下载文档原格式
电化学氟化石墨烯的原位拉曼光谱研究钟锦辉1，蔡伟伟2，任斌1,*1厦门大学化学化工学院，固体表面物理化学国家重点实验室，厦门，3610052厦门大学物理系，厦门，361005*Email: bren@石墨烯是零带隙的半导体材料，需打开其带隙以扩展其应用范围。
实验1与理论2的研究都发现对石墨烯进行氟化可打开其带隙。
目前氟化石墨烯的方法条件苛刻且难以控制氟化程度。
我们发展了电化学氟化石墨烯的方法，原位电化学－拉曼光谱研究表明石墨烯在高电位下可被氟化。
以石墨烯为工作电极（WE），铂为对电极（CE），饱和甘汞电极（SCE）为参比电极（RE），在0.2 M NaF 溶液中进行现场电化学拉曼光谱研究。
在纯净的石墨烯上没有观察到缺陷峰（D）。
在NaF溶液中，施加电位后D峰出现（~0.9 V vs. SCE）且强度随电位正移而逐渐增强，可能是由于石墨烯在NaF溶液中发生了氟化。
通过对反应条件（电化学电位及反应时间）的调控有望控制石墨烯的氟化程度进而调控其电子性质与电化学活性。
关键词：石墨烯；氟化；电化学；拉曼光谱参考文献[1] Robinson, J. T.; Burgess, J. S.; Junkermeier, C. E. et al. Nano Lett.2010, 10: 3001.[2] Leenaerts, O.; Peelaers, H.; Hernández-Nieves, A. D. et al. Phys. Rev. B2010, 82: 195436.Electrochemical fluorination of graphene as probed by in-situelectrochemical Raman spectroscopyJin-Hui Zhong1, Weiwei Cai2, Bin Ren1,*1State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 3610052Department of Physics, Xiamen University, Xiamen, 361005Graphene is a zero band gap semiconductor with unique structural and electronic properties. Inducing a gap in graphene is crucial for its application as electronic devices. Functionalization of graphene, such as fluorination, is an effective way to open a gap. However, the existing methods for the fluorination of graphene involve either critical chemical conditions or high temperatures. Here we demonstrate that graphene could be fluorinated effectively under a mild electrochemical condition, as probed by in-situ electrochemical Raman spectroscopy.The Raman spectroelectrochemistry measurement was carried out in a three-electrode cell, in which graphene was used as the working electrode (WE). Pt wire and saturated calomel electrode (SCE) were used as the counter electrode (CE) and reference electrode (RE), respectively. The absence of defect (D) peak indicates the high quality of the pristine graphene sample. The D band appears when a potential of ~0.9 V (vs. SCE) was applied on graphene in a solution of 0.2 M NaF, suggesting the graphene may be fluorinated under high potential. The intensity of D band increases with increasing positive potential, thus by tuning the applied potential we may be able to control the degree of fluorination and finally tune the electronic properties and electrochemical activity of graphene.。
2020年03月[9]Qian Y.,Han N.,Zhang Z.,et al.Enhanced thermal-to-flexi⁃ble phase change materials based on cellulose/modified graphene composites for thermal management of solar energy[J].ACS Applied Materials &Interfaces.2019,11(49):45832-45843.[10]Yuan P.,Zhang P.,Liang T.,et al.Effects of surface func⁃tionalization on thermal and mechanical properties of graphene /polyethylene glycol composite phase change materials[J].Applied Surface Science,2019,485:402-412.[11]Zheng F.,Jiang P.,Hu L.,et al.Functionalization of gra⁃phene oxide with different diisocyanates and their use as a rein⁃forcement in waterborne polyurethane composites[J].Journal of Mac⁃romolecular Science:Part A -Chemistry,2019,56(12):1071-1081.[12]Vu M.,Bae Y.,Yu M.,et al.Thermally conductive adhesives from covalent-bonding of reduced graphene oxide to acrylic copoly⁃mer[J].The Journal of Adhesion,2018,95(10):887-910.[13]Xiang M.,Yang R.,Yang J.,et al.Fabrication of polyamide 6/reduced graphene oxide nano-composites by conductive cellulose skeleton structure and its conductive behavior[J].Composites Part B:Engineering,2019,167:533-543.作者简介：董熠哲(1999-)，男，汉族，河南洛阳，安徽理工大学材料科学与工程学院，研究方向：聚合物基石墨烯导热复合材料。
一、项目名称低维系统的拓扑电子态、缺陷和界面效应二、申报奖种山东省自然科学奖三、申报单位山东大学四、推荐单位意见我单位认真审阅了该项目推荐书及其附件材料，确认全部材料真实有效，相关栏目均符合山东省科学技术奖励委员会办公室的填写要求。
项目发展了多种理论模型并得到了实验验证，揭示了低维材料电子结构的调控规律, 为器件应用提供了理论依据。
主要发现点有：1) 提出传统二维半导体到二维拓扑绝缘体转变的理论模型，预言了具有超大的拓扑非平庸带隙的二维材料。
2) 提出了半导体点缺陷的电子自旋极化和磁有序的理论模型，揭示了不同缺陷结构对载流子类型、导电性能及电子激发特性的调控规律。
3) 发展了一维、二维以及固液界面的理论模型，揭示了界面压力和摩尔结构对石墨烯电子结构的调控规律，预言一维同轴核壳界面的电荷分离特性以及界面对DNA的电子能级和电荷转移激发态的影响。
在Adv. Mater., Nano Lett.,和Phys. Rev. Lett.等国际著名期刊上发表了20篇有重要影响力的科研论文，其中1篇入选ISI TOP %1高被引论文，多个著名学术期刊如：Rev. Mod. Phys.、Nat Nanotech.等发表论文评价他们的工作。
引用这包括诺贝尔奖金获得者A.K.Geim教授。
8篇代表性论文他引428次，20篇论文总他引645次。
对照山东省科学技术奖授奖条件，推荐该项目申报山东省自然科学奖一等奖。
五、项目简介该项目属于物理学中的凝聚态物学领域。
低维材料的独特结构和优异性能是当前凝聚态物理领域的研究热点。
特别是利用低维材料的新奇电子结构可以突破传统硅半导体器件的摩尔极限，在新型纳米电子器件领域有广泛而重要的应用。
该项目针对一维和二维纳米材料中的拓扑电子态以及缺陷和界面效应在电子结构调控中的作用开展了系统深入的理论研究，提出了一系列理论模型并被多个实验所验证，为低维材料的器件应用提供了重要依据。
主要科学发现点如下：1.提出了利用表面修饰和施加应力将普通二维半导体材料调控为二维拓扑绝缘体的方法，证明了表面修饰和应力会造成费米面附近的能带翻转，在自旋-轨道耦合作用下，成为二维拓扑绝缘体。
石墨烯碳纳米管复合材料工艺流程英文回答：The process of fabricating graphene carbon nanotube (CNT) composites involves several steps. Here is a general outline of the process:1. Preparation of graphene: Graphene can be prepared through various methods such as mechanical exfoliation, chemical vapor deposition, or epitaxial growth. The chosen method will depend on the desired quality and quantity of graphene.2. Preparation of carbon nanotubes: Carbon nanotubes can be synthesized using techniques like chemical vapor deposition, arc discharge, or laser ablation. The choice of method will depend on the desired properties of the nanotubes.3. Dispersion of graphene and carbon nanotubes: Thenext step is to disperse the graphene and carbon nanotubes in a suitable solvent. This is typically done using sonication or mechanical stirring to ensure uniform distribution.4. Mixing and functionalization: The dispersed graphene and carbon nanotubes are then mixed together and subjected to functionalization processes. Functionalization can enhance the interfacial interactions between the graphene and carbon nanotubes, leading to improved mechanical and electrical properties.5. Composite fabrication: The mixture of graphene and carbon nanotubes is then processed to fabricate the composite material. Common methods include vacuumfiltration, spray coating, or direct mixing with a polymer matrix. The choice of fabrication method depends on the desired application and properties of the composite.6. Post-processing: After the composite material is fabricated, it may undergo post-processing steps such as annealing, chemical treatment, or mechanical shaping tofurther enhance its properties.7. Characterization: Finally, the fabricated graphene carbon nanotube composite is characterized using techniques like scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and spectroscopy to evaluate its structural, morphological, and functional properties.中文回答：制备石墨烯碳纳米管复合材料的工艺流程包括以下几个步骤：1. 石墨烯的制备，石墨烯可以通过多种方法制备，如机械剥离、化学气相沉积或外延生长。
序号分散剂/活性剂的名称简介结构1N-甲基-吡咯化合物（烷酮）2十二烷基苯磺酸钠(SDBS)分子式：C18H29NaO3S；分子量：348.48；固体，白色或淡黄色粉末，易溶于水，易吸潮结块；无毒3聚乙烯吡咯烷酮(PVP)分子式：(C6H9NO)n；白色或乳白色粉末或颗粒；4阴离子型表面活性剂：木质素磺酸钠（SLS)多聚物；分子量不定；化学结构尚未确定5胆酸钠（SC)分子式：C24H39Nao5；分子量：430.55；白色结晶或无色粉末6高浓度的胆酸钠7十六烷基三甲基溴化铵(CTAB)分子式： C16H33(CH3)3NBr；分子量：364.446；白色微晶性粉末，吸湿性，在酸性溶液中稳定，易溶于乙醇8聚氧乙烯月桂醚（Brij 35）棕色粘稠液，易溶于水，具有乳化、润湿、分散能力标准情况下熔点约为27℃沸点约100℃密度接近于水约为1.00g/mL，闪点大于110℃折射率 1.462可以用作乳化润湿剂，在橡胶工业中用作分散剂，石油工业和环境保护行业中用作溢油分散剂的组分之一。
也可用作醚酯类非离子型表面活性剂9吐温80分子式：C64H124O26 ；分子量：1309.5 ；浅黄色粘稠液体10曲拉通X100聚乙二醇对异辛基苯基醚；分子式：C34H62O11；分子量：646.86；对人体有害。
11氧化二丁基锡分子式：C8H18OSn ，分子量：248.95 ，白色到微黄色粉末。
熔点 >300℃，水溶性 4.0 mg/L（20℃）。
溶于盐酸，不溶于水及有机溶剂。
遇火自燃；剧毒12Disperbyk-163分散剂 Disperbyk-163 是一种相对分子质量为 17000,的嵌段共聚物，包括亲颜料端的胺基和亲溶剂端的酯基和羧基。
13赖氨酸14聚间亚苯亚乙烯衍生物（PmPV）15DsPE16聚乙烯醇(PVA) 17聚丙烯酰胺购买/自行合成出现的文章结构/机理优缺点These solvents areexpensive and requirespecial care whenhandling可购买liquid phase production ofgraphene by exfoliation ofgraphite insurfactent/water solutions合成工艺成熟、成本价低，可以得到高品质的石墨烯，具有较广阔的应用前景，但是此方法制备的石墨烯浓度较低。
Triton Minerals LtdASX:ABN:Street address:Postal address:Tel:Fax:Email:**************************.au Web:.auProjects:Balama NorthAncuabeBalama SouthTMG PRODUCES GRAPHENEHIGHLIGHTS∙Trial production of Graphene Oxide completed∙Graphene Oxide readily produced from different graphite concentrate grades∙Commercial grade Graphene Oxide produced∙Graphene successfully produced∙TMG product range expandedTriton Minerals Limited(ASX: TON, Triton or Company) is pleased to announce the positive initial Graphene Oxide tests conducted on the TMG concentrates.Triton’s Managing Director & CEO Brad Boyle said: “The successful production of the Graphene Oxide and Graphene through standard industrial techniques, once again demonstrates the high quality and versatility of the TMG products.The remarkable properties of Graphene are well known and now that TMG has shown to be ideally suited to create the wonder material, this now creates further possibilities for Triton to expand their market presence and to explore an even broader client base and revenue streams.”GRAPHENE OXIDEIn tests conducted by a Government-sponsored laboratory in Singapore, Graphene Oxide has been successfully produced from various graphite concentrate grades of TMG product.Commercial-grade Graphene Oxide was readily produced from a broad range of TMG concentrates, using the standard extraction methods. These initial results are considered by Triton to be encouraging.In these industry-standard production runs only 1.5 grams of TMG concentrate was required to produce approximately 250ml of high concentration graphene oxide solution.Research has found that graphene oxide solution is sold commercially in a diluted form (concentration at 4mg/ml) and can sell for of up to $400 for 250ml. Triton considers that the economics of producing graphene oxideand subsequently graphene from TMG are very encouraging.The Company will continue to explore opportunities to refine the production of Graphene Oxide. As the predicted global demand for graphene oxide and graphene grows, Triton is well positioned to help meet that supply demand, with the ability to produce high purity and volume of graphite concentrate.Figure 1. Image of the Graphene Oxide solution (left) created from TMG concentrates. SEM Imaging of fine Graphene Oxide flakes (right) created from TMG concentrate. The size of the flakes ranged from approximately 100 nm to 3 μm.GRAPHENETriton confirms the same Singapore laboratory has also successfully created Graphene powder from the TMG products by simply reducing (drying) the TMG Graphene Oxide solution. Once the Graphene powder has been created it is actually insoluble in water.WHAT IS GRAPHENE OXIDEGraphene oxide (GO) is a unique material that can be viewed as a single monomolecular layer of graphite with various oxygen containing functionalities.Interest in GO has increased dramatically after graphene, a single layer of graphite, was first isolated and studied.Reduced GO can be made as a thin film from an aqueous dispersion of GO in water and has moderate conductivity, it is attractive for use in electronic devices. In addition to being components in electronic devices, GO and reduced GO have been used in nanocomposite materials, polymer composite materials, energy storage,biomedical applications, catalysis,and as a surfactant with some overlaps between these fields (Source: ).Figure 3. Graphene oxide (concentration level at 4 mg/mL, dispersion in H2O) PROPERTIES OF GRAPHENE OXIDEGraphene oxide is its easy dispersability in water and other organic solvents, as well as in different matrixes, due to the presence of the oxygen. The is a very important property when mixing the material with ceramic or polymer matrixes when trying to improve their electrical and mechanical properties. However, on the other hand, the electrical conductivity of GO is reduced and sometimes described as an electrical insulator, due to the bonding of the oxygen molecules (Source: ).There are many ways in which GO can be functionalized, depending on the desired application. For optoelectronics, biodevices or as a drug-delivery material, for example, it is possible to substitute amines for the organic covalent functionalization of graphene to increase the dispersability of chemically modified graphenes in organic solvents. It has also been proved that porphyrin-functionalized primary amines and fullerene-functionalized secondary amines could be attached to graphene oxide platelets, ultimately increasing nonlinear optical performance (Source: ).In order for GO to be usable as an intermediary in the creation of monolayer or few-layer graphene sheets, it is important to develop an oxidization and reduction process that is able to separate individual carbon layers and then isolate them without modifying their structure.GRAPHENE OXIDE APPLICATIONSThere are many applications which use GO and the list continues to grow. There are many obstacles needed to be overcome before GO can be used commercially in most areas but advancements are being made every day and some of the key areas of development for GO include bioengineering, composite materials, energy technology and nanotechnology.Energy StorageNanocomposites of reduced GO have been used for high capacity energy storage in lithium ion batteries. In these studies, electrically insulating metal oxide nanoparticles were adsorbed onto reduced GO to increase the performance of these materials in batteries. High surface area of reduced GO has been made using microwaves for exfoliation and reduction of GO. The high surface area reduced GO formed is useful as an energy storage material in super capacitors (Source: ).Graphene based micro-supercapacitors will likely be developed for use in low energy applications such as smart phones and portable computing devices. Graphene-enhanced lithium ion batteries could be used in much higher energy usage applications such as electrically powered vehicles, or they can be used as lithium ion batteries are now, in smartphones, laptops and tablet PCs but at significantly lower levels of size and weight (Source: ).Photovoltaic CellsOffering very low levels of light absorption (at around 2.7% of white light) whilst also offering high electron mobility means that graphene can be used as an alternative to silicon or ITO in the manufacture of photovoltaic cells. Silicon is currently widely used in the production of photovoltaic cells, but while silicon cells are very expensive to produce, graphene based cells are potentially much less so. When materials such as silicon turn light into electricity it produces a photon for every electron produced, meaning that a lot of potential energy is lost as heat. Recently published research has proved that when graphene absorbs a photon, it actually generates multiple electrons. Also, while silicon is able to generate electricity from certain wavelength bands of light, graphene is able to work on all wavelengths, meaning that graphene has the potential to be as efficient as, if not more efficient than silicon, ITO or (also widely used) gallium arsenide. Being flexible and thin means that graphene based photovoltaic cells could be used in clothing; to help recharge your mobile phone, or even used as retro-fitted photovoltaic window screens or curtains to help power your home (Source: ).ElectronicsIt is predicted that Optoelectronics; specifically touchscreens, liquid crystal displays (LCD) and organic light emitting diodes (OLEDs) will soon be using GO in a commercial volumes (Source: ). Other Electronic devices using GO as a starting material for at least one of the key components, including the field effect transistor (FET) that uses reduced GO as a chemical sensor and biosensor to detect hormonal catecholamine molecules, avidin and DNA. Whilst, another study had GO functionalised with glucose oxidase and deposited on an electrode was used as an electrochemical glucose sensor. (Source: ).UltrafiltrationAnother standout property of graphene is that while it allows water to pass through it, it is almost completely impervious to liquids and gases (even relatively small helium molecules). This means that graphene could be used as an ultrafiltration medium to act as a barrier between two substances. The benefit of using graphene is that it is only 1 single atom thick and can also be developed as a barrier that electronically measures strain and pressures between the 2 substances.This could mean that graphene is developed to be used in water filtration systems, desalination systems and efficient and economically more viable biofuel creation (Source: ).Composite MaterialsGraphene is strong, stiff and very light. Currently, aerospace engineers are incorporating carbon fibre into the production of aircraft as it is also very strong and light. However, graphene is much stronger whilst being also much lighter. Ultimately it is expected that graphene is utilized to create a material that can replace steel in the structure of aircraft, improving fuel efficiency, range and reducing weight. Due to its electrical conductivity, it could even be used to coat aircraft surface material to prevent electrical damage resulting from lightning strikes. In this example, the same graphene coating could also be used to measure strain rate, notifying the pilot of any changes in the stress levels that the aircraft wings are under. These characteristics can also help in the development of high strength requirement applications such as body armour for military personnel and vehicles (Source: ).Biomedical ApplicationsGO has been used as a component in drug delivery systems. Functionalized nanographene oxide has been used in several studies on targeted delivery of anti-cancer drugs (Source: ).BiosensorsGO and reduced GO have been used as components in several systems designed to detect biologically relevant molecules. Folic acid functionalized GO was used as a component in a system used to detect human cervical cancer and human breast cancer cells (Source: ).CONVERTING GRAPHITE TO GRAPHENE OXIDETriton confirms that there are many ways being developed by companies around the world to produce commercial volumes of GO and graphene, however, at the moment the most popular method to produce graphene is by using mechanical or thermal exfoliation, chemical vapour deposition (CVD), and epitaxial growth.Many modern procedures for the synthesis of GO are based on the method first reported by Hummers in which graphite is oxidized by a solution of potassium permanganate in sulphuric acid. Reduction of GO has been reported using hydrazine, NaBH4, ascorbic acid, and HI. GO can be reduced as a thin film or in an aqueous solution (Source: ).It appears the most effective way of synthesised graphene on a large scale is through chemical reduction of graphene oxide. However, it has been difficult for scientists to complete the task of producing graphene sheets of the same quality as mechanical exfoliation (Source: ). Interest in GO continues to grow as people search for a cheaper, simpler, more efficient and better yielding method of producing graphene, that can be scaled up massively compared to current methods, and be financially suitable for industrial or commercial applications. Once this issue is overcome, we can expect to see graphene become much more widely used in commercial and industrial applications (Source: ).CONCLUSIONS – What does this mean for Triton?The demand and use of Graphene Oxide and Graphene continues to grow rapidly around the world in areas of bioengineering, composite materials, energy technology and nanotechnology. Triton has successfully produced Graphene Oxide and Graphene, using industry-standard methods, from the TMG concentrate.This further demonstrates the high quality and versatility of the TMG concentrate products and creates further possibilities for Triton to expand their market presence and to explore a broader customer and application base and revenue stream.Triton is rapidly working towards establishing TMG as a new global graphite-industry benchmark, by aiming to offer the world's lowest cost and most diversified graphite product range together with the longevity of a reliable supply of high quality flake graphite.RegardsBrad BoyleCEO & Managing DirectorTriton Minerals LtdHolder of the world’s largest known combined graphite-vanadium resourceVisionLed by a highly experienced Board and Management team, Triton’s primary vision is to grow shareholders value through discovery and development of graphite, gold and other precious, base and industrial minerals deposits. Further, Triton will explore vertical integration opportunities to supplement its core business and to create valued revenue streams to ultimately benefit Triton’s shareholders.TMG and beyondTriton hopes to establish Triton Mozambique graphite, produced from its Mozambique graphite projects (TMG) as the global graphite-industry benchmark by aiming to offer the world’s lowest cost and most diversified graphite product range, together with the longevity of a reliable supply of high quality flake graphite.Triton hopes to establish Triton Mozambique graphite, produced from its Mozambique graphite projects (TMG) as the global graphite-industry benchmark.Triton is also actively pursuing vertical integration opportunities to be involved in all aspects of the graphite supply chain, which Triton believes will add significant value to the Company and its shareholders in the long term.For further information, please contact:Brad BoyleCEO & Managing DirectorTel: + 61 8 6489 2555Email: ****************************.auForward-Looking StatementsThis document may include forward-looking statements. Forward-looking statements include, but are not necessarily limited to, statements concerning Triton Minerals Limited’s planned exploration program and other statements that are not historic facts. When used in this document, th e words such as “could”, “plan”, “estimate” “expect”, “intend”, “may”, “potential”, “should” and similar expressions are forward-looking statements. Although Triton Minerals Limited believes that its expectations reflected in these are reasonable, such statements involve risks and uncertainties, and no assurance can be given that actual results will be consistent with these forward-looking statements.。
介孔聚多巴胺介导催化下载温馨提示：该文档是我店铺精心编制而成，希望大家下载以后，能够帮助大家解决实际的问题。
文档下载后可定制随意修改，请根据实际需要进行相应的调整和使用，谢谢!并且，本店铺为大家提供各种各样类型的实用资料，如教育随笔、日记赏析、句子摘抄、古诗大全、经典美文、话题作文、工作总结、词语解析、文案摘录、其他资料等等，如想了解不同资料格式和写法，敬请关注!Download tips: This document is carefully compiled by the editor. I hope that after you download them, they can help you solve practical problems. The document can be customized and modified after downloading, please adjust and use it according to actual needs, thank you!In addition, our shop provides you with various types of practical materials, suchas educational essays, diary appreciation, sentence excerpts, ancient poems, classic articles, topic composition, work summary, word parsing, copy excerpts, other materials and so on, want to know different data formats and writing methods, please pay attention!标题：介孔聚多巴胺介导催化：新颖纳米材料在催化领域的应用摘要：催化技术一直是化学领域的热点之一，其在环境保护、能源转化等方面发挥着重要作用。
点击化学的进展及应用点击化学（Click chemistry），又称“链接化学”、“动态组合化学”，意为通过小的化学单元的连接，以较高的产率快速地进行化学合成，得到目标产物。
这一概念最早由Barry Sharpless于2001年提出，在化学合成领域引起极大的关注，点击化学的主要特征有产率高，无副产物或副产物无害，反应原料易得，条件简单，选择性强，需较高热力学驱动力等[1]。
经过十余年的发展，点击化学在有机合成方面有着很大的贡献，更是在药物开发和生物医用材料合成等诸多领域中成为最为吸引人的合成理念。
本文主要介绍了一些经典的点击化学反应体系，并且结合其在有机合成中的实际应用，着重探讨与其相关的一些科研成果，主要包括组织再生，靶向药物递送，纳米材料表面修饰等几个方面。
点击化学反应主要有4种类型，环加成反应、亲核开环反应、非醇醛的羰基化学以及碳碳多键的加成反应。
环加成反应中，Huisgen环加成（CuAAC）是点击化学反应最为经典的体系，即叠氮化物与末端或内部炔烃之间在一价铜催化下，进行1,3—偶极环加成，得到1,2,3—三唑。
叠氮化物与末端炔基容易安装在分子中，且较为稳定，该反应速率快，副产物少，广泛应用于在聚合物偶联、后修饰中，但催化所需的一价铜的毒性限制了其应用。
因此，环张力引发的叠氮—炔环加成（SPAAC）被提出，由环烯和叠氮化物进行反应。
此反应最大的改善在于无铜点击化学反应，避免了一价铜的毒性，通过叁键的角应变以及存在于环烯中的环应变提高了反应速率。
但上面两个反应中用到叠氮化物，在反应的过程中具有一定的危险性。
另外，我们极为熟悉的Diels—Alder反应，即共轭双烯与取代烯烃反应生成取代环己烯，也属于点击化学的这一类型[1]。
图1 Huisgen环加成反应图2 叠氮—炔环加成反应图3 Diels—Alder反应巯基—烯反应是碳碳多键加成类型的主要反应，具有立体选择性、高产率等点击化学的特性，可在光或热引发下进行，常用于树枝状聚合物的合成与材料表面修饰，在材料和生物医学科学中有很多应用。
ORIGINAL PAPERFunctionalization of graphene with Prussian blue and its application for amperometric sensing of H 2O 2Su-Juan Li &Ji-Min Du &Yun-Feng Shi &Wan-Jun Li &Shui-Ren LiuReceived:27September 2011/Accepted:9January 2012/Published online:28January 2012#Springer-Verlag 2012Abstract As a two-dimensional carbon material with high surface area and conductivity,graphene shows great prom-ise for designing composite nanomaterials to achieve high-performance electrochemical devices.In this work,we prepared graphene-based nanocomposite material by electrochemically depositing Prussian blue (PB)nanoparticles on the surface of graphene.Fourier transform infrared spectra,SEM,and cyclic voltammetry were used to characterize the successful immobilization of pared with PB films and graphene sheets,the PB –graphene composite films showed the largest current response to the reduction of H 2O 2,probably due to the synergistic effects between gra-phene sheets and PB nanoparticles.Therefore,a fast and highly sensitive amperometric sensor for H 2O 2was obtained with a detection sensitivity of 1.6μA μM −1H 2O 2per cm 2and a linear response range of 50∼5,000μM.The detection limit of H 2O 2was 20nM at a signal-to-noise ratio of 3.These obtained results are much better than those reported for carbon nanotubes-based amperometric sensors.Keywords Prussian blue .Graphene .Hydrogen peroxide sensorIntroductionGraphene,a single layer of carbon atoms in a closely packed honeycomb two-dimensional lattice,has attracted extensive attention because of its unique nanostructure and extraordinaryproperties,including high conductivity,high surface area,and low manufacturing cost [1,2].These unique properties make graphene a promising supporting component for potential applications in the fields of batteries,supercapacitors,nano-electronics and electrochemical sensors,etc.[3–6].Recently,numerous investigations have been focused on graphene-based hybrid nanomaterials to achieve the functionalities of gra-phene,for further expanding the application range and enhanc-ing the performance of graphene-based materials [7,8].Toward this objective,many graphene-based nanocomposites such as polymer/graphene,metal/graphene,and metal oxides/graphene have been successfully designed toward applications in technological fields of catalyst and biosensors.For example,Pt or Pt –Ru/graphene nanocomposite have been used as an electrocatalyst for methanol oxidation,showing better electro-catalytic activity than carbon nanotubes (CNTs)and vulcan-supported Pt or Pt –Ru catalyst [9–11].It is also reported that Au NPs/graphene [12]or MnO 2/graphene oxide [13]nano-composite materials could be an ideal nonenzymatic sensor for hydrogen peroxide (H 2O 2).Therefore,integration of functional materials on graphene sheets may hold great promise for enhancing the performance of the graphene-based hybrid materials.Prussian blue (PB)is a kind of attractive inorganic ma-terial with well-known electrochromic and electrocatalytical properties.Due to its high activity and selectivity toward the reduction of hydrogen peroxide,PB is usually recognized as an “artificial enzyme peroxidase ”and has been extensively utilized in constructing electrochemical sensors based on measuring H 2O 2[14–17].However,as pointed out recently by Li et al.[18],there are some problems that restrain the full development of PB-based amperometric sensor:PB films are usually operated in acidic conditions to avoid being decomposed,which is in conflict with near-neutral physiological solutions for biosensing analysis.Besides,PBS.-J.Li (*):J.-M.Du :Y .-F.Shi :W.-J.Li :S.-R.LiuSchool of Chemistry and Chemical Engineering,Anyang Normal University,Anyang 455002,Chinae-mail:lisujuan1981@J Solid State Electrochem (2012)16:2235–2241DOI 10.1007/s10008-012-1653-3films present lower electrochemical stability,thus resulting in a reduced lifetime of the biosensor.In order to solve these problems,much endeavor has been devoted to searching for novel supports that can improve the sensor’s stability and activity.A general solution to the problem is the utilization of CNTs/PB composites due to the enhanced stability of the composite material[19–21].Nevertheless,when constructing CNTs/PB composites based electrochemical sensors,multi-step processes are usually required to prepare in advance,such as purifying CNTs or presynthesizing PB nanoparticles[22]. These complicated processes limit its large-scale application. Therefore,developing new support materials with simple preparation approach to enhance the stability of PB-based amperometric sensor is still greatly demanded.Of several possibilities for applications of PB,ampero-metric detection of H2O2is one of the most exciting. Detection of low levels of hydrogen peroxide is important in many areas such as modern medicine,environmental protection,food control,and also a key factor in the devel-opment of efficient biosensors,since H2O2is a product of classic reaction catalyzed by oxidase enzymes[23].By monitoring the electrochemical response of H2O2,the con-centration of the enzymatic substrate can be obtained due to their proportional relationship.Inspired by the unique properties of graphene and its electrocatalytic activity toward reduction of H2O2,we rea-son that when it combined with PB nanoparticles,the resul-tant PB/graphene nanocomposite electrochemical sensor may bear with improved sensitivity in detecting H2O2,due to the synergistic effect between graphene and PB nano-particles.Hence,in this research,we developed a reliable and fast determination method for H2O2based on PB/gra-phene nanocomposite material.PB nanoparticles were syn-thesized on the surface of preimmobilized graphene with an electrochemical deposition method to fabricate a PB/gra-phene-modified glassy carbon electrode(GCE).Fourier transform infrared(FTIR)spectra,scanning electron micros-copy(SEM),and cyclic voltammetry were used to charac-terize the successful immobilization of PB.The results demonstrate that PB nanoparticles immobilized on graphene support exhibit higher stability than PB films directly on GCE surface.The PB/graphene/GCE presents low potential, high sensitivity,and long-term stability towards electro-chemical determination of H2O2,which is potential for the development of bioelectronic devices and biosensors. ExperimentalReagents and apparatusSpectral graphite(about50μm;Shanghai Carbon Co.,Ltd.) was used for synthesis of graphite oxide(GO)by using the modified Hummers method[4,24].The as-synthesized GO was suspended in water to give a brown dispersion,which was subjected to dialysis for1week to completely remove residual salts and acids.Exfoliated GO was obtained by ultrasound of the0.5wt.%GO dispersion.H2O2,iron chlo-ride hexahydrate(FeCl3·6H2O),and potassium ferricyanide (K3Fe(CN)6)were purchased from the Chemical Reagent Company of Tianjin(China)and was used without further purification.Other reagents were all of analytical grade.All aqueous solutions were prepared with deionized water.Electrochemical measurements were performed on a CHI 650electrochemical workstation(Shanghai Chenhua Instrument Company,China).A three-electrode system was employed with a Ag/AgCl(3mol L−1KCl)electrode as the reference electrode,a platinum foil as the counter electrode,and the PB/graphene/GCE as the working elec-trode.All experiments were carried out at room temperature (25±1°C).Cyclic voltammetric experiments were per-formed with a scan rate of50mV s−1unless otherwise stated.FTIR measurements were obtained with a Bruker IFS-66v/S spectrometer(Germany)with a KBr plate.SEM (Hitachi,S-4800,Japan)images were used to characterize the morphology of synthesized PB/graphene nanocomposite material.Preparation of the modified electrodesPrior to the electrode modification,the GC electrodes with a diameter of3mm were successively polished with1.0,0.3, and0.05μm alumina powder,and then ultrasonicated in ethanol and water,each for3min.The graphene-modified electrodes were prepared by a reported method of electrochem-ically reduction of GO precursor[25].Typically,6μL of the GO dispersion(0.5mg mL−1)was cast onto the GC electrode and then dried in air at room temperature.The electrochemical conversion of GO to graphene was achieved by applying a cathodic potential of−1.5V on GO/GCE in20mM KH2PO4 solution for10min.Then,the following electrochemical deposition of the PB nanoparticles on graphene was carried out in an aqueous solution of2.0mM K3Fe(CN)6+2.0mM FeCl3·6H2O+10mM HCl+0.1M KCl by the CV method for 20circles between0.0and1.0V until a stable cyclic voltam-mogram was obtained.The prepared PB/graphene/GCE was rinsed with deionized water and then dried in air for the subsequent electrochemical measurements.In a control exper-iment,PB nanoparticles were prepared on GC electrode by using the same20circles in CV as mentioned above.A0.1M phosphate buffer solution(PBS,pH5.8)was used as supporting electrolyte for the determination of H2O2.Before and after every measurement,the PB/graphene/GCE was acti-vated by successive cyclic voltammetric sweeps between−0.2 and0.4V at50mV s−1in0.1M pH5.8PBS.Results and discussionSEM characterization of synthesized graphene and PB/graphene compositeThe morphology of the prepared graphene and PB/graphene composites modified GCE were characterized by SEM in Fig.1A ,B .It is clear that slices of crumpled silk veil waves that were wrinkled and scrolled are observed on graphene surface (Fig.1A ).The section of wrinkled structure is at-tributed to the π–πinteraction within sheets of graphene.It is just this wrinkled nature that renders the graphene sheets stable and beneficial for maintaining a high surface area on the electrode.From the SEM images of PB/graphene com-posite,some of PB nanoparticles are uniformly spread out on the surface of graphene sheets (Fig.1B ),which guaran-teed efficient electrochemical properties of PB/graphene nanocomposites.These results suggest that our electrochem-ical deposition method we used can effectively produce homogeneous high-loading PB nanoparticles supported on graphene sheets.FTIR spectra of PB/graphene compositeFTIR spectra of the prepared PB/graphene composite film are shown in Fig.2.Meanwhile,the FTIR spectra of GO were also displayed.Curve a shows the pure GO;the bands around 976,1,056,1,226,1,276,1,384,1,580,and 1,727cm −1are attributed to the oxygen-containing func-tional groups on GO [25,26],while the band at ca.1,619cm −1could be due to the O –H stretching deformation vibration of intercalated water.After the reduction and then modification with PB nanoparticles,the FTIR adsorption bands of oxygen functionalities decrease significantly and even disappear (curve b),which confirmed the successful conversion of GO into graphene.Besides,a new strong absorption band at 2,100cm −1is attributed to the C 0N stretching vibrations of PB [27].Thus,these are the indica-tors that PB had been assembled on the surface of graphene through electrochemical deposition method.Cyclic voltammetric behavior of the PB/graphene/GCE Cyclic voltammogram of the PB/graphene/GCE in a 0.5-M KCl aqueous solution was carried out at a scan rate of 50mV s −1.As shown in Fig.3,a pair of peaks located at 0.254/0.215V (vs.Ag/AgCl)corresponding to the revers-ible conversion of PB to Prussian white is observed.The potential separation of the redox peaks is only 39mV ,which is very close to the theoretical value,indicating that fast charge transfer occurs in the modified PB/graphene com-posite.This phenomenon could be ascribed to the highly electrical conductivity of graphene.The effect of the poten-tial scan rate on the reduction current of PB was investigated in the range of 5to 1,000mV s −1.A linear relationship between the peak currents and the scan rates from 5to 30mV s −1is observed (inset A),indicating that the present electrochemical reactions are a surface-controlled process.At higher scan rates from 40to 1,000mV s −1,the peak currents are found proportional to the square root of the scan rate (inset B),suggesting that the reaction kinetics change from a surface process to a diffusion controlled process.These results are consistent with those reported previously [14,16,28].The stability of the PB/graphene-modified electrode was verified by investigating its cyclic electrochemical behavior in a blank solution of 0.5mol L −1KCl solution at a potential scan range of 0∼1.2V .As can be observed in Fig.4A ,PB/graphene/GCE shows the typical redox characteristics of PB;apart from the redox pair at ca.0.2V corresponding to the conversion of PB to Prussian white,another redox pair at 0.974/0.857V corresponding to the reversible con-version of PB to Berlin green is observed.After successive scans in the first 30cycles,it is clear from Fig.4A that no expressive changes or current decreases are observed in the CV profiles of the PB/graphene-modified electrode,indicat-ing that this PB/graphene composite presents high stability for both the transition between PB and Prussian white and between PB and Berlin pared with PB-modified electrode as Fig.4B demonstrated,the stability of PB electro-chemically deposited on graphene sheet is greatly enhanced.1µm 1µmA BFig.1SEM images ofgraphene (A )and PB/graphene composite (B )Therefore,it is reasonable to conclude that the support of graphene not only maintains the good electrochemical activity of PB but also protect the structure of PB to be not damaged by the intercalation/deintercalation of potassium cations,which means that the present PB/graphene composite is an ideal material for constructing a stable sensor devices.Electrocatalytic reduction of H 2O 2at the PB/graphene-modified electrodeIn this section,we investigated the electrocatalytic behavior of the PB/graphene nanocomposite on GC electrode toward the reduction of H 2O 2.To distinguish the contribution of individ-ual modified components and the potential synergistic effects among them,control experiments on the bare GCE,graphene/GCE,and PB/GCE were also carried out.Figure 5A –C shows the voltammograms resulting from the bare GCE,graphene/GCE,and PB/GCE in 0.1M PBS without (black curve)and with 5mM H 2O 2(red curve)addition.As can be observed,there is no electrocatalytic activity of the bare GCE toward the reduction of H 2O 2.However,in terms of graphene/GCE and PB/GCE,with the addition of 5mM H 2O 2,an obvious increased reduction current is observed,indicating that both graphene and PB show electrocatalytic activity toward H 2O 2,which is in accordance with reports of literature.Besides,the onset potential of PB/GCE for electrochemically reduction of H 2O 2is found at 0.21V (vs.Ag/AgCl).When the two electro-catalysts are integrated together to form PB/graphene nano-composite film modified electrode,a remarkable reduction current,which is the largest among all of the electrode,can be observed from the cyclic voltammograms presented in Fig.5D ,recorded in a PBS aqueous solution containing 5mM H 2O 2.Therefore,the synergistic effects are estimated to occur between graphene and PB nanoparticles.The elec-trochemical reduction of hydrogen peroxide on the PB/gra-phene/GCE starts at 0.25V (vs.Ag/AgCl),which is more positive than the onset potential of PB/GCE.This 40-mV positive shift of the onset potential for the reduction of H 2O 2on the PB/graphene nanocomposite demonstrates that intro-duction of graphene support enhances the electrocatalytic activity of the loaded PB nanoparticles.In this process,gra-phene in the composite films improves the electronic and potassium ionic transport capacity,and the PB nanoparticles act as an electron mediator between the graphene and the hydrogen peroxide in solution.Based on the results discussed above,the working poten-tial for the amperometric sensing of H 2O 2was optimized in the potential range of 0.3to −0.3V .Figure 6shows the amperometric response curves of PB/graphene/GCE at dif-ferent detection potentials ranging from 0.3V to −0.3V (vs.Ag/AgCl)in 2-mM H 2O 2solutions.Obviously,the reduc-tion currents increase with negative shift of detection poten-tial,and reach a plateau at a potential of −0.2V as displayed in inset of Fig.6.Therefore,the working potential for the amperometric H 2O 2sensor was defined as −0.2V to ensure enough sensitivity and lower background current.Figure 7shows typical amperometric response of the PB/graphene composite film electrode to successive addition of H 2O 2in pH 5.8PBS at −0.2V.For comparison,the responses of PB/GCE,graphene/GCE,and a bare GC elec-trode under the same conditions were also displayed.Obviously,with the addition of H 2O 2,a stable and increas-ing amperometric response could be seen on the three mod-ified electrodes,while this phenomenon is not observed at the bare GC electrode.These results are consistent with that obtained from cyclic pared with the three modified electrode,it can be observed that the response of PB/graphene composite film electrode is the largest,220020001800160014001200100080016191226b2100aWave number (cm -1)17271580138410569761276T r a n s m i t t a n c e %Fig.2FTIR spectra of GO (a )and PB/graphene composite film (b )0.00.10.20.30.40.50.60.7-150-100-500501001505101520253010203040506070AC u r r e n t /AScan rate/mV.s -15101520253035100200300400500600700BC u r r e r n t /AC u r r e n r APotential/VFig.3Cyclic voltammograms of the PB –graphene/GCE in 0.5M KCl solution at a scan rate of 50mV s −1.Inset :plot of the reduction peak current at 0.215V vs.the scan rate in the range of 5to 30mV s −1(A );plot of the peak current at 0.215V vs.the square root of scan rate in the range of 40to 1,000mV s −1(B )presenting a current of 4.21μA with 50μM H 2O 2addition.The PB/GCE and graphene/GCE only yields a current of 1.79and 1.27μA upon addition of 50μM H 2O 2.Adding the current of PB/GCE and graphene/GCE together,it is found that this value (3.06μA)is still smaller than that of PB/graphene composite electrode (4.21μA).This further indi-cates that a synergistic effect between graphene and PB nano-particles occurs toward the electrochemical reduction of H 2O 2.The calibration curves obtained from the three modified electrodes are displayed in Fig.8.The resultant PB/GCE shows a narrow linear response range (50∼950μM),with further increasing of H 2O 2concentration,the current response keeps constant and even lowers due to the instability of PB films.Regarding the PB/graphene/GCE,the linear range spans the concentration of H 2O 2from 50μM to 5mM (R 00.9955)with linear equation of I (in microamperes)08.2098+0.0552C (in micromolars),and the detection limit is 0.02μM (S/N 03),which is lower than those at PB/multiwalled carbon nanotubes (MCNT)-modified Au electrode (0.023μM)[27],CNTs/chitosan-modified electrode (10.3μM)[28],chitosan/multiwalled carbon nanotubes/Hb/AgNPs/GCE (0.347μM)[29],CNT/AuNPs/PB (3.36μM)[30],chemically reduced graphene oxide based sensors (0.05μM)[26],graphene/Au NPs/GCE (0.44μM,−0.2V vs.Ag/AgCl)[12],PB/ordered mesoporous carbon composite-based sensor (1μM)[31],etc.In addition,the sensitivity of the sensor (obtained from the slope of the linear part of the calibration curve)is 1.6μA μM −1H 2O 2per cm 2,which is much higher than that reported at PB/MCNT-modified Au electrode (0.856μA μM −1cm −2).Thus,the present H 2O 2sensor based on the PB/graphene-basedC u r r e n t Potential/VC u r r e n t APotential/VFig.4Cyclic voltammograms of the PB –graphene/GCE (A )and PB/GCE (B )in 0.5M KCl solution at a scan rate of 50mV s −1(30first cycles)-0.20.00.20.40.6-4-3-2-101234C u r r e n t APotential/VPBS5 mM H 2O 2AC u r r e n t /APotential/VC u r r e n t Potential/VC u r r e n t APotential/VFig.5Cyclic voltammograms of the bare GCE (A ),graphene/GCE (B ),PB/GCE (C ),and PB/graphene/GCE (D )in 0.1M PBS (pH 5.8)without (black curve )and with (red curve )5mM H 2O 2at a scan rate of 50mV s −1hybrid material is fast,sensitive,and efficient.It demonstratesthat using graphene and some inorganic or metal nanoparticles holds great potentials for constructing biosensors and other bioelectronic devices.InterferencesThe possible interference of some inorganic ions and organ-ic compounds,which might coexist with H2O2in real sam-ples,was investigated with the method of amperometric detection of50μM H2O2.The result showed that500-fold of Cl−,SO4−,CO32−,NO3−,and citric acid did not cause significant interference with deviations below5%,indicat-ing that these species did not affect the determination of H2O2.Ten-fold of glucose,creatinine,trioxypurine,dopa-mine,uric acid,tyrosine,serine,glycin,lysine did not interfere with the oxidation signal of50μM H2O2.However, fivefold of Cu2+and Fe3+cause a signal(peak current of H2O2) change of about8.6%and10.2%,respectively.The possible reason is the catalytic ability of Cu2+and Fe3+to the electro-catalytic reduction of H2O2.Therefore,when the two cations are present,a separation procedure is required before determination.Reproducibility and stabilityHere,the reproducibility and stability of the PB/graphene composite-modified GC electrodes were investigated by measuring the current responses of the electrode upon addi-tion of50μM H2O2in PBS.The average relative standard deviation(RSD)of the sensor response to50μM H2O2was 4.8%for ten successive measurements.In a series of eight sensors named PB/graphene composite prepared in the same way,an RSD of5.6%was obtained,indicating an excellent reproducibility of this sensor.The prepared electrode was stored at room temperature.In order to investigate the sta-bility of the sensor,the current response to50μM H2O2was recorded every5days.It was found that the current could retain90.5%of its original signal after a month storage, which showed a long-term stability.ConclusionsIn summary,the PB/graphene nanocomposite film has been successfully deposited on glassy carbon electrode with an electrochemical deposition method.The as-prepared PB/ graphene/GCE exhibited a high electrocatalytic activity for the H2O2detection,showing a high sensitivity,a low limit detection,and a wide linear range.The synergetic effectCurrent/Time/sFig.6Current traces of2mM H2O2recorded at PB/graphene/GCE,the inset figure is the relationship of the amperometric current withdetection potentialsFig.7Current traces recorded at the PB/graphene/GCE,PB/GCE,graphene/GCE,and the bare GC electrode.Steps represent theresponses of the electrodes to the successive addition of50,500μMH2O2to the PBS(pH5.8)solutionCurrent/µAConcentration/µMFig.8Calibration curves for H2O2detection at the PB/graphene/GCE,PB/GCE,and graphene/GCE in PBS(pH5.8)between PB and graphene occurred,which combined the high catalytic nature of PB with the large surface area of graphene.Therefore,the PB/graphene nanocomposite film holds the promise for applications in other fields including bioelectronics devices,electrochromic displays,nonenzy-matic sensor,biofuel cells,and so on.Acknowledgment This work was supported by the Grants from the Natural Science Foundation of China(No21105002),Anyang Tech-nology Research Program(208),and the Innovative Foundation for the College students of Anyang Normal University(ASCX/2011-Z12). References1.Shao YY,Wang J,Wu H,Liu J,Aksay IA,Lin YH(2010)Electroanalysis22:1027–10362.Chen D,Tang LH,Li JH(2010)Chem Soc Rev39:3157–31803.Hou S,Kasner ML,Su S,Patel K,Cuellari R(2010)J Phys ChemC114:14915–149214.Kovtyukhova NI,Ollivier PJ,Martin BR,Mallouk TE,ChizhikSA,Buzaneva EV,Gorchinskiy AD(1999)Chem Mater11:771–7785.Titov A V,Kral P,Pearson R(2009)ACS Nano4:229–2346.Kang X,Wang J,Wu H,Liu J,Aksay IA,Lin Y(2010)Talanta81:754–7597.Hu Y,Jin J,Wu P,Zhang H,Cai C(2010)Electrochim Acta56:491–5008.Wang C,Zhang L,Guo Z,Xu J,Wang H,Zhai K,Zhuo X(2010)Microchim Acta169:1–69.Zhou YG,Chen JJ,Wang FB,Sheng ZH,Xia XH(2010)ChemCommun46:5951–595310.Bong S,Kim YR,Kim I,Woo S,Uhm S,Lee J,Kim H(2010)Electrochem Commun12:129–13111.Liu S,Wang J,Zeng J,Ou J,Li Z,Liu X,Yang S(2010)J PowerSourc195:4628–463312.Fang Y,Guo S,Zhu C,Zhai Y,Wang E(2010)Langmuir26:11277–1128213.Li L,Du Z,Liu S,Hao Q,Wang Y,Li Q,Wang T(2010)Talanta82:1637–164114.Nossol E,Zarbin AJG(2009)Adv Funct Mater19:1–715.Yu H,Sheng QL,Li L,Zheng JB(2007)J Electroanal Chem606:55–6216.Li J,Qiu JD,Xu JJ,Chen HY,Xia XH(2007)Adv Funct Mater17:1574–158017.Xian Y,Hu Y,Liu F,Xian Y,Feng L,Jin L(2007)BiosensBioelectron22:2827–283318.Li Z,Chen J,Li W,Chen K,Nie L,Yao S(2007)J ElectroanalChem603:59–6619.Zhai J,Zhai Y,Wen D,Dong S(2009)Electroanalysis21:2207–221220.Zhang W,Wang L,Zhang N,Wang G,Fang B(2009)Electroanalysis21:2325–233021.Zhang Y,Wen Y,Liu Y,Li D,Li J(2004)Electrochem Commun6:1180–118422.Cao L,Liu Y,Zhang B,Lu L(2010)Appl Mater Interf2:2339–234623.Itaya K,Ataka T,Toshima S(1982)J Am Chem Soc104:476724.Hummers WS,Offeman RE(1958)J Am Chem Soc80:1339–133925.Guo HL,Wang XF,Qian QY,Wang FB,Xia XH(2009)ACSNano3:2653–265926.Zhou M,Zhai Y,Dong S(2009)Anal Chem81:5603–561327.Du D,Wang M,Qin Y,Lin Y(2010)J Mater Chem20:1532–153728.Qian L,Yang X(2006)Talanta68:721–72729.Li Y,Li Y,Yang Y(2011)J Solid State Electrochem.doi:10.1007/s10008-011-1503-830.Li MY,Zhao GQ,Yue ZL,Huang SS(2009)Microchim Acta167:167–17231.Bai J,Qi B,Ndamanisha JC,Guo LP(2009)MicroporousMesoporous Mater119:193–199。
