Visible‐light‐driven self‐cleaning SERS substrate of silver nanoparticles and graphene oxide decorated nitrogen‐doped titania nanotube array

Graphene oxide (GO) and silver nanoparticles (Ag NPs) sequentially decorated nitrogen‐doped titania nanotube array (N‐TiO₂ NTA) had been designed as visible‐light‐driven self‐cleaning surface‐enhanced Raman scattering (SERS) substrate for a recyclable SERS detection application. N‐TiO₂ NTA was fabricated by anodic oxidation and then doping nitrogen treatment in ammonia atmosphere, acting as a visible‐light‐driven photocatalyst and supporting substrate. Ag/GO/N‐TiO₂ NTA was prepared by decorating GO monolayer through an impregnation process and then depositing Ag NPs through a polyol process on the surface of N‐TiO₂ NTA, acting as the collection of organic molecule and Raman enhancement. The SERS activity of Ag/GO/N‐TiO₂ NTA was evaluated using methyl blue as an organic probe molecule, revealing the analytical enhancement factor of 4.54 × 10⁴. Ag/GO/N‐TiO₂ NTA was applied as active SERS substrate to determine a low‐affinity organic pollutant of bisphenol A, revealing the detection limit of as low as 5 × 10^?7 m . Ag/GO/N‐TiO₂ NTA could also achieve self‐cleaning function for a recycling utilization through visible‐light‐driven photocatalytic degradation of the adsorbed organic molecules. Ag/GO/N‐TiO₂ NTA has been successfully reused for five times without an obvious decay in accuracy and sensitivity for organic molecule detection. The unique properties of this SERS substrate enable it to have a promising application for the sensitive and recyclable SERS detection of low‐affinity organic molecules. Copyright © 2016 John Wiley & Sons, Ltd.     

ZnGa2O4 Nanorod Arrays Decorated with Ag Nanoparticles as Surface‐Enhanced Raman‐Scattering Substrates for Melamine Detection

The availability of sensitive, reproducible, and stable substrates is critically important for surface‐enhanced Raman spectroscopy (SERS)‐based applications, but it presently remains a challenge. In this work, well‐aligned zinc gallate (ZnGa₂O₄) nanorod arrays grown on a Si substrate by chemical vapor deposition were used as templates to fabricate SERS substrates by deposition of Ag nanoparticles onto the ZnGa₂O₄ nanorod surfaces. The coverage of the Ag nanoparticles on the ZnGa₂O₄ nanorod surfaces was easily controlled by varying the amount of AgNO₃. SERS measurements showed that the number density of Ag nanoparticles on the ZnGa₂O₄ nanorod surfaces had a great effect on SERS activity. The SERS signals collected by point‐to‐point and SERS mapping images showed that as‐prepared SERS substrates exhibited good spatial uniformity and reproducibility. Detection of melamine molecules at low concentrations (1.0×10^?7 M ) was used as an example to show the possible application of such a substrate. In addition, the effect of benzoic acid on the detection of melamine was also investigated. It was found that the SERS signal intensity of melamine decreased greatly as the concentration of benzoic acid was increased.     

Recent Developments in the Plant‐Mediated Green Synthesis of Ag‐Based Nanoparticles for Environmental and Catalytic Applications

Among different metallic nanoparticles, sliver nanoparticles (Ag NPs) are one of the most essential and fascinating nanomaterials. Importantly, among the metal based nanoparticles, Ag NPs play a key role in various fields such as biomedicine, biosensors, catalysis, pharmaceuticals, nanoscience and nanotechnology, particularly in nanomedicine. A main concern about the chemical synthesis of Ag NPs is the production of hazardous chemicals and toxic wastes. To overcome this problem, many research studies have been carried out on the green synthesis of Ag NPs using green sources such as plant extracts, microorganisms and some biopolymers without formation of hazardous wastes. Among green sources, plants could be remarkably valuable to exploring the biosynthesis of Ag NPs. In this review, the green synthesis of Ag‐based nanocatalysts such as Ag NPs, AgPd NPs, Au?Ag NPs, Ag/AgPd NPs, Ag/Cu NPs, Ag@AgCl NPs, Au?Ag@AgCl nanocomposite, Ag?Cr‐AC nanocomposite and Ag NPs immobilized on various supports such as Natrolite zeolite, bone, ZnO, seashell, hazelnut shell, almond shell, SnO₂, perlite, ZrO₂, TiO₂, α‐Al₂O₃, CeO₂, reduced graphene oxide (rGO), h‐Fe₂O₃@SiO₂, and Fe₃O₄ using numerous plant extracts as reducing and stabilizing agents in the absence of hazardous surfactant and capping agents has been focused. This work describes the state of the art and future challenges in the biosynthesis of Ag‐based nanocatalysts. The fact about the application of living plants in metal nanoparticle (MNPs) industry is that it is a more economical and efficient biosynthesis biosynthetic procedure. In addition, the catalytic activities of the synthesized, Ag‐based recyclable nanocatalysts using various plant extracts in several chemical reactions such as oxidation, reduction, coupling, cycloaddition, cyanation, epoxidation, hydration, degradation and hydrogenation reactions have bben extensively discussed.     

Gas-Phase Deposited Plasmonic Nanoparticles Supported on 3D-Graphene/Nickel Foam for Highly SERS Detection

In this work, we proposed a novel three-dimensional (3D) plasmonic nanostructure based on porous graphene/nickel foam (GNF) and gas-phase deposited Ag nanoparticles (NPs).Ag NPs with high density were directly deposited on the surface of 3D GNF by performing a novel cluster beam deposition approach. In comparison with traditional Ag substrate(SiO₂/Ag), such hot-spots enriched 3D nanostructure showed extremely high electromag-netic field enhancement under incident light irradiation which could be used as a sensitive chemical sensor based on surface enhanced Raman scattering (SERS). The experimental results demonstrated that the proposed nanostructure showed superior SERS performance in terms of Raman signal reproducibility and sensitivity for the probe molecules. 3D full-wave simulation showed that the enhanced SERS performance in this 3D hierarchical plasmonic nanostructure was mainly obtained from the hot-spots between Ag NPs and the near-field coupling between Ag NPs and GNF sca olds. This work can provide a novel assembled SERS substrate as a SERS-based chemical sensor in practical applications.     

Effect of TiO2 on Altering Direction of Interfacial Charge Transfer in a TiO2‐Ag‐MPY‐FePc System by SERS

Interfacial charge transfer (CT) is of interest owing to its effect on the performance of molecular photovoltaic (PV) devices. The characteristics and structures of interfacial materials, such as TiO₂ nanoparticles (NPs) in some solar cells, are employed to adjust the CT process. In this study, three kinds of interfacial systems, including a solar cell‐like TiO₂‐Ag‐ p‐mercaptopyridine (MPY)‐ iron phthalocyanine (FePc) system, are compared to investigate the interfacial CT process using surface‐enhanced Raman scattering (SERS) spectroscopy. The SERS results show the significance of TiO₂ NPs in the system on altering the direction and path of the interfacial CT, which is closely associated with the CT enhancement contribution to SERS in such an interfacial system. SERS spectroscopy is expected to be a promising technique for the exploration and estimation of the interfacial CT behavior in PV devices, which may further extend the applications of SERS in the field of solar cells.     

Highly Selective and Active Pd‐In/three‐dimensional Graphene with Special Structure for Electroreduction CO2 to Formate

Electrocatalytic reduction of CO₂ to formate on carbon based electrodes is known to suffer from low electrochemical reaction activity and product selectivity. Pd/three‐dimensional graphene (Pd/3D‐RGO), In/3D‐RGO and Pd‐In/3D‐RGO for the electrochemical reduction of CO₂ were prepared by a mild method that combines chemical and hydrothermal. The metal/3D‐graphenes (metal/3D‐RGO) were characterized by scanning electron microscopy, X‐ray diffraction, transmission electron microscopy and X‐ray photoelectron spectroscopy (XPS). Cyclic voltammetry and the ion chromatography were performed to investigate the electrochemical performance of the metal/3D‐RGO. The morphology and dispersion of metal/3D‐RGO are 3D structure with amount of interconnected pores with metal NPs loading on the fold. And the Pd_0.5‐In_0.5/3D‐RGO show excellent surface performance with well dispersion and smallest particle size (12.8 nm). XPS reveal that binding energy of Pd (In) NPs is shifted to negative energy, for the metal lose electrons in metal and combine with C, which is demonstrated in the HNO₃ experiment. The peak potential of Pd_0.5‐In_0.5/3D‐RGO is −0.70 V (vs. Ag/AgCl), which is more positive than In_1.0/3D‐RGO (−0.73 V) and Pd_1.0/3D‐RGO (−1.2 V). The highest faradaic efficiency (85.3 %) happens in Pd_0.5‐In_0.5/3D‐RGO at −1.6 V vs. Ag/AgCl. In these experiments, the special structure that metal NPs combine with C and the bimetal NPs give a direction to convert CO₂ to formate.     

Biocompatible Triplex Ag@SiO2@mTiO2 Core–Shell Nanoparticles for Simultaneous Fluorescence‐SERS Bimodal Imaging and Drug Delivery

Herein, we report the synthesis of biocompatible triplex Ag@SiO₂@mTiO₂ core–shell nanoparticles (NPs) for simultaneous fluorescence‐surface‐enhanced Raman scattering (F‐SERS) bimodal imaging and drug delivery. Stable Raman signals were created by typical SERS tags that were composed of Ag NPs for optical enhancement, a reporter molecule of 4‐mercaptopyridine (4‐Mpy) for a spectroscopic signature, and a silica shell for protection. A further coating of mesoporous titania (mTiO₂) on the SERS tags offered high loading capacity for a fluorescence dye (flavin mononucleotide) and an anti‐cancer drug (doxorubicin (DOX)), thereby endowing the material with fluorescence‐imaging and therapeutic functions. The as‐prepared F‐SERS dots exhibited strong fluorescence when excited by light at 460 nm whilst a stable, characteristic 4‐Mpy SERS signal was detected when the excitation wavelength was changed to longer wavelength (632.8 nm), both in solution and after incorporation inside living cells. Their excellent biocompatibility was demonstrated by low cytotoxicity against MCF‐7 cells, even at a high concentration of 100 μg mL^?1. In vitro cell cytotoxicity confirmed that DOX‐loaded F‐SERS dots had a comparable or even greater therapeutic effect compared with the free drug, owing to the increased cell‐uptake, which was attributed to the possible endocytosis mechanism of the NPs. To the best of our knowledge, this is the first proof‐of‐concept investigation on a multifunctional nanomedicine that possessed a combined capacity for fast and multiplexed F‐SERS labeling as well as drug‐loading for cancer therapy.     

Preparation of chitosan functionalized end‐capped Ag‐NPs and composited with Fe3O4‐NPs: Controlled release to pH‐responsive delivery of progesterone and antibacterial activity against pseudomonas aeruginosa (PAO‐1)

In this work, functionalized chitosan end‐capped Ag nanoparticles (NPs) and composited with Fe₃O₄‐NPs was prepared as pH‐responsive controlled release carrier for gastric‐specific drug delivery. The structure of prepared material was characterized by FE‐SEM, XRD, EDS and FT‐IR analysis. The loading behavior of the progesterone onto this novel material was studied in aqueous medium at 25°C and their release was followed spectrophotometrically at 37°C in seven different buffer solutions (pH 1.2, 2.2, 3.2, 4.2, 5.2, 6.2 and 7.2) to simulate intestine and gastric media which experimental results reveal more release rate in pH 1.2 (gastric medium) with respect to other buffers. This observation is attributed to dependency of the CS‐IMBDO‐Ag‐Fe₃O₄‐NPs and progesterone structure with buffer pH that candidate this new material as prospective pH‐sensitive carrier for gastric‐targeted drug delivery. On the other hand, the antibacterial properties of this material against gram‐negative bacterium pseudomonas aeruginosa (PAO‐1) in agar plates was studied and accordingly based on broth micro dilution the minimum bactericidal concentration (MBC) and minimum inhibitory concentration (MIC) with respect to standard CLSI in different concentrations of CS‐IMBDO‐Ag‐Fe₃O₄‐NPs was calculated. The results reveal that MIC and MBC values are 50 and 1250 μg/mL, respectively. In addition, extracts of Portulaca oleracea leaves was prepared and its antibacterial activity in single and binary system with CS‐IMBDO‐Ag‐Fe₃O₄‐NPs as synergies effect against PAO‐1 was tested and results shown that these materials have significant synergistic effect for each other.     

A 3D Polyoxometalate‐Based Framework Constructed from Ag/trz Metal‐Organic Ribbons and P2W18 Polyoxoanions: Synthesis,Structure and Electrochemical Properties

A Wells‐Dawson Polyoxometalate‐based hybrid, Ag₉(trz)₃(Htrz)₄ (H₂O)(P₂W₁₈O₆₂)·3H₂O ( 1 ) (Htrz = 1,2,4‐1H‐triazole) was hydrothermally synthesized through using trz ligand and silver nitrate in the presence of [P₂W₁₈O₆₂]^6– polyoxoanion. In the 3D framework structure of compound 1 , two kinds of wave‐like Ag/trz chains originated from trz ligands and silver cations are aggregated in a “2+1” mode by {Ag₂/trz} linkages to result in a 1D Ag/trz metal‐organic ribbon, which is further extended into a 3D framework structure by [P₂W₁₈O₆₂]^6– polyoxoanions through Ag‐O covalent bonds. Additionally, the electrochemical properties of compound 1 have also been investigated.     

Mn Oxide‐Silver Composite Nanowires for Improved Thermal Stability,SERS and Electrical Conductivity

Redox transformation reaction between aqueous AgNO₃ and Mn(CH₃COO)₂ at low temperature (～80 °C) has been adopted for industrial‐scale production of uniform Ag–MnOOH composite nanowires for the first time. Varying amounts of incorporated Ag in the composite retain the 1D morphology of the composite. Nanowires upon annealing evolve Ag–MnO₂ nanocomposites, once again with the retention of the parental morphology. Just 4 % of silver incorporation in the composite demonstrates metal‐like conducting performance from the corresponding semiconducting material. Transition of MnO₂ to Mn₂O₃ to Mn₃O₄ takes place upon heat treatment in relation to successive increase in Ag concentrations in the nanowires. The composites offer resistance to the observed oxide transformation. This is evidenced from the progressive increase in transition temperature. In situ Raman, ex situ thermal and XRD analysis corroborate the fact. The composite with 12 % Ag offers resistance to the transformation of MnO₂, which is also verified from laser heating. Importantly, Ag nanoparticle incorporation is proved to offer a thermally stable and better surface enhanced Raman scattering (SERS) platform than the individual components. Both the Ag–MnOOH and Ag–MnO₂ nanocomposites with 8 atomic % Ag show the best SERS enhancement (enhancement factor ～10¹⁰). The observed enhancement relates to charge transfer as well as electromagnetic effects.     

Synthesis,Structures, and Properties of a Series of New Coordination Polymers Built from 2‐Ethyl‐1H‐imidazole‐4,5‐dicarboxylate Ligand

A series of new coordination polymers, namely, [Sr(H₂EIDC)₂(H₂O)₂]_n ( 1 ),{[Pb(H₂EIDC)₂(H₂O)](H₂O)₃}_n ( 2 ), [Ag(H₂EIDC)]_n ( 3 ), and [Ba(H₂EIDC)₂(H₂O)]_n ( 4 ) (H₂EIDC = 2‐ethyl‐1H‐imidazole‐4,5‐dicarboxylate), were synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, X‐ray diffraction and thermogravimetric analyses. Complex 1 is a 2D infinite gridlike (4,4)topological layer structure. Complex 2 is a 2D corrugated layer constructed by Pb^II atoms and H₂EIDC^– anions. Complex 3 is a 2D corrugated sheet consisting of 1D chains linked by short Ag ··· Ag interactions, and the three complexes are extended into 3D supramolecular structures by weak intermolecular forces such as hydrogen bonds and π–π stacking interactions. Complex 4 exhibits a 3D framework with 1D channels. Furthermore, the luminescent properties of complexes 1 , 2 , and 3 are also investigated.     

Two 3D Polyoxometalate‐based Frameworks Constructed from Silver(I)‐triazole/tetrazole Units: Hydrothermal Syntheses,Crystal Structure and Properties

Two polyoxometalate‐based compounds constructed by Keggin/Ag/ L , namely [Ag₁₀( L₁ )₆(H L₁ )₂][HPMo₂^VMo^VI₁₀O₄₀] ( 1 ) and [Ag₁₀( L₂ )₈(H₂SiMo₁₂O₄₀)] ( 2 ) ( L₁ = 1,2,4‐1H‐triazole and L₂ = 1H‐tetrazole), were synthesized under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction, elemental analyses, and IR spectroscopy. In compound 1 , the tetra‐nuclear Ag cycles constructed by four L₁ ligands, two Ag1 ions, and two Ag2 ions. Compound 1 exhibits a two dimensional (2D) metal‐organic layer containing adjacent tetra‐nuclear Ag cycles. Furthermore, the adjacent 2D layers are further extended by Ag ions to form a three dimensional (3D) channel‐like framework, with Keggin anions embedding in the channels. Compound 2 is isostructural with 1 . Additionally, the electrochemical and photocatalytic properties of the title compounds were investigated.     

pH‐Switchable Redox Reactions and Bioelectrocatalytic Processes Using Au Nanoparticles‐Modified Electrodes

Boronate ester complexes generated between methylene blue (MB⁺)‐functionalized Au nanoparticles (NPs) and electrode surfaces are implemented to stimulate the bioelectrocatalyzed reduction of H₂O₂ in the presence of horseradish peroxidase (HRP). Two kinds of Au NPs are prepared: Class I includes MB⁺/phenylboronic acid as a modifying layer, whereas Class II includes MB⁺/dithiothreitol as a mixed capping layer. The Class I or II NPs form boronate ester complexes with a dithiothreitol‐ or phenylboronic acid‐functionalized Au electrodes, respectively. By the cyclic loading of the NPs on the electrodes (pH 8.1), and the removal of the NPs (pH 1.5), switchable bioelectrocatalyzed reduction of H₂O₂ is demonstrated.     

Urchin‐like Ag Nanowires as Non‐enzymatic Hydrogen Peroxide Sensor

Urchin‐like Ag nanowires were prepared by reacting AgNO₃(aq) with Cu metal in the presence of cetyltrimethylammonium chloride and HNO₃(aq) on a screen printed carbon electrode at room temperature. The diameters of the nanowires were about 100 nm, while the lengths were up to 10 μm. Cyclic voltammetric experiments using the Ag nanowires as the working electrode showed electrocatalytic H₂O₂ reduction. The electrode exhibited a high sensitivity of 4705 μA mM^‐1 mg^‐1 cm^‐2 from 50 μM to 10.35 mM and a measurable detection limit of 10 μM in amperometric detection. This is the first report on Ag NWs for non‐enzymatic H₂O₂ sensing.     

A Surfactant‐Encapsulating Polyoxometalate Nanowire Assembly as a New Carrier for Nanoscale Noble‐Metal Catalysts

The loading of noble‐metal nanoparticles (NMNPs) onto various carriers to obtain stable and highly efficient catalysts is currently an important strategy in the development of noble metal (NM)‐based catalytic reactions and their applications. We herein report a nanowire supramolecular assembly constructed from the surfactant‐encapsulating polyoxometalates (SEPs) CTAB‐PW₁₂, which can act as new carriers for NMNPs. In this case, the Ag NPs are loaded onto the SEP nanowire assembly with a narrow size distribution from 5 to 20 nm in diameter; the average size is approximately 10 nm. The Ag NPs on the nanowire assemblies are well stabilized and the over agglomeration of Ag NPs is avoided owing to the existence of well‐arranged polyoxometalate (POM) units in the SEP assembly and the hydrophobic surfactant on the surface of the nanowire assembly. Furthermore, the loading amount of the Ag NPs can be adjusted by controlling the concentration of the AgNO₃ aqueous solution. The resultant Ag/CTAB‐PW₁₂ composite materials exhibit high activity and good stability for the catalytic reduction of 4‐nitrophenol (4‐NP) with NaBH₄ in isopropanol/H₂O solution. The NMNPs‐loaded SEP nanoassembly may represent a new composite catalyst system for application in NM‐based catalysis.     

Hybrid Coordination Networks Constructed from ɛ‐Keggin‐Type Polyoxometalates and Rigid Imidazole‐Based Bridging Ligands as New Carriers for Noble‐Metal Catalysts

Three hybrid coordination networks that were constructed from ?‐Keggin polyoxometalate building units and imidazole‐based bridging ligands were prepared under hydrothermal conditions, that is, H[(Hbimb)₂(bimb){Zn₄PMo^V8Mo^VI₄O₄₀}] ? 6 H₂O ( 1 ), [Zn(Hbimbp)(bimbp)₃{Zn₄PMo^V8Mo^VI₄O₄₀}] ? DMF ? 3.5 H₂O ( 2 ), and H[Zn₂(timb)₂(bimba)₂Cl₂{Zn₄PMo^V8Mo^VI₄O₄₀}] ? 7 H₂O ( 3 ) (bimb=1,4‐bis(1‐imidazolyl)benzene, bimbp=4,4′‐bis(imidazolyl)biphenyl, timb=1,3,5‐tris(1‐imidazolyl)benzene, bimba=3,5‐bis(1‐imidazolyl)benzenamine). All three compounds were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and single‐crystal X‐ray diffraction. The mixed valence of the Mo centers was analyzed by XPS spectroscopy and bond‐valence sum calculations. In all three compounds, the ?‐Keggin polyoxometalate (POM) units acted as nodes that were connected by rigid imidazole‐based bridging ligands to form hybrid coordination networks. In compound 1 , 1D zigzag chains extended to form a 3D supramolecular architecture through intermolecular hydrogen‐bonding interactions. Compound 2 consisted of 2D curved sheets, whilst compound 3 contained chiral 2D networks. Because of the intrinsic reducing properties of ?‐Keggin POM species, noble‐metal nanoparticles were loaded onto these POM‐based coordination networks. Thus, compounds 1 – 3 were successfully loaded with Ag nanoparticles, and the corresponding composite materials exhibited high catalytic activities for the reduction of 4‐nitrophenol.     

基于2,4′-二羧基二苯甲酮构筑的具有一维梯状链和一维隧道的三维超分子体系

采用水热法设计合成了两个新型三维超分子化合物H₂L·H₂O (1)和[Ag(bpy)₂]·HL·H₂O (2) (其中bpy=2,2'-联吡啶, H₂L=2,4′-二羧基二苯甲酮),晶体结构分析表明,它们均是通过氢键采用不同的连接方式拓展而成。其中,化合物1 是2,4′-二羧基二苯甲酮和水分子通过O–H···O氢键形成的一维梯状链扩展构筑的三维超分子体系;化合物2 则是2,4′-二羧基二苯甲酮和水分子通过两种氢键形成含有一维隧道的三维超分子体系。有趣的是,[Ag(bpy)₂]⁺ 阳离子通过π–π 堆积和弱的Ag···Ag相互作用连在一起,进而以客体形式填充其中。荧光性质研究表明,由于存在bpy的螯合与堆积效应,化合物2相比配体和化合物1,其荧光发射峰发生红移。     

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.     

Palladium Nanoparticles Embedded into Graphene Nanosheets: Preparation,Characterization, and Nonenzymatic Electrochemical Detection of H2O2

A novel nonenzymatic H₂O₂ sensor based on a palladium nanoparticles/graphene (Pd‐NPs/GN) hybrid nanostructures composite film modified glassy carbon electrode (GCE) was reported. The composites of graphene (GN) decorated with Pd nanoparticles have been prepared by simultaneously reducing graphite oxide (GO) and K₂PdCl₄ in one pot. The Pd‐NPs were intended to enlarge the interplanar spacing of graphene nanosheets and were well dispersed on the surface or completely embedded into few‐layer GN, which maintain their high surface area and prevent GN from aggregating. XPS analysis indicated that the surface Pd atoms are negatively charged, favoring the reduction process of H₂O₂. Moreover, the Pd‐NPs/GN/GCE could remarkably decrease the overpotential and enhance the electron‐transfer rate due to the good contact between Pd‐NPs and GN sheets, and Pd‐NPs have high catalytical effect for H₂O₂ reduction. Amperometric measurements allow observation of the electrochemical reduction of H₂O₂ at 0.5 V (vs. Ag/AgCl). The H₂O₂ reduction current is linear to its concentration in the range from 1×10^?9 to 2×10^?3 M, and the detection limit was found to be 2×10^?10 M (S/N=3). The as‐prepared nonenzymatic H₂O₂ sensor exhibits excellent repeatability, selectivity and long‐term stability.     

Doping and metallic‐support effect evidenced on SERS spectra of polyaniline thin films

Surface‐enhanced Raman scattering (SERS) is a process with origins, electromagnetic and chemical. The electromagnetic enhancement consists of the excitation of surface plasmons in the metallic support of the thin film. With only the electromagnetic enhancement mechanism, the surface spectra should not differ from volume Raman spectra. However, between SERS and volume Raman spectra, there are differences resulting from the chemical reactions taking place at the polymer/metal interface, intermediated by solvent molecules, that finally depend on the types of polymers and metallic supports. Polyaniline (PAN) is an excellent material to emphasize the chemical component of SERS. This is due to its particular structure with a repeating unit that contains two entities at different weights—a reduced state and an oxidized state–that, in turn, react differently with a metallic substrate. SERS spectra depend on the oxidizing properties of the metal surface, which involves an intermediate compound of the types Ag₂O and Au₂O₃ when N‐methyl‐2‐pyrrolidinone is used as the solvent. This article presents new results concerning the surface chemical effects that produce variations of the PAN SERS spectra. The SERS spectra of the PAN emeraldine base (PAN‐EB) layered on Au support are characterized by a semiquinoid structure that we believe is induced on the intermediate compound Au₂O₃. In the presence of H₂SO₄, the SERS spectra change gradually as the degree of acid protonation doping increases. The SERS spectra of the fully protonated PAN‐EB are identical to those obtained on PAN emeraldine salt (PAN‐ES) synthesized by cyclic voltammetry in an acid medium and are invariable with the type of metallic support. The SERS spectra show that the emeraldine salt can be partially or totally deprotonated with water or NH₄OH. The deprotonation is complete for the Ag support and partial for the Au support. The SERS spectra of the fully protonated PAN‐EB are characterized by a double band with maxima at about 1330 and 1370 cm⁻¹. Although the generation process of positive charge on the macromolecular chain of PAN‐EB doped in the presence of (C₄H₉)₄NBF₄ is similar to that due to protonic acid doping, involving cation addition (C₄H or H⁺ ions, respectively) in SERS spectra, the complex band situated at about 1330–1370 cm⁻¹ no longer appears. The doping of PAN‐EB with FeCl₃ produces two polymer forms: a salt type characterized by a protonated structure similar to that found for PAN‐ES and a base type similar to the leucoemeraldine form. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2599–2609, 2000