterize the structure and optical properties of the sample. The obtained sample exhibited strong photodegradation of methyl orange (MO) under visible light irradiation, which were attributed to both the surface plasmon resonance of Ag NPs and the visible light actived AgI. The photodegradation was accomplished by the transfer of photoexcited electrons from the Ag NPs to the acid-etched TiO₂ nanobelts. After four cycles of photodegradation the photocatalyst was still stable. This novel photocatalyst had a high potential application in wastewater-treatment and biomedical engineering.     

Nitrile‐functionalized Hg(II)‐ and Ag(I)‐N‐heterocyclic carbene complexes: synthesis,crystal structures,nuclease and DNA binding activities

Various nitrile‐functionalized benzimidazol‐2‐ylidene carbene complexes of Hg(II) and Ag(I) were synthesized by the interaction of 1‐benzyl/1‐butyl‐3‐(cyano‐benzyl)‐3 H‐benzimidazol‐1‐ium mono/dihexafluorophosphate with Hg(OAc)₂/Ag₂O in acetonitrile. Two of the benzimidazolium salts were structurally characterized by single crystal X‐ray diffraction technique. Structures of reported compounds were characterized by ¹ H, ¹³C NMR, FT‐IR, UV–visible spectroscopic techniques, and molar conductivity and elemental analyses. For bis‐benzimidazolium salt, dinuclear Hg(II)– and Ag(I)–carbene complexes were obtained. Nuclease activity and binding interactions of the synthesized benzimidazolium salts and their Ag(I)–carbene complexes with DNA were studied using agarose gel electrophoresis and, absorption spectroscopy and viscosity measurements, respectively. Ag(I)–carbene complexes showed higher DNA binding activity compared to their respective benzimidazolium salts. However, a benzimidazolium salt and two of the Ag(I) complexes showed remarkably higher nuclease activity both, in the presence and absence of an oxidizing agent. Copyright © 2012 John Wiley & Sons, Ltd.     

Surface Plasmon Resonance‐Enhanced Visible‐NIR‐Driven Photocatalytic and Photothermal Catalytic Performance by Ag/Mesoporous Black TiO2 Nanotube Heterojunctions

Ag/mesoporous black TiO₂ nanotubes heterojunctions (Ag‐MBTHs) were fabricated through a surface hydrogenation, wet‐impregnation and photoreduction strategy. The as‐prepared Ag‐MBTHs possess a relatively high specific surface area of ≈85 m² g^?1 and an average pore size of ≈13.2 nm. The Ag‐MBTHs with a narrow band gap of ≈2.63 eV extend the photoresponse from UV to the visible‐light and near‐infrared (NIR) region. They exhibit excellent visible‐NIR‐driven photothermal catalytic and photocatalytic performance for complete conversion of nitro aromatic compounds (100 %) and mineralization of highly toxic phenol (100 %). The enhancement can be attributed to the mesoporous hollow structures increasing the light multi‐refraction, the Ti³⁺ in frameworks and the surface plasmon resonance (SPR) effect of plasmonic Ag nanoparticles favoring light‐harvesting and spatial separation of photogenerated electron–hole pairs, which is confirmed by transient fluorescence. The fabrication of this SPR‐enhanced visible‐NIR‐driven Ag‐MBTHs catalyst may provide new insights for designing other high‐performance heterojunctions as photocatalytic and photothermal catalytic nanomaterials.     

Ag@AgCl修饰的锐钛矿相TiO2纳米管的制备及其光催化性能

首先采用水热合成法和双氧水处理制备了具有锐钛矿相的TiO2纳米管,然后通过沉淀和光化学反应将Ag@AgCl纳米粒子负载于其上,从而制得TiO2纳米管负载的表面等离子体光催化剂.结果表明,经Ag@AgCl纳米粒子修饰后,锐钛矿相TiO2纳米管因表面等离子共振效应而对可见光具有明显的响应,光生电子-空穴对更容易分离,因而T...     

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.