还原氧化石墨烯/金纳米修饰电极在新冠病毒检测中的应用

研究使用电化学沉积法在丝网印刷碳电极表面制备了还原氧化石墨烯和金纳米颗粒,构建了一种用于新冠病毒检测的石墨烯电化学传感器。通过扫描电子显微镜(SEM)和相应的电化学方法对纳米复合材料在电极表面的成功修饰进行了表征分析。并采用差分脉冲伏安法对传感器的性能进行检测,实验构建的电化学传感器具有良好的灵敏度,该传感器检线性范围为10_-10^-10_-6^mol/L,具有良好的重复性和特异性。     

Surface‐Plasmon‐Enhanced Band Emission of ZnO Nanoflowers Decorated with Au Nanoparticles

A simple strategy was used to enhance band emission through the transfer of defect emission from ZnO to Au by using the energy match between the defect emission of ZnO and the surface plasmon absorbance of Au NPs through decorating the surface of ZnO nanoflowers with Au nanoparticles (Au NPs). The ZnO nanostructure, which was comprised of six nanorods that were attached on one side in a flower‐like fashion, was synthesized by using a hydrothermal method. The temperature‐dependent morphology and detailed growth mechanism were studied. The influence of the density of the Au NPs that were deposited onto the surface of ZnO on photoluminescence was investigated to optimize the configuration of the ZnO/Au system in terms of the maximum band emission. The sequential transfer of defect energy from ZnO to Au and electron transfer from excited Au to ZnO was proposed as a possible mechanism for the enhanced band emission.     

Selective and Simultaneous Determination of Dihydroxybenzene Isomers Based on Green Synthesized Gold Nanoparticles Decorated Reduced Graphene Oxide

In the present study, we report the simultaneous electrochemical determination of hydroquinone (HQ), catechol (CC) and resorcinol (RC) at gold nanoparticles (Au‐NPs) decorated reduced graphene oxide (RGO) modified electrode. An enhanced and well defined peak current response with a better peak separation of HQ, CC and RC is observed at RGO/Au‐NPs composite than that of RGO and Au‐NPs modified electrodes. The fabricated modified electrode shows a wide linear response in the concentration range of 3–90 µM, 3–300 µM and 15–150 µM for HQ, CC and RC, respectively. The detection limit of HQ, CC and RC is found as 0.15 µM, 0.12 µM and 0.78 µM, respectively.     

有序介孔三氧化二铟/还原氧化石墨烯纳米复合材料的制备及可见光催化性能

以有序介孔三氧化二铟(m-In2O3)和还原氧化石墨烯(RGO)为原料,采用紫外光照射法合成了介孔三氧化二铟/还原氧化石墨烯(m-In2O3-RGO)复合光催化剂.利用N2吸附-脱附、X射线衍射(XRD)、透射电子显微镜(TEM)、漫反射吸收光谱(DRS)和光电流测试等手段对样品进行表征.在可见光照射下,以对氯苯酚(4-CP)为目标污染物,考察了m-In2O3-RGO光催化剂的催化性能.结果表明,m-In2O3-RGO光催化剂具有完整的晶型和规则的孔道结构,有利于光生电子和空穴的分离.同时,作为固态电子受体与传输体的RGO促进了光生电子-空穴对的传输和分离,有效提高了可见光催化性能.掺杂2%(质量分数)RGO的复合光催化剂性能最佳,4 h可将4-CP降解96%以上,催化剂经多次循环使用后,其光催化活性基本保持不变.     

Direct Photocatalysis for Organic Synthesis by Using Plasmonic‐Metal Nanoparticles Irradiated with Visible Light

Recent advances in direct‐use plasmonic‐metal nanoparticles (NPs) as photocatalysts to drive organic synthesis reactions under visible‐light irradiation have attracted great interest. Plasmonic‐metal NPs are characterized by their strong interaction with visible light through excitation of the localized surface plasmon resonance (LSPR). Herein, we review recent developments in direct photocatalysis using plasmonic‐metal NPs and their applications. We focus on the role played by the LSPR of the metal NPs in catalyzing organic transformations and, more broadly, the role that light irradiation plays in catalyzing the reactions. Through this, the reaction mechanisms that these light‐excited energetic electrons promote will be highlighted. This review will be of particular interest to researchers who are designing and fabricating new plasmonic‐metal NP photocatalysts by identifying important reaction mechanisms that occur through light irradiation.     

Plasmon‐Enhanced Photocurrent Generation from Click‐Chemically Modified Graphene

The visible‐light response of Au nanoparticles (AuNPs) assembled on rGO through different molecular bridges was investigated by transient photocurrent generation. We prepared rGO with two self‐assembled monolayers (SAMs), one linear and the other with aromatic triazoles through a click cycloaddition reaction. A fivefold photocurrent enhancement was observed for triazole linkers over the aminopropyltrimethoxysilane (APTMS) linker. Cyclic voltammetry (CV) and impedance measurements also suggest fast electron transfer on account of the low resistance offered by the click‐modified rGO surface whereby introduction of triazoles offers the efficient bridge between the donor AuNPs and acceptor rGO.     

微接触印刷技术转移Au纳米粒子及氧化石墨烯复合图案及其性质研究

通过改良的“Hummers方法”制得氧化石墨烯,利用聚二甲基硅氧烷（PDMS）弹性印章的微接触印刷技术,以Au膜和氧化石墨烯溶液为“墨水”,通过二次印章转移,分别将Au纳米粒子和氧化石墨烯（Graphene Oxide,GO）转移至修饰了(3-氨基丙基)三乙氧基硅烷（APTES）的ITO基底（APTES/ITO）表面. 利用场发射扫描电子显微镜（FE-SEM）、原子力显微镜（AFM）等表征图案,结果表明转移的AuNPs和GO组成的复合图案均匀,致密性较好. 利用表面电势显微镜（Surface Potential Microscope,SEPM,KFM）测定了各部分的表面电势,以APTES/ITO基底表面为表面电势零点,各部分表面电势大小为：APTES/ITO > GO > Au（0,-11.6,-44.2 mV）.     

Multilayer‐Functionalized Reduced Graphene Oxide Decorated with Gold Nanoparticles as a Designed Nanonanocatalyst for the Selective Oxidation of Cyclohexene by Molecular Oxygen in a Solvent‐Free System

The aerobic oxidation of cyclohexene is of great significance from the viewpoints of both fundamental and industry studies as it can transfer the petrochemical feedstock into valuable chemicals. In this research, gold nanoparticles were synthesized on the multi‐layer functionalized reduced graphene oxide . The surface of reduced graphene oxide (rGO) was modified with hydrophobic and hydrophilic layers to create the rGO with scattered hydrophilic positions. The gold nanoparticles were synthesized and immobilized simultaneously in small hydrophilic micro reactors in a mild condition. Characterization of synthesized nanocatalyst was confirmed with different techniques such as TEM, XRD, FT‐IR, and SEM. TEM images of synthesized catalyst show the gold nanoparticles have diameters less than 5 nm. Designed nanonanocatalyst was investigated for the selective liquid phase oxidation of cyclohexene with molecular oxygen in solvent free condition which after optimized conditions a maximum of 88% conversion and 91% selectivity was obtained.     

Photocatalysis by ZnS nanoparticles of the formation of ZnS/Au heterostructure in the reduction of complex ions of gold

The photocatalytic activity of ZnS nanoparticles during the reduction of the KAu(CN)₂ complex was found. The spectral characteristics of the nanocomposite ZnS/Au⁰ and also the principal kinetic relationships involved in its formation were studied. It was shown that the photoreaction has equilibrium character resulting from oxidation of the obtained gold by holes in the valence band of the zinc sulfide. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 41, No. 6, pp. 343–347, November–December, 2005.     

紫外光照射制备具有光学活性的银纳米粒子

以脱氧胆酸钠（NaDC）为还原剂、稳定剂,经紫外光辐照AgNO₃溶液在室温下制备出尺寸30nm左右的类球形的银纳米粒子。用紫外-可见光谱、透射电镜、圆二色谱和傅立叶变换红外光谱等测试手段对所制备的脱氧胆酸钠包裹的银纳米粒子进行了表征。红外光谱结果表明,在紫外光激发下,脱氧胆酸钠甾环上12α-OH发生氧化反应,同时还原Ag⁺为单质银,并聚集生成银纳米粒子。溶液的pH值对光化学氧化还原反应速度有着重要的影响,增加溶液的pH值,Ag⁺的还原反应速度明显加快。在吸附在银粒子表面的脱氧胆酸钠的手性氛围诱导下,生成的银纳米粒子在其表面等离子体共振区域出现手性信号。     

紫外光照射制备具有光学活性的银纳米粒子

以脱氧胆酸钠(NaDC)为还原剂、稳定剂,经紫外光辐照AgNO3溶液在室温下制备出尺寸30 nm左右的类球形的银纳米粒子。用紫外-可见光谱、透射电镜、圆二色谱和傅立叶变换红外光谱等测试手段对所制备的脱氧胆酸钠包裹的银纳米粒子进行了表征。红外光谱结果表明,在紫外光激发下,脱氧胆酸钠甾环上12α-OH发生氧化反应,同时还原Ag+为单质银,并聚集生成银纳米粒子。溶液的pH值对光化学氧化还原反应速度有着重要的影响,增加溶液的pH值,Ag+的还原反应速度明显加快。在吸附在银粒子表面的脱氧胆酸钠的手性氛围诱导下,生成的银纳米粒子在其表面等离子体共振区域出现手性信号。     

Novel Multifunctional Graphene Sheets with Encased Au/Ag Nanoparticles for Advanced Electrochemical Analysis of Organic Compounds

This work is the first presentation of the synthesis of few‐layer graphene decorated with gold and silver nanoparticles (Gr–Au–Ag) by chemical vapor deposition over a catalytic system formed of bimetallic Au–Ag nanoclusters supported on MgO and with methane used as the source of carbon. The sheetlike morphology of the graphene nanostructures, with mean sizes in the range of hundreds of nanometers, was observed by high‐resolution electron microscopy. The distinctive feature found in all the samples was the regular rectangular or square shapes. This multi‐component organic–inorganic nanomaterial was used to modify a platinum substrate and subsequently employed for the detection of carbamazepine, an anti‐convulsion drug. UV/Vis spectroscopy revealed that a strong hypochromism occurred over time, after mixing solutions of graphene–Au–Ag with carbamazepine. This can be attributed to π–π stacking between the aromatic groups of the two compounds. Linear sweep voltammetry (LCV) provided evidence that the modified platinum substrate presented a significant electrocatalytic reaction toward the oxidation of carbamazepine. The intensity of the current was found to increase by up to 2.5 times, and the oxidation potential shifted from +1.5 to +1.35 V(Ag/AgCl) in comparison with the unmodified electrode. Electrochemical impedance spectroscopy (EIS) was further used to thoroughly assess the activity of the platinum electrode that was modified by the deposition of the Gr‐Au‐Ag composites in the presence of various concentrations of carbamazepine. The experimental EIS records were used for the generation of an equivalent electrical circuit, based on the charge‐transfer resistance (R_ct), Warburg impedance (Z_D), solution resistance (R_s), and a constant phase element (CPE) that characterizes the non‐ideal interface capacitive responses.     

Zeolite‐Supported Gold Nanoparticles for Selective Photooxidation of Aromatic Alcohols under Visible‐Light Irradiation

With new photocatalysts of gold nanoparticles supported on zeolite supports (Au/zeolite), oxidation of benzyl alcohol and its derivatives into the corresponding aldehydes can proceed well with a high selectivity (99 %) under visible‐light irradiation at ambient temperature. Au/zeolite photocatalysts were characterised by UV/Vis, X‐ray photoelectron spectroscopy (XPS), TEM, XRD, energy‐dispersive spectroscopy (EDS), Brauner–Emmet–Teller (BET) analyses, IR and Raman techniques. The surface plasmon resonance (SPR) effect of gold nanoparticles, the adsorption capability of zeolite supports and the molecular polarities of aromatic alcohols were demonstrated to have an essential correlation with the photocatalytic performances. In addition, the effects of light intensity, wavelength range and the role of molecular oxygen were investigated in detail. The kinetic study indicated that the visible‐light irradiation required much less apparent activation energy for photooxidation compared with thermal reaction. Based on the characterisation data and the photocatalytic performances, we proposed a possible photooxidation mechanism.     

Surfactant‐Free Nonaqueous Synthesis of Plasmonic Molybdenum Oxide Nanosheets with Enhanced Catalytic Activity for Hydrogen Generation from Ammonia Borane under Visible Light

Plasmonic materials have drawn emerging interest, especially in nontraditional semiconductor nanostructures with earth‐abundant elements and low resistive loss. However, the actualization of highly efficient catalysis in plasmonic semiconductor nanostructures is still a challenge, owing to the presence of surface‐capping agents in their synthetic procedures. To fulfill this, a facile non‐aqueous procedure was employed to prepare well‐defined molybdenum oxide nanosheets in the absence of surfactants. The obtained MoO_3‐x nanosheets display intense absorption in a wide range attributed to the localized surface plasmon resonances, which can be tuned from the visible to the near‐infrared region. Herein, we demonstrate that such plasmonic semiconductor nanostructures could be used as highly efficient catalysts that dramatically enhance the hydrogen‐generation activity of ammonia borane under visible light irradiation.     

SiO2-Coated ZnO Nanoflakes Decorated with Ag Nanoparticles for Photocatalytic Water Oxidation

Many strategies have been adopted to improve the photoinduced features of zinc oxide nanostructures for different application fields. In this work, zinc oxide has been synthesised and decorated by plasmonic metal nanoparticles to enhance its photocatalytic activity in the visible range. Furthermore, an insulating layer of SiO₂ has been grown between the surface of zinc oxide nanoflakes and silver nanoparticles. A synthetic procedure that allows the accurate modulation of the insulating layer thickness in the range 5–40 nm has been developed. Evidences highlight the crucial role of the SiO₂ layer in dramatically increasing photocatalytic water oxidation promoted by the nanostructure under both UV and visible illumination. An ideal thickness value of about 10 nm has been demonstrated to guarantee the plasmon-induced resonance energy-transfer process and to quench the Förster resonance energy-transfer mechanism; thus, optimising the local surface plasmon resonance effect and water oxidation properties.     

Oxidation Ability of Plasmon‐Induced Charge Separation Evaluated on the Basis of Surface Hydroxylation of Gold Nanoparticles

The oxidation ability of plasmonic photocatalysts, which has its origins in plasmon‐induced charge separation and has not yet been studied quantitatively and systematically, is important for designing practical photocatalytic systems. Oxidation ability was investigated on the basis of surface hydroxylation of Au nanoparticles on TiO₂ at various irradiation wavelengths and electrolyte pH values. The reaction proceeds only when the sum of the flat band potential of TiO₂ and the irradiated photon energy is close to, or more positive than, the theoretical potential for the reaction.     

Control of Surface Plasmon Resonance of Au/SnO2 by Modification with Ag and Cu for Photoinduced Reactions under Visible‐Light Irradiation over a Wide Range

Gold particles supported on tin(IV) oxide (0.2 wt % Au/SnO₂) were modified with copper and silver by the multistep photodeposition method. Absorption around λ=550 nm, attributed to surface plasmon resonance (SPR) of Au, gradually shifted to longer wavelengths on modification with Cu and finally reached λ=620 nm at 0.8 wt % Cu. On the other hand, the absorption shifted to shorter wavelength with increasing amount of Ag and reached λ=450 nm at 0.8 wt % Ag. These Cu‐ and Ag‐modified 0.2 wt % Au/SnO₂ materials (Cu‐Au/SnO₂ and Ag‐Au/SnO₂) and 1.0 wt % Au/SnO₂ were used for mineralization of formic acid to carbon dioxide in aqueous suspension under irradiation with visible light from a xenon lamp and three kinds of light‐emitting diodes with different wavelengths. The reaction rates for the mineralization of formic acid over these materials depend on the wavelength of light. Apparent quantum efficiencies of Cu‐Au/SnO₂, Au/SnO₂, and Ag‐Au/SnO₂ reached 5.5 % at 625 nm, 5.8 % at 525 nm, and 5.1 % at 450 nm, respectively. These photocatalysts can also be used for selective oxidation of alcohols to corresponding carbonyl compounds in aqueous solution under visible‐light irradiation. Broad responses to visible light in formic acid mineralization and selective alcohol oxidation were achieved when the three materials were used simultaneously.     

Enhancing Hematite Photoanode Activity for Water Oxidation by Incorporation of Reduced Graphene Oxide

Two effective methods to prepare reduced graphene oxide (rGO)/hematite nanostructured photoanodes and their photoelectrochemical characterization towards water splitting reactions are presented. First, graphene oxide (GO) is reduced to rGO using hydrazine in a basic solution containing tetrabutylammonium hydroxide (TBAOH), and then deposited over the nanostructured hematite photoanodes previously treated at 750 °C for 30 min. The second method follows the deposition of a paste containing a mixture of hematite nanoparticles and rGO sheets by the doctor‐blade method, varying the rGO concentration. Since hematite suffers from low electron mobility, a low absorption coefficient, high recombination rates and slow reaction kinetics, the incorporation of rGO in the hematite can overcome such limitations due to graphene's exceptional properties. Using the first method, the rGO incorporation results in a photocurrent density increase from 0.56 to 0.82 mA cm^?2 at 1.23 V_RHE. Our results indicate that the rGO incorporation in the hematite photoanodes shows a positive effect in the reduction of the electron–hole recombination rate.     

Visible‐Light‐Induced Electron Transport from Small to Large Nanoparticles in Bimodal Gold Nanoparticle‐Loaded Titanium(IV) Oxide

A key to realizing the sustainable society is to develop highly active photocatalysts for selective organic synthesis effectively using sunlight as the energy source. Recently, metal‐oxide‐supported gold nanoparticles (NPs) have emerged as a new type of visible‐light photocatalysts driven by the excitation of localized surface plasmon resonance of Au NPs. Here we show that visible‐light irradiation (λ>430 nm) of TiO₂‐supported Au NPs with a bimodal size distribution (BM‐Au/TiO₂) gives rise to the long‐range (>40 nm) electron transport from about 14 small (ca. 2 nm) Au NPs to one large (ca. 9 nm) Au NP through the conduction band of TiO₂. As a result of the enhancement of charge separation, BM‐Au/TiO₂ exhibits a high level of visible‐light activity for the one‐step synthesis of azobenzenes from nitrobenzenes at 25 °C with a yield greater than 95 % and a selectivity greater than 99 %, whereas unimodal Au/TiO₂ (UM‐Au/TiO₂) is photocatalytically inactive.     

Enhanced Magneto‐optical Properties of Semiconductor EuS Nanocrystals Assisted by Surface Plasmon Resonance of Gold Nanoparticles

Remarkable magneto‐optical properties of a new isolator material, that is, europium sulfide nanocrystals with gold (EuS–Au nanosystem), has been demonstrated for a future photo‐information technology. Attachment of gold particles that exhibit surface plasmon resonance leads to amplification of the magneto‐optical properties of the EuS nanocrystals. To construct the EuS–Au nanosystems, cubic EuS and spherical Au nanocrystals have been joined by a variety of organic linkers, that is, 1,2‐ethanedithiol (EDT), 1,6‐hexanedithiol (HDT), 1,10‐decanedithiol (DDT), 1,4‐bisethanethionaphthalene (NpEDT), or 1,4‐bisdecanethionaphthalene (NpDDT) . Formation of these systems was observed by XRD, TEM, and absorption spectra measurements. The magneto‐optical properties of the EuS–Au nanosystem have been characterized by using Faraday rotation spectroscopy. The Faraday rotation angle of the EuS–Au nanosystem is dependent on the Au particle size and interparticle distance between EuS and Au nanocrystals. Enhancement of the Faraday rotation of EuS–Au nanosystems was observed. The spin configuration in the excited state of the EuS–Au nanosystem was also investigated using photo‐assisted electron paramagnetic resonance.