低电压电沉积类金刚石碳膜的研究

采用电化学沉积法,在较低电压下(4.0～8.0 V)以甲酸作为主要碳源,甲酸钠作为辅助碳源,二甲基亚砜与去离子水作为溶剂,在不锈钢表面制备了类金刚石碳薄膜,研究了沉积电压对碳膜形貌和成分的影响。电化学沉积含氢类金刚石碳薄膜致密、均匀,膜的电导率与沉积电压呈负相关关系,电导率介于金属与半导体之间。拉曼光谱在1332 cm^-1处出现金刚石的特征峰,sp³碳成分随沉积电压的增加而增加。傅里叶红外变换光谱显示沉积的类金刚石碳膜为含氢碳膜。X射线光电子能谱分析显示这些薄膜中存在sp²和sp³键碳原子。     

自支撑石墨烯/聚苯胺纳米纤维薄膜的制备及其电化学电容行为

用真空抽滤氧化石墨（GO）与聚苯胺（PANI）纳米纤维的混合分散溶液,流动组装得到自支撑GO/PANI复合薄膜,再利用气态水合肼还原其中的GO,最后重新氧化和掺杂还原态PANI,制备了自支撑石墨烯（GN）/PANI薄膜.扫描电子显微镜（SEM）结果显示,GN/PANI薄膜为层状结构,且PANI纳米纤维均匀插层于GN片间.PANI纳米纤维在复合薄膜中的存在有效增大了GN之间的层间距,有利于电解液离也GN充分接触.GN的高电导性则有利于PANI氧化还原过程中的电荷传输.电化学测试表明,GN/PANI薄膜在1 mol·L^-1HCl电解液中具有良好的电化学电容性能,在0.1 A·g^-1的电流密度下的比容量为495 F·g^-1,在3A·g^-1时为313 F·g^-1.经过2000次连续充放电,其具有90%的电容保持率,表明该复合材料具有良好的电化学稳定性.     

MnO2/H-TiO2纳米异质阵列的调控制备及超电容特性

采用目标调控的阳极氧化工艺制备了超大比表面、管与管相互分离的有序TiO₂纳米管阵列（TiO₂ NTAs）基体,进而分别采用电化学氢化法和循环浸渍沉积法对晶化退火后的TiO₂ NTAs实施电化学氢化和高比电容MnO₂沉积的双重功能化改性,调控构筑了一种新型MnO₂/H-TiO₂纳米异质阵列电极材料。利用场发射扫描电子显微镜（FESEM）、高分辨透射电子显微镜（TRTEM）、X射线衍射仪（XRD）、X光电子能谱仪（XPS）、拉曼光谱（Raman）和电化学工作站等对样品进行综合表征与超电容特性测试,结果表明：电化学氢化改性有效提高了H-TiO₂ NTAs的导电性和电化学特性,当电流密度为0.2 mA·cm^-2时H-TiO₂ NTAs的面积电容达到7.5 mF·cm^-2,是相同电流密度下TiO₂ NTAs的75倍;经过2个浸渍循环所获得的MnO₂/H-TiO₂ NTAs-2样品在电流密度为3 mA·mg^-1时比电容可达481.26 F·g^-1,电流密度为5 mA·mg^-1时循环充放电1000圈后比电容仅下降约11%。     

硼-氮共掺杂垂直石墨烯电极的制备及其葡萄糖检测性能

采用电子辅助热丝化学气相沉积技术制备了垂直石墨烯(VG)、硼掺杂垂直石墨烯(BVG)、氮掺杂垂直石墨烯(NVG)及硼-氮共掺杂垂直石墨烯(BNVG)薄膜,采用扫描电子显微镜、透射电子显微镜、X射线光电子能谱及Raman光谱仪表征了形貌、微结构及成分,并采用电化学方法分析了其作为表皮传感电极的电化学性能。结果表明,BNVG薄膜由垂直于基片生长的二维纳米片排列成了三维多孔网结构,这些纳米片的硼和氮原子分数达到3.78%和2.75%。BNVG薄膜电极的皮肤接触电阻低至4.5 kΩ,对于葡萄糖的响应浓度范围在0.001～10 000μmol·L^-1,检测限低至0.03μmol·L^-1,具有良好的抗干扰能力及长期稳定性。     

不同碳源催化化学气相沉积制备自支撑C/Ni-Fiber复合电极材料的电容脱盐性能

以甲烷、乙烯、乙醇和正丁醇为碳源,通过催化化学气相沉积在具有三维开放网络结构的烧结8μm-Ni金属纤维上沉积碳的方法,制备了以金属Ni纤维网络为集流极、沉积碳为离子存储库的薄层大面积自支撑C/Ni-fiber复合电极材料.用扫描电子显微镜（SEM）、透射电子显微镜（TEM）、热重分析（TGA）、X射线衍射（XRD）、N₂-吸脱附等温线和循环伏安与电化学阻抗谱对电极材料进行了表征,并考察了其作为电极的电容脱盐性能.乙烯、甲烷、正丁醇和乙醇为碳源的沉积碳形态分别为鱼骨状碳纳米管（CNTs）、石墨烯面取向与轴平行的CNTs、棒状和蠕虫状碳纳米纤维（CNFs）.C/Ni-fiber复合电极材料对NaCl的电吸附容量顺序为:乙烯>正丁醇>甲烷>乙醇,这与复合电极的电化学特性、孔结构和碳的纳米结构相关.在1.2 V的工作电压下,以乙烯为碳源制备的C/Ni-fiber复合电极材料对水溶液中NaCl(100 mg·L^-1)的电吸附容量达159μmol·g^-1.     

锂磷氧氮(LiPON)薄膜电解质和全固态薄膜锂电池研究

采用电子束热蒸发Li₃PO₄与氮等离子体辅助相结合的方法制备了含氮磷酸锂(LiPON)电解质薄膜,已测得该非晶态电解质薄膜在温度为300K时的离子导电率为6.0×10^-7 S/cm,电子电导率低于10^-10 S/cm,电化学稳定窗口为5.0V.以脉冲激光沉积法(PLD)制备的非晶态Ag_0.5V₂O₅薄膜为阴极,真空热蒸发法制备的金属锂为阳极,LiPON薄膜为电解质,成功地制备了一个新的Li/LiPON/Ag_0.5V₂O₅全固态薄膜锂电池.该电池以14μA/cm²电流充/放电时,首次放电容量达到62 μAh·cm^-2·μm^-1,10次循环后容量衰减缓慢,衰减率约为0.2%,循环寿命达到550次以上.     

电化学法制备部分还原氧化石墨烯薄膜及其光电性能

提供了一种快速制备氧化石墨烯(GO)薄膜的方法, 并通过调节GO薄膜的含氧量来调控其能级结构.采用阳极电泳及阴极电化学还原联用的方法在F掺杂SnO₂(FTO)导电玻璃上制备出不同层数及含氧量的GO薄膜, 并通过扫描电镜(SEM)、X射线衍射(XRD)、紫外可见(UV-Vis)光谱、X射线光电子能谱(XPS)、拉曼光谱及电化学分析对样品进行表征. 用20-350 s 不同时间电泳沉积得到层数约为77-570层的GO薄膜. 经过不同时间阴极还原的GO薄膜的禁带宽度为1.0-2.7 eV, 其导带位置及费米能级也随之改变. GO作为p型半导体, 与FTO导电膜之间会形成p-n 结, 在光强为100 mW·cm^-2的模拟太阳光照射下, 电泳300 s 且电化学还原120 s时GO薄膜阳极光电流密度达到5.25×10^-8 A·cm^-2.     

溶剂热电化学还原氯仿制备类金刚石碳膜的研究

报道了采用溶剂热电化学法还原氯仿制备类金刚石碳膜(DLC)的新体系. 实验在－1.2或－1.6 V (vs. Ag/AgCl/Cl^－)下, 对溶解在以Bu₄NCl作为支持电解质的碳酸丙烯酯(PC)溶液中的氯仿进行电化学还原. 研究了温度、氯仿/PC比例和电极材料对沉积的影响. 采用拉曼光谱, SEM, FTIR, XPS等方法对产物进行表征. 结果表明,在100 ℃,氯仿/PC比例为1∶3, Pt电极上沉积的DLC膜含有较高的sp³杂化态碳. 论文还提出了电化学还原氯仿沉积DLC薄膜的机理.     

石墨烯/钴镍双氢氧化物复合材料的制备及其超电容特性

采用氧化石墨(GO)还原法制备石墨烯(GNS),以氨水为沉淀剂,在石墨烯存在的情况下,通过Co²⁺和Ni²⁺化学共沉积的方法合成了石墨烯/钴镍双氢氧化物复合电极材料,采用红外光谱(FT-IR)、X射线衍射(XRD)、场发射扫描电子显微镜(FE-SEM)、比表面积测试(BET)等技术手段表征了产物的组成、结构和形貌,用循环伏安、恒电流充放电等测试方法对复合材料的电化学性能进行了研究。 研究发现,石墨烯纳米片均匀分散在钴镍双氢氧化物中,改善了钴镍双氢氧化物的传导性和结构稳定性。 电化学测试表明,在1 A/g的电流密度下,复合材料比电容高达2770 F/g,且循环500次后,比电容仍能保持93.4%,呈示该复合材料具有优异的电化学性能。     

Ag+掺杂聚苯胺的制备及其电容特性研究

以苯胺为单体,采用界面聚合法合成了不同浓度的Ag⁺掺杂的聚苯胺(PANI/Ag⁺),使用傅里叶变换红外光谱（FT-IR）、X射线衍射（XRD）和场发射扫描电镜（SEM）等手段对其结构和形貌进行了分析和表征. 在0.5 mol•L^-1 Na₂SO₄电解液中,通过循环伏安（CV）、恒流充放电（CP）以及电化学阻抗（EIS）等技术研究了其电化学性能. 结果表明,当电流密度为5 mA•cm^-2时,PANI/0.12mol•L^-1 Ag⁺的比电容达529 F•g^-1,循环1000次后比电容保持51%,相对于无Ag⁺掺杂的PANI,表现出更优良的电化学电容特性.     

Approach to excellent superhydrophobicity and corrosion resistance of carbon-based films by graphene and cobalt synergism

A new series of carbon-based films doped with graphene oxide and cobalt (G-Co/a-C:H films) were successfully prepared on Si substrate via one-step electrochemical deposition of methanol as the carbon source and graphene oxide/cobalt as the dopant. G-Co/a-C:H films were fabricated at various graphene oxide concentration for comparative experiments. It can be found that the graphene oxide and cobalt were well embedded in amorphous carbon matrix to form superhydrophobic G-Co/a-C:H film at the doping GO concentration of 0.007 mg/mL, which was confirmed by transmission electron microscopy (TEM). It was noted that the superhydrophobicity of the resulting surface derives from its rough surface with hierarchical micro-nanostructures and the presence of the low-surface-energy GO components on it. The hierarchical micro-nanostructures are attributed to the corporate joint of GO and cobalt to form the multilevel nanoscale composite interface. Specially, the as-fabricated superhydrophobic G-Co/a-C:H film could exhibit excellent self-cleaning ability and corrosion resistance, revealed by the self-cleaning and corrosion tests.     

热辅助存储磁盘硅掺杂非晶碳薄膜氧化的ReaxFF反应力场分子动力学模拟

Heat-assisted magnetic recording (HAMR) is one of the promising ways to extend the magnetic recording area density to 1 Tb·in^-2 in hard disk drives (HDDs).High temperature induced by laser heating can cause carbon overcoat (COC) oxidation.Reactive molecular dynamics (MD) simulations are performed to investigate the oxidation process of silicon-doped amorphous carbon (a-C:Si) films for HAMR application.The atomic details of the structure evolution and oxidation process are investigated, and, the oxidation mechanism of the a-C:Si film is clarified.The effect of the duration of laser irradiation on the oxidation of the a-C:Si film is investigated.The oxidation occurs during heating and the beginning of cooling process.Both volume expansion during heating process and cluster of carbon atoms during cooling process increase the rate of sp² carbon.Because of the decrease in the amount of unsaturated silicon atoms and low diffusion coefficient of atomic oxygen, the oxidation rate of the a-C:Si film decreases with laser irradiation cycles.The molecular oxygen is the oxidant due to surface defect of a-C:Si film.The atomic strains break the O-O bonds in Si-O-O-Si linkages and rearrange the surface oxide layers, and process the oxidation of the a-C:Si film.     

Highly Sensitive and Selective Amperometric Sensor for Iodate Based on 9,10-Phenanthrenequinone Derived Graphene

We reported on a new amperometric sensor for the sensitive and selective determination of iodate in table salt. The iodate sensor was constructed by the integration of a novel nanocomposite which was made from 9,10-phenanthrenequinone(PQ) and graphene(GP) with a glassy carbon electrode(GCE). The synthesized graphene and the nanocomposite were well characterized by X-ray diffraction(XRD), transmission electron microscopy(TEM), Fourier transform infrared(FTIR) spectroscopy and Raman spectroscopy. We fully studied the electrochemical behavior and kinetic characteristics of the PQ/GP nanocomposite at GCE. The PQ/GP electrode shows a good electrochemical catalytic activity towards the reduction of iodate, which makes itself a sensitive and selective electrochemical sensor for iodate. The iodate sensor displays a high sensitivity(1.04 mA·mmol·L^-1), a low detection limit(1.0×10^-8 mol/L), a rapid response(less than 2 s), and a broad linear range(from 5.0×10^-8 mol/L to 6.0×10^-3 mol/L ). In addition, the sensor is interference free. The practical application of the proposed sensor was tested by the detection of iodate in table salt.     

Direct Electrochemistry and Electrocatalysis of Myoglobin Immobilized on Graphene‐CTAB‐Ionic Liquid Nanocomposite Film

This paper describes the direct electrochemistry and electrocatalysis of myoglobin immobilized on graphene‐cetylramethylammonium bromide (CTAB)‐ionic liquid nanocomposite film on a glassy carbon electrode. The nanocomposite was characterized by transmission electron microscopy, scanning electron microscopy, X‐ray photoelectron spectroscopy, and electrochemistry. It was found that the high surface area of graphene was helpful for immobilizing more proteins and the nanocomposite film could provide a favorable microenvironment for MB to retain its native structure and activity and to achieve reversible direct electron transfer reaction at an electrode. The ionic liquid may play dual roles here: it keeps the protein's activity and improves stability of the nanocomposite film; it also serves as a binder between protein and electrode, therefore, enhancing the electron transfer between the protein and the electrode. The nanocomposite films also exhibit good stability and catalytic activities for the electrocatalytic reduction of H₂O₂.     

Self-ion irradiation on hydrogenated amorphous carbon films at depth of adhesion interlayer: Radiation-induced atomic intermixing and degraded film properties

Hydrogenated amorphous carbon (a-C:H) films consisting of a top a-C:H layer, a gradient transient a-C:H:Ti layer, and a bottom Ti layer were irradiated by 1.1-MeV C⁺ ions, resulting in a maximum displacement damage of 1.0 dpa and a projected range inside the Ti layer. Time-of-flight secondary ion mass spectrometry, electron energy loss spectroscopy, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy analyses were performed to investigate the compositional and structural transitions of a-C:H films after self-ion irradiation. The results revealed that C⁺ ions passing through the top a-C:H layer induced C–H fracture and hydrogen diffusion in this layer and then resulted in atomic intermixing in the multilayered adhesion interlayer. After local energy deposition of C⁺ ions, the initial sharp interfaces in the a-C:H:Ti layer became ambiguous due to interfacial mixing. In addition, titanium carbides formed in the Ti layer, with a gradual phase transition from TiCx to TiC with a diffusion depth of 200 nm. The broken compositional gradients of the adhesion interlayer resulted in a significant decrease in the adhesion strength of the films, which eventually resulted in degraded antiwear properties of the irradiated film in dry sliding tribotests.     

单极脉冲一步合成聚苯胺/铁氰化镍杂化膜及其过氧化氢电催化还原活性

采用单极脉冲法在铂基体表面一步合成聚苯胺/铁氰化镍 (PANI/NiHCF) 有机-无机杂化膜,并分析了杂化膜高电势静电吸引沉积机理. 高电压聚合杂化膜避免了Fe(CN)₆^3-的还原,并形成单一“不可溶”结构NiHCF. 用扫描电镜（SEM）、X射线能谱仪（EDS）和傅立叶变换红外（FT-IR）光谱研究了杂化膜表面形貌及组成,并考察了不同单极脉冲电压制得杂化膜的电化学性能. 结果表明,单极脉冲电压1.0 V制得的PANI/NiHCF杂化膜有最佳的电活性和良好的稳定性. 使用计时电流法考察了杂化膜电极的过氧化氢（H₂O₂）的电催化还原活性,在0.5 mol·L^-1 KCl + 0.5 mol·L^-1 HCl电解液中,PANI/NiHCF杂化膜电极过氧化氢催化还原电流与其浓度（4.0×10^-4 ~ 1.6×10^-2 mol·L^-1）呈良好的线性关系,相关性系数R = 0.9991,检出限为6.09×10-5 mol·L-1,灵敏度为1075 mA·(mol·L-1)-1·cm-2.     

A Sensitive and Selective Nitrite Detection in Water Using Graphene/Platinum Nanocomposite

A glassy carbon electrode modified with reduced graphene oxide and platinum nanocomposite film was developed simply by electrochemical method for the sensitive and selective detection of nitrite in water. The electrochemical reduction of graphene oxide (GO) efficiently eliminates oxygen‐containing functional groups. Pt nanoparticles were electrochemically and homogeneously deposited on the ErGO surface. Field emission scanning electron microscopy (FE‐SEM), Raman spectroscopy, attenuated total reflectance‐fourier transform infrared spectroscopy (ATR‐FTIR), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV) were used to examine the surface morphology and electrocatalytic properties of the Pt‐ErGO nanocomposite film‐modified electrode surface. The fabricated nitrite sensor showed good electrochemical performance with two linear ranges; one from 5 to 100 µM (R²=0.9995) and the other from 100 to 1000 µM (R²=0.9972) and a detection limit of 0.22 µM. The proposed sensor was successfully applied for the detection of nitrite in tap water samples which proves performance of the Pt‐ErGO nanocomposite films.     

Synthesis and Characteristics of Fe_3C Nanoparticles Embedded in Amorphous Carbon Matrix

We proposed a new way to synthesize a nanocomposite consisted of cementite Fe3C nanoparticles and amorphous carbon by radio frequency plasma-enhanced chemical vapor deposition. Transmission electron microscope images show the existence of nanometric dark grains(Fe3C) embedded in a light matrix(amorphous carbon) in the samples. X-ray photoelectron spectroscopy experiment exhibit that the chemical bonding state in the films corresponded to sp3/sp2 amorphous carbon, sp3 C―N(287.3 eV) and C1s in Fe3C(283.5 eV). With increasing deposition time, the ratio of amorphous carbon increased. The magnetic measurements show that the value of in-plane coercivity increased with increasing carbon matrix concentration(from about 6.56×103 A/m for film without carbon structures to approximately 2.77×104 and 5.81×104 A/m for nanocomposite films at room temperature and 10 K, respectively). The values of saturation magnetization for the synthesized nanocomposites were lower than that of the bulk Fe3C (140 Am2/kg).     

聚苯胺-还原氧化石墨烯复合材料的比电容及超级电容性能

Flaky polyaniline-reduced graphene oxide (PANI-rGO) composites have larger specific capacitance due to the improved redox charge of PANI in the composites, fabricated by simultaneous reduction of PANI-GO. The structural and morphological analyses were carried out using scanning electron microscopy, UV-Vis spectroscopy, and thermogravimetry. The results showed that the composites are flaky in shape. PANI is uniformly coated on GO, and PANI-rGO has specific capacitance as high as 1069 F·g^-1 (1.71 F·cm^-2) at a current density of 20 A·g^-1, 5 times higher than PANI-GO; this is caused by the large surface and conductivity of the rGO in the composite.     

室温电子还原制备金纳米颗粒与琼脂糖复合膜的表征与应用

利用室温电子还原技术合成了一种金纳米颗粒与琼脂糖复合膜。合成过程采用氩气辉光放电为廉价电子源,方便快捷,绿色环保。通过紫外-可见(UV-Vis)分光光度计、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、X射线衍射(XRD)仪、光电子能谱(XPS)等表征,发现可以通过改变氯金酸浓度调控复合膜中金纳米颗粒的分布,加入聚乙烯吡咯烷酮(PVP)可有效控制金纳米颗粒的形貌。由于复合膜具有金纳米颗粒密集排布的结构,可作为表面增强拉曼散射(SERS)活性基底。实验表明,以对氨基苯硫酚为探针,该复合膜作为SERS基底,SERS平均增强因子超过了106,检测限达到了10-12mol?L-1。除此之外,作为SERS基底,复合膜具有良好的均一性和稳定性。