氧化石墨烯-金纳米粒子复合物的表面增强拉曼活性特性

通过水热法合成了氧化石墨烯-金纳米粒子复合物,利用透射电镜和紫外光谱对其进行表面特征和吸收特征分析,并以结晶紫为探针分子,利用拉曼技术分析其拉曼活性。研究结果表明,实验得到的氧化石墨烯-金纳米粒子复合物可以成功检测到10^-4 mol/L的结晶紫溶液,具有良好的拉曼活性。     

不同形状的氧化石墨烯-金纳米粒子对对硝基苯酚的表面增强拉曼活性特性分析

通过种子生长法合成了不同形态的金纳米粒子,之后加入至氧化石墨烯水分散液中超声震荡得到不同形状的氧化石墨烯-金纳米粒子复合物。运用扫描电子显微镜、X射线光电子能谱、拉曼光谱等表征手段,探究复合物的表面结构、结合能与电荷状态,通过对对硝基苯酚的检测以表征其拉曼活性,并分析造成不同增强效果的原因。结果表明,氧化石墨烯-金纳米粒子复合物表现出良好的表面增强拉曼活性,可以成功地检测到10^-5 mol/L的对硝基苯酚,且复合物的表面增强拉曼活性因金粒子的形状不同而有所差异。     

氧化石墨烯/铅复合材料的合成

石墨烯是最薄的二维材料,具有极大的比表面积,可以作为纳米颗粒的基底.将氧化石墨烯和金属纳米颗粒进行复合,发挥二者的协同作用,是一种拓展和增强这2种材料性能的优选方法.本文将乙酸铅引入分散在水中的氧化石墨烯体系,获得了负载铅纳米复合材料,发现在该体系中氧化石墨烯的还原性也得到了发挥.      

Ag/石墨烯复合涂层的制备及抗菌性能

首先用改进的Hummers法制备氧化石墨烯（GO）; 其次用原位还原法将银氨溶液中的Ag纳米粒子通过还原剂葡萄糖和GO复合, 获得Ag/GO胶体; 最后在真空干燥条件下得到Ag/GO涂层, 并用真空阶梯热还原技术制备Ag/还原氧化石墨烯(rGO)涂层. 利用X射线衍射、 扫描电子显微镜、 透射电子显微镜等方法对膜样品结构形貌进行表征, 并用润湿角测量仪和抑菌环方法分别检测样品的亲/疏水性和抗菌性能. 实验结果表明: 石墨烯基膜材料与基底结合较好, Ag纳米粒子在石墨烯片层间呈球形均匀分布, 粒径为20~50 nm; 纯GO和rGO膜表面未见菌落, 大肠杆菌与金黄色葡萄球菌均未出现有效抑菌环; 复合Ag纳米粒子后, 涂层的抑菌效果得到显著提高; 与Ag/GO复合膜相比, Ag/rGO复合膜呈更强的抗菌活性, 即低温退火有助于提高石墨烯基复合涂层的抗菌性能.     

Carbon-nitrogen/graphene composite as metal-free electrocatalyst for the oxygen reduction reaction

Sheet-like carbon-nitrogen (CNx)/graphene composites with a high content of nitrogen (x≤0.15) was prepared by the carbonization of polypyrrole (PPy)/reduced-graphene-oxide (rGO) composite at 600-800°C. We used rGO instead of graphene oxide (GO) sheets as a template and a substrate to immobilize PPy since the PPy/GO composite agglomerates easily because of the dehydration of excess oxygen-containing groups on the GO sheets during the drying process. The dried PPy/rGO intermediate and its derived CNx/graphene products retain their high dispersion and loose-powder features. The as-prepared CNx/graphene composites have a total nitrogen content of about 10 at% and their nitrogen state is mainly of pyridinic and graphitic type. CNx/graphene composites exhibit excellent performance for the oxygen reduction reaction (ORR) in terms of electrocatalytic activity, stability and immunity towards methanol crossover and CO poisoning, suggesting their potential as metal-free electrocatalysts for the ORR.     

氧化石墨烯的表面处理及其在生物医学领域的应用

氧化石墨烯（graphene oxide, GO）表面具有丰富的含氧基团。通过共价键结合、疏水作用、氢键作用等吸附药物和其他大分子对GO表面微观结构的修饰可提升其实用性。尤其是对生物相容性的增强使得功能化的GO可以在临床医学领域得到广泛应用。介绍了GO表面处理的原理,总结了近几年国内外研究人员在GO表面修饰方面的研究进展,归纳了修饰后具有优异性能的功能化氧化石墨烯（functionalized graphene oxide, FGO）在生物医学领域中的广泛应用,包括疫苗载体、癌症治疗、药物输送和基因治疗等方面。最后指出,通过加强对GO的进一步研究,可使其在未来的生物医学领域发挥关键作用。     

PVP-assisted laser ablation growth of Ag nanocubes anchored on reduced graphene oxide(rGO) for efficient photocatalytic CO_2 reduction

Metallic nanoparticles loaded graphene nanocomposites have been widely studied for various scientific and technological applications. In this study, a facile method was reported to realize a straightforward growth of shape and size-controllable of metallic nanoparticles, and the subsequent hybridization with graphene in solution by strategically coupling wet-chemical route and laser ablation. By mixing graphene oxide(GO) with a tunable concentration level of polyvinylpyrrolidone(PVP) in aqueous solution, Ag nanocubes with a face-centered cubic crystal structure were generated by pulsed laser ablation and then mounted on GO nanosheets with the assistance of PVP. The preferential adsorption of PVP to Ag(100) crystal face led to the production of Ag nanocubes with exposed(100) facet. The result showed that the morphological yield of spherical particles decreased with the increase in PVP concentration. X-ray diffraction(XRD) and UV–visible spectroscopy analyses confirmed that GO was partially reduced. In the reduction of CO_2 gas, the photocatalytic conversion rate could achieve 133.1 μmol g~(-1) h~(-1) in 6 hrs for cubic Ag-loaded reduced GO composites.     

PtCo alloy nanoparticles supported on graphene nanosheets with high performance for methanol oxidation

PtCo alloy nanoparticles are deposited onto graphene sheets through a facile and reproducible hydrothermal method.During the hydrothermal reaction,the reduction of graphene oxide and PtCo alloy nanoparticles loading can be achieved.X-ray diffraction (XRD) analyses reveal a good crystallinity of the supported Pt nanoparticles in the composites and the formation of PtCo alloy.X-ray photoelectron spectra (XPS) results depict that Pt mainly exists in the metallic form,while much of the cobalt is oxidized.Transmission electron microscope (TEM) observations show that the PtCo alloy nanoparticles are uniformly dispersed on graphene nanosheets compared with multiwalled carbon nanotubes (MWNTs).This PtCo-graphene composite exhibits excellent electrocatalytic activity and high poison tolerance toward poisoning species for methanol oxidation reaction,far outperforming the Pt-graphene or PtCo-MWNTs composites with the same feeding ratio of Pt/carbon.     

玻片表面硅烷/氧化石墨烯复合涂层的制备及其摩擦性能

使用硅烷偶联剂 3-氨丙基甲基二甲氧基硅烷(3-(dimethoxymethylsilyl)propylamine) 和不同氧化程度的氧化石墨烯(graphene oxide, GO)在玻片表面采用浸渍法制备了一种在水环境下具有较好润滑性能的氧化石墨烯涂层. 通过傅里叶变换红外光谱 (Fourier transform infrared spectrometer, FTIR)仪、拉曼光谱(Raman spectra)分析法、水接触角(water contact angle, WCA)测试等方法研究了涂层的表面形貌及其特征. 研究结果表明, 所制备的硅烷/氧化石墨烯涂层表面均一, 没有明显的缺陷. 摩擦测试结果显示, 涂层能够有效提高耐磨性能, 不同氧化程度的氧化石墨烯对抗磨性能有着不同的影响, 氧化程度越高, 抗磨性能越好.     

Organic dye removal and recycling performances of graphene oxide-coated biopolymer sponge

In this study, a biopolymer sponge (PS) with a crosslinked mixture of gelatin-chitosan-poly(vinyl alcohol) was dipped into graphene oxide (GO) solution to form a composite sponge (CS, GO-coated PS) by a combination of simple dip-coating and freeze-drying procedures, as a sponge-like adsorbent in organic dye removal applications. The morphological, chemical, crystalline, mechanical and thermal characterizations of the as-obtained sponges were further investigated for the possible changes in the structure of sponge-like adsorbent after coating the GO sheets on the 3D porous structure of PS. The results showed that the CS had possessed effectively organic dye removal performances comparing to the PS. In the adsorption, the Langmuir and pseudo-second-order models corresponding to a monolayer approach and a chemical adsorption were appropriated. The maximum adsorption capacity of Rhodamine B and Congo red reached 126.8 and 135.0 ?mg?g^?1; and 145.6 and 148.6 ?mg?g^?1 corresponding onto the PS and CS. It indicates that the maximum adsorption capacity on the CS enhanced significantly comparing to those on the PS owing to the functional GO sheets coated in the 3D porous structure of PS, which leads to supplying further functional adsorption sides on the whole 3D porous structure of CS. Notably, the sponges-like adsorbents could be regenerated and used again without a remarkable decrease of dye removal ability occurred in 9 adsorbing–desorbing cycles. Therefore, the CS prepared in this study can become a potential adsorbent for actual applications because of non-toxic materials, proper structural features, low-cost material and operation, and reliable recyclability.     

氧化石墨烯尺寸分级及细胞毒性研究进展

氧化石墨烯（graphene oxide, GO）是一种化学改性的石墨烯材料。作为化学法制备石墨烯的前驱产物,GO具有石墨烯固有的优异性能外,大量含氧官能团的存在还使其表现出两亲性,例如在诸多溶剂（尤其是水）中分散性能良好。不同尺寸的GO应用于不同领域。大尺寸GO因其结构完整,适用于于制备导电薄膜和整料。小尺寸GO因其优异的生物相容性和生物活性,常应用于生物医学领域。制备不同尺寸级别的GO,使其在不同领域中的应用发挥更好的作用很有必要。简单介绍了GO的制备方法及结构特性,重点总结了影响GO尺寸的因素、GO的尺寸分级方法以及GO细胞毒性的尺寸效应。     

高能GO/ TiO2制备及其光催化反渗透浓水性能

为高效率处理反渗透浓水,采用改良Hummers法、水热合成法制备具有良好的吸附以及光催化性能的氧化石墨烯/具有高能暴露面二氧化钛纳米复合材料（GO/TiO2）,通过扫描电镜（SEM）、X射线衍射（XRD）表征其微观形貌和物相组成;并以模拟反渗透浓水探究其性能、较佳反应条件及具有协同效应。结果表明,纳米材料中二氧化钛粒子的高能暴露面增多,有助于有效地提高其光催化活性,粒子的晶化度有所增加且均匀附着在氧化石墨烯表面,不仅增大了粒子的比表面积,还降低了二氧化钛粒子的宽带隙能,有助于提高其光催化效率;同时,由于氧化石墨烯接收的二氧化钛受激发释放的光生电子的存在,氧化石墨烯对重金属离子的静电吸附能力显著增强,提高了氧化石墨烯去除重金属离子的效率;所制备的氧化石墨烯/具有高能暴露面二氧化钛纳米复合材料具有良好的处理反渗透浓水性能,氧化石墨烯含量为80 mg的纳米复合材料与pH调节至4的模拟反渗透浓水在室温下避光搅拌3 h、光催化反应1.5 h为较佳反应条件,该纳米复合材料的Pb2+、Cd2+、Cr6+去除率分别为32.2%、19.8%、11.7%,具有协同效应。     

Functionalized graphene oxide based on p-phenylenediamine as spacers and nitrogen dopants for high performance supercapacitors

p-Phenylenediamine （PPD） functionalized graphene oxide （GO） materials （PPDG） were prepared through a one-step solvothermal process and their appli-cation as supercapacitors （SCs） were studied. The PPD is not only as the spacers to prevent aggregating and re-stacking of the graphene sheets in the preparing process but also as nitrogen sources to obtain the nitrogen-doped graphene. The structures of PPDG were characterized by Fourier transformed infrared spectroscopy （FT-IR）, X-ray diffraction spectroscopy （XRD）, Raman spectroscopy and X-ray photoelectron spectroscopy （XPS） and the results show that the nitrogen-doped graphene was achieved with nitrogen content as high as 10.85 at.%. The field emission scanning electron microscopy （FE-SEM） and high resolu-tion transmission electron microscopy （HR-TEM） have confirmed that the morphologies of PPDG were looselayered with less aggregation, indicating that PPD mole-cules, as spacers, effectively prevent the graphene sheets from restacking during the solvothermal reaction. The special loose textures make PPDG materials exhibit excellent electrochemical performance for symmetric SCs with superior specific capacitance （313 F/g at 0.1 A/g）, rate capability and cycling stability. The present synthesis method is convenient and may have potential applications as ultrahigh performance SCs.     

大粒径氧化石墨及石墨烯的制备与表征

以0.10、0.15、0.18、0.30 mm 4种不同粒径的石墨为原料,采用密闭氧化、氨-水合胼还原法,经过2个控温阶段制备了10~20 μm大粒径氧化石墨(GO)与石墨烯,并通过正交实验、单因素实验优化了制备条件. 测定了GO与石墨烯的傅里叶红外光谱、拉曼光谱及热稳定性.用扫描电镜、X线衍射光谱、原子力显微镜测试了产品的结构与石墨烯片层厚度. 实验结果表明:石墨粒径越小,片层剥离程度越高, GO的产率、热稳定性也均有提高. 石墨烯在800 ℃下残炭率高于80%,剥离层厚度约为1 nm. 本实验研究为制备大粒径GO与石墨烯提供了一种可行的实验方法.     

石墨烯量子点用于修复石墨烯结构缺陷及其薄膜导热性能研究

为解决GO制备过程中,不可避免引入的石墨烯拓扑结构缺陷对热传递性能的显著影响,研究采用石墨烯量子点(GQDs)作为外部碳源,通过在高温条件下修复石墨烯中的拓扑结构缺陷,制备出了自支撑的石墨化–氧化石墨烯/石墨烯量子点(g-GO/GQDs)散热薄膜。与原始的gGO膜相比,g-GO/GQDs薄膜的面内热导率提高了22.1%,达到739.04 W/(m·K)。通过进一步的薄膜结构分析,发现其热导率的提高可归因于石墨化过程中sp2碳晶格域的恢复和形成。石墨烯导热薄膜的散热性能研究表明,该研究结果可有效提高石墨烯薄膜的散热效果,为制备高性能散热薄膜提供了新思路。     

石墨烯负载Zn2GeO4光催化剂的制备及其 降解有机污染物的性能研究

采用溶剂热法制备Zn_2Ge O_4纳米晶;并将其负载到氧化石墨烯(GO)上。通过两步水热法制备了一系列Zn_2Ge O_4/GO复合光催化剂。利用X-射线衍射(XRD)、透射电子显微镜(TEM)、紫外可见吸收光谱(UV-Vis)等手段对催化剂的结构、形貌及光学性能进行了表征;并以罗丹明B(Rh B)作为目标降解污染物,对其进行了光催化性能测试。结果表明,Zn_2Ge O_4纳米晶均匀地分散在GO上,与单纯的Zn_2Ge O_4纳米晶相比,Zn_2Ge O_4/GO复合物的光催化性能有了明显的提高。当GO质量分数为5%时,罗丹明B降解率达到95.21%;且经过5次循环使用后,仍然保持较高的光催化活性,具有良好的稳定性。     

超临界乙醇制备TiO2/石墨烯纳米复合材料及其表征

以氧化石墨为载体、钛酸异丙酯为前驱体,利用超临界乙醇的超临界性能和还原性,制得了晶型完善的锐钛矿TiO2/石墨烯纳米复合材料.通过红外光谱（FTIR）、X射线光电子能谱（XPS）对采用Hummers法制得的氧化石墨（GO）进行表征;同时利用透射电子显微镜（TEM）、X射线衍射仪（XRD）对TiO2/石墨烯纳米复合材料进行研究.结果表明：成功制得了氧化石墨（GO）和晶型完善的锐钛矿TiO2/石墨烯纳米复合材料,并且发现二氧化钛在石墨烯纳米片层上呈现为有规则的颗粒,分散均匀,平均粒径为8.24 nm.     

Influence of graphene microstructures on electrochemical performance for supercapacitors

The influence of variant graphenes on electrochemical performance for supercapacitors was studied comparatively and systematically by using SEM, FTIR and Raman spectroscopy, cyclic voltammetry (CV), galvanostatic charge/discharge and electrochemical impedance spectroscopy (EIS). The results revealed that: 1) the nitrogen-doped graphene (N-G) electrode exhibited the highest specific capacitance at the same voltage scan rate; 2) the specific capacitance of the N-G reached up to 243.5 F/g at 1 A/g, while regular graphite oxide (GO) was 43.5 F/g and reduced graphene oxide (rGO) was 67.9 F/g; 3) N-G exhibited the best supercapacitance performance and the superior electrochemical properties, which made it an ideal electrode material for supercapacitors.     

HPEI接枝改性PAN/GO-PAA静电纺纳米复合纤维膜对Au(Ⅲ)的吸附

以丙烯酸(AA)为单体,过氧化苯甲酰(BPO)为引发剂,通过原位聚合法,在氧化石墨烯(GO)表面包覆聚丙烯酸(PAA),得到GO-PAA纳米复合物.将GO-PAA纳米复合物分散在聚丙烯腈(PAN)基体中,利用静电纺丝技术得到PAN/GO-PAA静电纺纳米复合纤维膜.利用化学接枝反应在PAN/GO-PAA静电纺纳米复合纤维膜表面接枝超支化聚乙烯亚胺(HPEI),构筑HPEI-g-PAN/GO-PAA静电纺纳米复合纤维膜.研究了HPEI-g-PAN/GO-PAA静电纺纳米复合纤维膜对Au(Ⅲ)的吸附性能.结果表明:HPEI-g-PAN/GO-PAA静电纺纳米复合纤维膜对Au(Ⅲ)的最大吸附量为1 808.60 mg·g^－1,在吸附过程中,部分Au(Ⅲ)被还原为片状和不规则颗粒状的Au单质.在共存离子体系中,HPEI-g-PAN/GO-PAA对Au(Ⅲ)具有较好的吸附选择性.     

石墨烯在金电极上固定方法的选择及免疫传感器的构建

分别利用重氮化法、滴涂法、非共价键合法及偶联法将石墨烯固定于电极表面,并对所得到的修饰电极进行电化学表征,分析结果显示重氮化法制备的石墨烯修饰电极性能更稳定,信号更灵敏,所以将其用于免疫传感器的制备.首先在金电极上制备对氨基苯硫酚和苯硫酚的混合自组装单分子膜(MSAM),再利用重氮化法将石墨烯固定在MSAM修饰电极表面,然后在其表面电沉积纳米金,最后通过金-氨键固定抗体(羊抗小鼠IgG),并对小鼠IgG进行了初步检测,线性范围为0.001～400μg/L,检测下限达到0.0014μg/L.结果表明,该传感器具有检测范围宽、灵敏度高的优良性能,在临床检验中具有广阔的应用前景.