Underpotential Deposition Preparation of Pt‐loading AuNPs/Reduced Graphene Oxide and Its Catalytic Detection of Catechol

Ultralow Pt‐loading Au nanoparticles have been fabricated on the surface of reduced graphene oxide (RGO) by using underpotential deposition (UPD) monolayer redox replacement process. The Pt/Au/RGO modified electrode exhibits an excellent electrocatalytic activity toward catechol and hydroquinone. Under the optimized condition, the separation of peak‐to‐peak between hydroquinone and catechol is 197 mV, which is wide enough to distinguish the isomers of benzenediol. Catechol is detected by the Pt/Au/RGO/GCE with a low detection limit in the presence of hydroquinone.     

Dual Amplified Electrochemical Immunosensor for Hepatitis B Virus Surface Antigen Detection Using Hemin/G‐Quadruplex Immobilized onto Fe3O4‐AuNPs or (Hemin‐Amino‐rGO‐Au) Nanohybrid

A sensitive electrochemical immunosensor for Hepatitis B virus surface antigen (HBsAg) detection was fabricated based on hemin/G‐quadruplex interlaced onto Fe₃O₄‐AuNPs or hemin ‐amino‐reduced graphene oxide nanocomposite (H‐amino‐rGO‐Au). G‐quadruplex DNAzyme, which is composed of hemin and guanine‐rich nucleic acid, is an effective signal amplified tool for its outstanding peroxidase activity and Fe₃O₄‐AuNPs or (H‐amino‐rGO‐Au) nanocomposites with quasi‐enzyme activity provide appropriate support for the immobilization of hemin/G‐quadruplex. The target protein was sandwiched between the primary antibody immobilized on the GO and secondary antibody immobilized on the Fe₃O₄‐AuNPs or (H‐amino‐rGO‐Au) nanocomposites and glutaraldehyde was used as linking agent for the immobilization of primary antibody on the surface of GO. Both Fe₃O₄‐AuNPs and H‐amino‐rGO‐Au nanocomposite and also hemin/G‐quadruplex can cooperate the electrocatalytic reduction of H₂O₂ in the presence of methylene blue as mediator. The proposed immunosensor has a wide linear dynamic range of 0.1 pg/ml to 300 pg/ml with a detection limit of 60 fg/ml when Fe₃O₄‐AuNPs was used for immobilization of hemin/G‐quadruplex, while the dynamic range and DL were 0. 1–1000 pg/mL and 10 fg/mL, respectively in the presence of H‐amino‐rGO‐ Au nanocomposite as platform for immobilizing of hemin/G‐quadruplex. The proposed immunosensor was also used for analysis of HBsAg in spiked human serum samples with satisfactory results.     

Tailored Synthesis of Various Nanomaterials by Using a Graphene‐Oxide‐Based Gel as a Nanoreactor and Nanohybrid‐Catalyzed CC Bond Formation

New graphene oxide (GO)‐based hydrogels that contain vitamin B₂/B₁₂ and vitamin C (ascorbic acid) have been synthesized in water (at neutral pH value). These gel‐based soft materials have been used to synthesize various metal nanoparticles, including Au, Ag, and Pd nanoparticles, as well as nanoparticle‐containing reduced graphene oxide (RGO)‐based nanohybrid systems. This result indicates that GO‐based gels can be used as versatile reactors for the synthesis of different nanomaterials and hybrid systems on the nanoscale. Moreover, the RGO‐based nanohybrid hydrogel with Pd nanoparticles was used as an efficient catalyst for C? C bond‐formation reactions with good yields and showed high recyclability in Suzuki–Miyaura coupling reactions.     

Photocatalytically Renewable Micro‐electrochemical Sensor for Real‐Time Monitoring of Cells

Electrode fouling and passivation is a substantial and inevitable limitation in electrochemical biosensing, and it is a great challenge to efficiently remove the contaminant without changing the surface structure and electrochemical performance. Herein, we propose a versatile and efficient strategy based on photocatalytic cleaning to construct renewable electrochemical sensors for cell analysis. This kind of sensor was fabricated by controllable assembly of reduced graphene oxide (RGO) and TiO₂ to form a sandwiching RGO@TiO₂ structure, followed by deposition of Au nanoparticles (NPs) onto the RGO shell. The Au NPs‐RGO composite shell provides high electrochemical performance. Meanwhile, the encapsulated TiO₂ ensures an excellent photocatalytic cleaning property. Application of this renewable microsensor for detection of nitric oxide (NO) release from cells demonstrates the great potential of this strategy in electrode regeneration and biosensing.     

Self‐Assembly and Compartmentalization of Nanozymes in Mesoporous Silica‐Based Nanoreactors

Herein, to mimic complex natural system, polyelectrolyte multilayer (PEM)‐coated mesoporous silica nanoreactors were used to compartmentalize two different artificial enzymes. PEMs coated on the surface of mesoporous silica could serve as a permeable membrane to control the flow of molecules. When assembling hemin on the surface of mesoporous silica, the hemin‐based mesoporous silica system possessed remarkable peroxidase‐like activity, especially at physiological pH, and could be recycled more easily than traditional graphene–hemin nanocompounds. The hope is that these new findings may pave the way for exploring novel nanoreactors to achieve compartmentalization of nanozymes and applying artificial cascade catalytic systems to mimic cell organelles or important biochemical transformations     

Core shell‐structured NiFe2O4@TiO2 nanoparticle‐anchored reduced graphene oxide for rapid degradation of rhodamine B

In this work, the NiFe₂O₄@TiO₂/reduced graphene oxide (RGO) ternary nanocomposites with high saturation magnetization and catalytic efficiency have been synthesized through the following steps. First, graphene oxide was prepared using the modified Hummer's method. Second, the NiFe₂O₄ nanoparticles were successfully prepared using the hydrothermal method. Third, the core shell‐structured NiFe₂O₄@TiO₂/RGO nanocomposite precursors were easily obtained through hydrolysis reaction. The morphology of NiFe₂O₄@TiO₂/RGO nanocomposites was characterized from scanning electron microscope (SEM) and transmission electron microscope (TEM) images. Moreover, the results of X‐ray diffraction (XRD) patterns proved that the TiO₂ coating shell consisted of anatase. The vibrating sample magnetometer (VSM) measurements showed that the saturation magnetization value of NiFe₂O₄@TiO₂/RGO ternary nanocomposites was 25 emu/g. The X‐ray photoelectron spectroscopy (XPS) analysis confirmed that only part of the graphite oxide (GO) was reduced to RGO in the ternary nanocomposite. The degradation experiments proved that NiFe₂O₄@TiO₂/RGO nanocomposite exhibited the high catalytic efficiency and outstanding recyclable performance for rhodamine B (RhB).     

Poly(N‐vinylpyrrolidone)‐Decorated Reduced Graphene Oxide with ZnO Grown In Situ as a Cathode Buffer Layer for Polymer Solar Cells

A ZnO@reduced graphene oxide–poly(N‐vinylpyrrolidone) (ZnO@RGO‐PVP) nanocomposite, prepared by in situ growth of ZnO nanoparticles on PVP‐decorated RGO (RGO‐PVP) was developed as a cathode buffer layer for improving the performance of polymer solar cells (PSCs). PVP not only favors homogeneous distribution of the RGO through the strong π–π interactions between graphene and PVP molecules, but also acts as a stabilizer and bridge to control the in situ growth of sol–gel‐derived ZnO nanoparticles on the surface of the graphene. At the same time, RGO provides a conductive connection for independent dispersion of ZnO nanoparticles to form uniform nanoclusters with fewer domain boundaries and surface traps. Moreover, the LUMO level of ZnO is effectively improved by modification with RGO‐PVP. Compared to bare ZnO, a ZnO@RGO‐PVP cathode buffer layer substantially reduces the recombination of carriers, increases the electrical conductivity, and enhances electron extraction. Consequently, the power conversion efficiency of an inverted device based on thieno[3,4‐b]thiophene/benzodithiophene (PTB7):[6,6]‐phenyl C₇₁‐butyric acid methyl ester (PC₇₁BM) with ZnO@RGO‐PVP as cathode buffer layer was greatly improved to 7.5 % with improved long‐term stability. The results reveal that ZnO@RGO‐PVP is universally applicable as a cathode buffer layer for improving the performance of PSCs.     

Formation of PdNiZn thin film at oil‐water interface: XPS study and application as Suzuki‐Miyaura catalyst

Nanosheet of PdNiZn and nanosphere of PdNiZn/reduced‐graphene oxide (RGO) with sub‐3 nm spheres have been successfully synthesized through a facile oil‐water interfacial strategy. The morphology and composition of the films were determined by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive analysis of X‐ray (EDAX) and elemental mapping. In the present study, we have developed a method to minimize the usage of precious Pd element. Due to the special structure and intermetallic synergies, the PdNiZn and PdNiZn/RGO nanoalloys exhibited enhanced catalytic activity and durability relative to Pd nanoparticles in Suzuki‐Miyaura C‐C cross‐coupling reaction. Compared to classical cross‐coupling reactions, this method has the advantages of a green solvent, short reaction times, low catalyst loading, high yields and reusability of the catalysts.     

Label‐free Electrochemical Aptasensor for Carcino‐embryonic Antigen Based on Ternary Nanocomposite of Gold Nanoparticles,Hemin and Graphene

In this report, a label‐free electrochemical aptasensor for carcino‐embryonic antigen (CEA) was successfully developed based on a ternary nanocomposite of gold nanoparticles, hemin and graphene nanosheets (AuNPs‐HGNs). This nanocomposite was prepared by decorating gold nanoparticles on the surface of hemin functionalized graphene nanosheets via a simple wet‐chemical strategy. The aptamer can be assembled on the surface of AuNPs‐HGNs/GCE (glassy carbon electrode) through Au‐S covalent bond to form the sensing interface. Hemin absorbed on the graphene nanosheets not only acts as a protective agent of graphene sheets, but also as an in situ probe base on its excellent redox properties. Gold nanoparticles provide with both numerous binding sites for loading CEA binding aptamer (CBA) and good conductivity to promote the electron transfer. The current changes, which are caused by CEA specifically binding on the modified electrode, are exploited for the label‐free detection of CEA in a very rapid and convenient protocol. Therefore, the method has advantages of high sensitivity, wide linear range (0.0001–10 ng mL^?1), low detection limit (40 fg mL^?1) and attractive specificity. The results illustrate that the proposed label‐free electrochemical aptasensor has a potential application in the biological or clinical target analysis for its simple operation and low cost.     

一步法制备还原态氧化石墨烯载铂纳米粒子及其对甲醇氧化的电催化性能

以天然石墨为原料,采用改进的Hummers法制备氧化石墨.然后采用简单的一步化学还原法在乙二醇(EG)中同时还原氧化石墨烯(GO)和H₂PtCl₆制备高分散的铂/还原态氧化石墨烯(Pt/RGO)催化剂.采用傅里叶变换红外(FTIR)光谱、X射线衍射(XRD)和透射电子显微镜(TEM)对催化剂的微结构、组成和形貌进行表征.结果表明, GO已被还原成RGO, Pt纳米粒子均匀分散在RGO表面,粒径约为2.3 nm.采用循环伏安法和计时电流法评价催化剂对甲醇氧化的电催化性能,测试结果表明, Pt/RGO催化剂对甲醇氧化的电催化活性和稳定性与Pt/C和Pt/CNT相比有了很大提高.另外其对甲醇电催化氧化的循环伏安图中正扫峰电流密度(I_f)和反扫峰电流密度(I_b)的比值高达1.3,分别是Pt/C和Pt/CNT催化剂的2.2和1.9倍,表明Pt/RGO催化剂具有高的抗甲醇氧化中间体CO_ad的中毒能力.     

Hemin‐Functionalized Reduced Graphene Oxide Nanosheets Reveal Peroxynitrite Reduction and Isomerization Activity

Facile and efficient reduction of graphene oxide (GO) and novel applications of the reduced graphene oxide (RGO) based materials are of current interest. Herein, we report a novel and facile method for the reduction of GO by using a biocompatible reducing agent dithiothreitol (DTT). Stabilization of DTT by the formation of a six‐membered ring with internal disulfide linkage upon oxidation is responsible for the reduction of GO. The reduced graphene oxide is characterized by several spectroscopic and microscopic techniques. Dispersion of RGO in DMF remained stable for several weeks suggesting that the RGO obtained by DTT‐mediated reduction is hydrophobic in nature. This method can be considered for large scale production of good quality RGO. Treatment of RGO with hemin afforded a functional hemin‐reduced graphene oxide (H‐RGO) hybrid material that exhibited remarkable protective effects against the potentially harmful peroxynitrite (PN). A detailed inhibition study on PN‐mediated oxidation and nitration reactions indicate that the interaction between hemin and RGO results in a synergistic effect, which leads to an efficient reduction of PN to nitrate. The RGO also catalyzes the isomerization of PN to nitrate as the RGO layers facilitate the rapid recombination of ^.NO₂ with Fe^IV=O species. In the presence of reducing agents such as ascorbic acid, the Fe^IV=O species can be reduced to Fe^III, thus helping to maintain the PN reductase cycle.     

Electrografted Poly(N‐mercaptoethyl acrylamide) and Au Nanoparticles‐Based Organic/Inorganic Film: A Platform for the High‐Performance Electrochemical Biosensors

In this study, we describe the use of the combination of eletrografting poly(N‐mercaptoethyl acrylamide) and Au nanoparticles in the construction of high‐performance biosensors. The poly(N‐mercaptoethyl acrylamide) was electrografted onto the glassy carbon electrode surface, which provided a strongly adhering primer film for the stable attachment of Au nanoparticles and horseradish peroxidase (HRP) enzymes. The performances of the biosensors based on the HRP immobilized in the Au/poly(N‐mercaptoethyl acrylamide) composite film were investigated. A couple of redox peaks were obtained, indicating that the Au nanoparticles could facilitate the direct‐electron transfer between HRP and the underlying electrode. The biosensor showed an excellent electrocatalytic activity toward the reduction of hydrogen oxide and long‐term stability, owing to the stable electrografted film and biocompatible Au nanoparticles. Our results demonstrate that the combination of electrografting and Au nanoparticles provides a promising platform for the immobilization of biomolecules and analysis of redox enzymes for their sensing applications.     

Electrochemical Biosensor Utilizing Supramolecular Association of Enzyme on Sol−gel Matrix Embedded Gold Nanoparticles Supported Reduced Graphene Oxide−cyclodextrin Nanocomposite

Herein we present β‐cyclodextrin (CD)‐functionalized reduced graphene oxide (RGO) nanosheets supported on silicate sol‐gel matrix‐embedded gold nanoparticles (Au NPs) modified electrode as a new affinity binding nanocomposite. The modified electrode is fabricated through layer‐by‐layer drop casting followed by immobilization of chemically modified enzyme conjugate (horse radish peroxidase (HRP)?adamantane carboxylic acid (ADA)). This affinity system is based on the supramolecular association between CDs and HRP?ADA and is mimicking the biological avidin?biotin interactions. CDs‐functionalized RGO (RGO?CD) functions as a macrocyclic host to form stable supramolecular inclusion complexes with enzyme conjugate. Besides Au NPs improve the interfacial interaction with RGO?CD nanosheets, and thus exhibit synergistic electrocatalytic effect toward H₂O₂ reduction in the presence of 1 mM hydroquinone.     

A Ternary Composite Based on Graphene,Hemin, and Gold Nanorods with High Catalytic Activity for the Detection of Cell‐Surface Glycan Expression

A novel graphene‐family ternary composite with high catalytic activity has been developed by using simple synthetic methods. The graphene‐based ternary composite has abundant positively charged Au NRs, which greatly improved the catalytic properties of the graphene‐family of peroxidase mimetics, because of the high electron‐transfer rate of graphene and the synergistic interaction of three components. Sensitive detection of glycan expression on K562 cell surface can be achieved with a low detection limit of 10 cells. This finding constitutes a novel graphene‐family hybrid nanomaterials‐based peroxidase mimetic that is expected to be applied widely in the construction of simple, sensitive, and selective biosensors for nucleic acids and proteins both inside and outside of cells through catalytic reaction of H₂O₂.     

Tunable Catalytic Performance and Selectivity of a Nanoparticle–Graphene Composite through Finely Controlled Nanoparticle Loading

Graphene‐based composites offer enhanced catalytic performance of metal and semiconductor nanoparticles, but their development is challenging because catalytic performance strongly depends on the structure and composition of the composite. Herein we show that the catalytic performance of a nanoparticle–graphene composite is very dependent on catalyst loading, which can be optimized for simultaneous enhancement of activity and selectivity. A glassy carbon working electrode has been modified with a gold nanoparticle–graphene (Au–G) composite with a varied number of gold nanoparticles per graphene, so that the conducting property of graphene and the electrocatalytic property of the metal were effectively coupled to give the best catalytic activity and selectivity. The modified electrode was used for simultaneous electrochemical detection of a mixture of electroactive species with high sensitivity. This result shows that the catalytic performance of a graphene‐based composite is sensitive to the catalyst loading and should be optimized for the best performance.     

Preparation of FePd‐RGO Bimetallic Composites with High Catalytic Activity for Formic Acid Electro‐Oxidation

FePd‐RGO composites through the growth of uniformly dispersed iron‐palladium bimetallic nanoparticles (NPs) on reduced graphene oxide (RGO) nanosheets were prepared by a two‐step method. The firstly formed Fe is used as the seed for the subsequent Pd growth. The formation of Fe NPs on RGO in the first step is performed by an in‐situ reduction reaction with the reducer ethylene glycol under oil bath at 180°C. NPs in the as‐prepared FePd‐RGO have an average particle size of 6.5 nm, and Pd is added to one side of Fe which leads to the formation of Fe‐Pd bimetallic interfaces. As compared with the commercial Pd black at the same loading, the composites have higher electro‐catalytic activity, better electrochemical stability and higher resistance to CO poisoning for formic acid electro‐oxidation.     

Preparation of Cu nanoparticle‐doped ZIF‐8/RGO composites for effective photodegradation of organic pollutant

Cu nanoparticle‐connected ZIF‐8/reduced graphite oxide (RGO) composite was successfully prepared through a facile hydrothermal reaction using sulfate in this paper. The crossover mechanism of metal nanoparticles loading and RGO decoration to enhance the photocatalytic efficiency of pristine ZIF‐8 was studied. The results showed that the prepared Cu‐S@ZIF‐8/RGO has a strong ability to take advantage of sunlight, indicating an appreciable application prospect. RGO can act as a base to support the whole structure and serve as an electron sink to accept photoexcited electrons, realizing the formation of reactive oxygen species (ROS) and inhibition of electron–hole pair recombination. Cu nanoparticles act as connectors between ZIF‐8 and RGO to transfer electrons and realize the formation of partial ROS on its surface. The doped sulfate radical can promote to extend the utilization of the wavelength range by generating surface states. Cu‐S@ZIF‐8/RGO showed the best photocatalytic activity in simulated sunlight for eliminating rhodamine B and 4‐chlorophenol among all the prepared samples, the structure kept intact even in the presence of different kinds of anions. The crossover study of metal loading and RGO decoration can develop a new way for only UV‐responsive metal–organic frameworks to remove organic contaminants under sunlight irradiation.     

Investigation of Platinum Dispersed on Reduced Graphene Oxide‐supported Tungsten Carbide via Sacrificial Cu Adlayers for Methanol Oxidation

Reduced graphene oxide‐supported tungsten carbide composite (WC/RGO) was prepared by program‐controlled reduction‐carburization technique. Scanning electron microscope (SEM) and transmission electron microscope (TEM) show that WC nanoparticles with a narrow distribution (10–20 nm) are highly dispersed both on the edge and between the layers of RGO. And then it was used as a support to load different low contents (no more than 0.4 wt%) of Pt via sacrificial Cu adlayers. The morphology and the electrocatalytic activity of the prepared catalysts were characterized by TEM and cyclic voltammograms (CV), respectively. The results indicate that a small amount of isolated Pt atoms show low or even no activity for methanol oxidation. With the increasing deposition cycles, the content of Pt and the ensembles of neighboring Pt atoms are increased, which makes the onset potential shift negatively and mass current density increase. The results demonstrate that controllable amount of Pt can be deposited on WC/RGO by galvanic displacement with Cu, and the extent and domain of Pt loading affect the electrochemical performance. Meanwhile, this research also provides another route to prepare a catalyst with ultra low noble metal on WC/RGO for solving the problem of high cost of the catalyst.     

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.     

Highly sensitive electrochemical determination of Sunset Yellow based on gold nanoparticles/graphene electrode

An electrochemical sensor was prepared using Au nanoparticles and reduced graphene successfully decorated on the glassy carbon electrode (Au/RGO/GCE) through an electrochemical method which was applied to detect Sunset Yellow (SY). The as-prepared electrode was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM) and electrochemical measurements. The results of cyclic voltammetry (CV) proved that Au/RGO/GCE had the highest catalytic activity for the oxidation of SY as compared with GCE, Au/GCE, and RGO/GCE. Differential pulse voltammetry (DPV) showed that the linear calibration curves for SY on Au/RGO/GCE in the range of 0.002 μM–109.14 μM, and the detection limit was estimated to be 2 nM (S/N = 3). These results suggested that the obtained Au/RGO/GCE was applied to detect SY with high sensitivity, low detection limit and good stability, which provided a promising future for the development of portable sensor in food additives.