还原石墨/氧化锌复合薄膜的制备及其光电转换性能

本工作研究不同过程还原的氧化石墨rGO/ZnO(reduced graphite oxide/ZnO)复合膜的可见光激发光电转换性能。氧化石墨(GO)经KOH还原处理或NaBH₄还原处理后, 和氧化锌溶胶混合, 通过旋涂法和热处理在F掺杂SnO₂薄膜导电玻璃(FTO)衬底上形成复合薄膜。采用XRD、FTIR、FE-SEM、XPS、UV-Vis等方法对复合薄膜的晶相结构、微观形貌等进行表征, 并测试了复合薄膜在可见光照射下的光电转换性能。GO的预处理过程对复合薄膜的结构影响显著, 采用NaBH₄对GO处理更有利于形成均匀薄膜。光电流测试结果表明不同复合薄膜均能实现可见光照射下产生光电流, 其原理为rGO的光激发电子跃迁到ZnO, 而空穴在rGO中迁移, 在rGO与ZnO界面实现光生载流子分离。其中NaBH₄处理后的rGO/ZnO复合薄膜光电流密度最大, 达6×10^-7 A·cm^-2。     

ZnO/RGO复合材料的结构及其光催化性能研究

本实验以ZnSO₄和氧化石墨(Graphite Oxide,GO)原料,在低温环境下(60 ℃)制备了层状ZnO/RGO(ZnO/Reduced Graphite Oxide)复合材料。通过对ZnO/RGO复合材料进行XRD、FTIR、XPS和FE-SEM等测试,表征了产物的晶相结构、界面状况及微观形貌特征。氧化石墨在与ZnO的复合反应过程中其活性基团消失或减弱,氧化石墨自身被还原为一种类石墨物质(Reduced GO,RGO);GO的预处理过程对产物的形貌有较大影响,采用稀碱溶液对石墨的剥离处理有利于产物的层状结构形成。本文还以甲基橙为目标降解物,考察了不同条件下所得催化剂的紫外光催化性能。研究表明,ZnO/RGO纳米复合材料大大提高了ZnO紫外光催化活性。光致发光谱(PL)显示,ZnO/RGO复合材料的荧光发射峰强度比纯ZnO有较大降低,说明ZnO的光激发电子在氧化石墨的还原产物RGO和ZnO纳米颗粒之间存在界面电子转移效应,因而抑制了ZnO中光生电子-空穴对的复合,从而提高了ZnO的光催化性能。     

硒/氧化石墨烯/二氧化钛复合薄膜的制备及光电转换性质

将氧化石墨烯(GO)掺入钛酸溶胶中,以导电玻璃(ITO)为基底,经浸渍-涂覆-煅烧得到GO/TiO2复合薄膜;采用电沉积技术在GO/TiO2薄膜表面沉积Se纳米微粒,得到Se/GO/TiO2复合薄膜;利用扫描电子显微镜和X射线衍射仪分析了复合薄膜的形貌和晶体结构,采用紫外可见光谱仪测定了其光谱学性质,利用光电转换实验测定了其光电转换性质.结果表明,所制备的Se/GO/TiO2复合薄膜各组分分布均匀,具有锐钛矿相结构的TiO2颗粒粒径为20nm,与TiO2结合的GO具有分散片层结构,薄膜中的Se颗粒粒径为60～80nm.与此同时,在Se和GO的共同作用下,Se/GO/TiO2复合薄膜对可见光有很好的光电转换效应.     

可见光响应Bi2WO6薄膜的制备与光电化学性能

采用非晶态配合物-提拉法在ITO导电玻璃基底上制备得到Bi2WO6薄膜. 采用FE-SEM、XRD、Raman、DRS、光电流响应谱、IPCE等手段, 研究了Bi2WO6薄膜的形貌、结构、光电性能以及薄膜结构与光电性能的关系. 结果表明, 450 ℃以上煅烧可以得到Bi2WO6结晶薄膜, 薄膜由沿(131)晶面趋向生长的Bi2WO6纳米颗粒组成, 颗粒的粒度随煅烧温度的升高而增大, 同时颗粒之间的间距也相应增大. ITO/Bi2WO6薄膜电极在可见光(λ>400 nm)照射下可以产生光电流, 光电流强度与光强度线性相关; 光电流强度和光电转换量子效率受Bi2WO6薄膜结构的影响, 通过控制薄膜的煅烧温度等制备条件, 可以提高薄膜光电极的光电转换量子效率.     

碳网封装Fe3O4/还原氧化石墨烯锂离子电池负极材料

通过简单有效的溶剂热法将Fe3 O4颗粒与氧化石墨烯(GO)进行复合,得到Fe3 O4/GO复合材料.将Fe3 O4/GO与葡萄糖进行碾磨.在高温下将GO还原成还原氧化石墨烯(rGO)的同时在Fe3 O4/rGO表面制备网状结构的导电碳层,得到三维网络传输结构C/Fe3 O4/rGO复合材料.由碳网和还原氧化石墨烯组成...     

氧化石墨烯在氧化锌衬底上的电化学还原及其光电性能

采用阳极电泳法,在氧化锌(ZnO)衬底上沉积氧化石墨烯(GO)以形成GO-ZnO双层复合膜;采用阴极恒电位法,对复合膜上的GO进行还原。对不同还原时间的GO,通过X射线光电子能谱(XPS),傅里叶变换红外(FTIR)光谱,场发射扫描电子显微镜(FESEM)等手段对其结构变化进行表征,采用紫外-可见(UV-Vis)分光光度法和电化学测试手段对其能级演变进行考察,并对两者的对应关系进行了讨论。研究发现,当GO膜达到最大还原态后,随还原时间增加还会出现进一步的结构转变,并最终碎裂生成边缘羧基增多的小尺寸GO。GO能隙均减小至可见光范围,其能级位置及半导体极性也产生了不同的改变。由对复合膜的光电化学测试可见,除1800 s GO能级不再与ZnO匹配外,60 s到600 s GO-ZnO复合膜均可作为阳极光电极进行太阳光电转换。对光电性能差异的讨论则可得,GO膜碎裂造成叠层形貌向无序形貌的转变有利于光电转换性能的提升。     

CdS/石墨烯复合材料的制备及其可见光催化分解水产氢性能

以氧化石墨烯和CdS为原料, 在乙醇水溶液中采用CdS光催化还原法制备了CdS/石墨烯复合光催化材料, 并用透射电子显微镜(TEM)、X射线衍射(XRD)、傅里叶变换红外(FTIR)光谱、X射线光电子能谱(XPS)和瞬态光电流等技术对复合材料的结构和光电性能进行了表征. 可见光照射下(λ≥420 nm), 研究了该复合材料光催化分解水产氢的性能. 结果表明, 可见光照射下CdS的光生电子可有效地还原氧化石墨烯, 得到CdS与石墨烯之间具有强相互作用力的CdS/石墨烯复合材料. 与CdS相比, 复合材料中石墨烯作为良好的电子受体和传递介质, 可明显加快CdS光生电子的迁移速率, 提高光生载流子的分离效率, 从而增强复合材料的光电性能和光催化分解水产氢的活性.     

新型可见光光电材料NiNb2O6的合成及其光电化学性质

本文报道了"软化学"法合成得到的新型光电转换材料NiNb2O6的合成及其在可见光照射下的光电化学性质。采用X-射线衍射(XRD)、扫描电子显微镜(SEM)以及紫外-可见漫反射谱(DRS)等手段研究了合成材料的晶型结构、形貌以及光物理性质。结果表明,该材料具有与Nb2O5完全不同的新型结构,且具有两个明显的吸收带,相应的禁带宽分别为3.02和2.30 eV,具有较好的可见光(λ>420 nm)吸收性能。在可见光下照射下NiNb2O6薄膜光电极上观察到有光电流的产生,表明其具有较好的光电转换性能。     

液相沉积法制备ZnO/CdS复合纳米棒阵列薄膜及其光电性质

采用两步化学溶液沉积法在氧化铟锡(ITO)导电玻璃衬底上制备了ZnO/CdS复合纳米棒阵列薄膜.利用X射线衍射(XRD)仪、扫描电子显微镜(SEM)、紫外-可见(UV-Vis)吸收分光光度计、荧光(PL)光谱仪及表面光电压谱(SPS)研究了不同CdS沉积时间对复合薄膜的晶体结构、形貌、光电性质的影响.研究结果表明:ZnO纳米棒阵列表面包覆CdS纳米颗粒后,其吸收光谱可拓展到可见光区;与吸收光谱相对应在可见光区出现新的光电压谱响应区,这一现象证实,通过与CdS复合可显著提高ZnO纳米棒阵列在可见光区的光电转换性能;随着CdS纳米颗粒沉积时间的延长,复合纳米棒阵列薄膜在大于383nm波长区域的光电压强度逐渐减弱,而在小于383nm波长区域的光电压强度逐渐增强.用两种不同的电荷产生和分离机制对这一截然相反的光响应过程进行了详细的讨论和解释.     

CdS量子点敏化ZnO纳米棒阵列电极的制备和光电化学性能

采用连续式离子层吸附与反应法制备了CdS量子点敏化的ZnO纳米棒电极.应用扫描电子显微镜(SEM)、X射线衍射(XRD)和透射电子显微镜(TEM)对CdS量子点/ZnO纳米棒电极的形貌、晶型和颗粒尺寸进行了分析和表征;采用光电流-电位曲线和光电流谱研究了不同CdS循环沉积次数及不同沉积浓度对复合电极的光电性能影响.结果表明,前驱体浓度都为0.1mol·L-1且沉积15次敏化后的ZnO纳米棒阵列电极光电性能最好.与单纯的ZnO纳米棒阵列电极和单纯的CdS量子点电极相比,其光电转换效率显著提高,单色光光子-电流转换效率(IPCE)在380nm处达到76%.这是因为CdS量子点可以拓宽光的吸收到可见光区,并且在所形成的界面上光生载流子更容易分离.荧光光谱实验进一步说明了光电增强的原因是,两者间形成的界面中表面态大大减少,有利于减少光生电子和空穴的复合.     

Applied bias photon-to-current conversion efficiency of ZnO enhanced by hybridization with reduced graphene oxide

The role of reduced graphene oxide(rGO) in the enhancement of photo-conversion efficiency of ZnO films for photoelectrochemical(PEC) water-splitting applications was analyzed. ZnO and rGO-hybridized ZnO(rGO/ZnO) films were prepared via a two-step electrochemical deposition method followed by annealing at 300 °C under argon gas flow. The physical, optical and electrochemical properties of the films were characterized to identify the effect of rGO-hybridization on the applied bias photon-to-current efficiency(ABPE) of ZnO. Scanning electron microscopy and X-ray diffraction indicated the formation of verticallyaligned, wurtzite-phase ZnO nanorods. Diffuse-reflectance UV–visible spectroscopy indicated that rGO-hybridization was able to increase the light absorption range of the rGO/ZnO film. UPS analysis showed that hybridization with rGO increased the band gap of ZnO(3.56 eV) to 3.63 eV for rGO/ZnO sample,which may be attributed to the Burstein–Moss effect. Photoluminescence(PL) spectra disclosed that rGOhybridization suppressed electron-hole recombination due to crystal defects. Linear sweep voltammetry of the prepared thin films showed photocurrent density of 1.0 and 1.8 m A/cm~2 for ZnO and rGO/ZnO at+0.7 V, which corresponded to an ABPE of 0.55% and 0.95%, respectively. Thus, this report highlighted the multi-faceted role of rGO-hybridization in the enhancement of ZnO photo-conversion efficiency.     

Reassessing the Necessity of the Drying Step in Hummer's Method for Graphene Oxide Synthesis

The necessity of drying the graphene oxide suspension (GOsus) using Hummer's Method to produce graphene oxide (GO) powder was studied. The undried GOsus was compared to the dried GO. The GO materials were used as Pt supports via NaBH₄ reduction for O₂ reduction. XRD patterns showed similar d-spacing in both while the half-cell tests of the Pt/rGOsus and Pt/rGO catalysts were similar. GOsus film, deposited onto Toray Carbon Paper and electrochemically reduced in aq. H₂SO₄ was tested as a capacitor. The suspension and dried graphene-based capacitor showed similar XRD and XPS patterns and the erGOsus capacitor displayed increased capacitance.     

Manganese Oxide Nanoparticles/Reduced Graphene Oxide as Novel Electrochemical Platform for Immobilization of FAD and its Application as Highly Sensitive Persulfate Sensor

In this study, manganese oxide nanoparticles/reduced graphene oxide(MnOxNPs/rGO) was used as support for strong immobilization of flavin adenine dinucleotide(FAD). A thin film of rGO cast on the electrode surface, followed by performing electrodeposition of MnOxNPs at applied constant potential of +1.4 V vs. Ag/AgCl for 200 s. Finally, FAD was electrodeposited onto the rGO/MnOxNPs film by potential cycling between 1.0 to ?1.0 V in solution containing 1 mg ml^?1 FAD. Electrochemical properties and catalytic activity of GCE/rGO‐MnOxNPs/FAD toward persulfate (S₂O₈^2?) reduction was investigated. Under optimized condition, the concentration calibration range, detection limit, and sensitivity were 0.1 μM–2 mM, 90 nM and 125.8 nA/μM, respectively, using hydrodynamic amperometry technique.     

Sodium‐Ion Storage Properties of FeS–Reduced Graphene Oxide Composite Powder with a Crumpled Structure

The sodium‐ion storage properties of FeS–reduced graphene oxide (rGO) and Fe₃O₄‐rGO composite powders with crumpled structures have been studied. The Fe₃O₄‐rGO composite powder, prepared by one‐pot spray pyrolysis, could be transformed to an FeS‐rGO composite powder through a simple sulfidation treatment. The mean size of the Fe₃O₄ nanocrystals in the Fe₃O₄‐rGO composite powder was 4.4 nm. After sulfidation, FeS nanocrystals of size several hundred nanometers were confined within the crumpled structure of the rGO matrix. The initial discharge capacities of the FeS‐rGO and Fe₃O₄‐rGO composite powders were 740 and 442 mA h g^?1, and their initial charge capacities were 530 and 165 mA h g^?1, respectively. The discharge capacities of the FeS‐rGO and Fe₃O₄‐rGO composite powders at the 50th cycle were 547 and 150 mA h g^?1, respectively. The FeS‐rGO composite powder showed superior sodium‐ion storage performance compared to the Fe₃O₄‐rGO composite powder.     

γ-Ray Irradiation-Derived MnO/rGO Composites for High Performance Lithium Ion Batteries

We report a γ-ray irradiation reduction method to prepare MnO/reduced graphene oxide (rGO) nanocomposite for the anode of lithium ion batteries. γ-Ray irradiation provides a clean way to generate homogeneously dispersed MnO nanoparticles with finely tuned size on rGO surface without the use of surfactant. The MnO/rGO composite enables a fully charge/discharge in 2 min to gain a reversible specific capacity of 546 (mA·h)/g which is 45% higher than the theoretical value of commercial graphite anode.     

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

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

Composite films of polyaniline and molybdenum oxide formed by electrocodeposition in aqueous media

Composite films of polyaniline (PANI) and molybdenum oxide (MoO_x) were afforded through a convenient route of electrocodeposition from aniline and (NH₄)₆Mo₇O₂₄. The composite films showed characteristic redox behaviors of PANI and MoO_x, respectively, on the cyclic voltammograms. Chlorate and bromate were catalytically electroreduced with an enlarged current on the composite film at a potential ca. 0.2 V more positive than that on MoO_x. The potential window for the composite film to display pseudocapacitive properties in 1.0 mol·dm⁻³ NaNO₃ was −0.6 ∼ 0.6 V vs SCE. The cathodic potential limit shifted at least 0.4 V negatively from that of polyaniline (PANI)-based materials reported so far. The specific capacitance was 363.6 F·g⁻¹ when the composite film was charged–discharged at 1.5 mA·cm⁻², about two times of that of the similarly prepared PANI. The composite film was characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Molybdenum existed in a mixed state of +5 and +6 in the composite film based on XRD and XPS investigations. Figure PANI and (MoO_x) were electrocodeposited in aqueous solutions from aniline and (NH₄)₆Mo₇O₂₄. The composite film obtained displayed catalytic activities toward the electroreduction of oxoanions. The pseudocapacitance of the composite film is nearly two times of that of PANI with the potential window extended negatively up to −0.6 V vs SCE     

中空分级结构Fe3O4@C/rGO复合材料的合成及其储锂性能

以氧化石墨烯(GO)为基底,Fe(NO_3)_3·9H_2O、异丙醇、甘油为原料,通过溶剂热法和后续热处理过程2步合成了Fe_3O_4@C/rGO复合材料,实现了碳包覆的Fe_3O_4纳米粒子自组装形成的分级结构空心球在氧化石墨烯片上的原位生长。采用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)和恒流充放电等手段分析了材料的物理化学性能与储锂性能。结果表明,该复合材料在5.0 A·g~(-1)的电流密度下,仍有437.7 mAh·g~(-1)的可逆容量,在1.0 A·g~(-1)下循环200圈后还有587.3 mAh·g~(-1)的放电比容量。这主要归因于还原态氧化石墨烯(rGO)对碳包覆Fe_3O_4分级空心球整体结构稳定性和导电性的提高。     

电解液成分、厚度及表面改性对旋涂法制备的BiVO4膜层光电化学性能的影响

采用旋涂法在FTO（SnO₂∶F）导电玻璃衬底上沉积得到BiVO₄多孔薄膜用以光解水,改变前驱体的浓度和旋涂次数以调控薄膜的厚度。研究了电解液成分、膜层厚度及表面改性等因素对刚经历过退火处理的BiVO₄薄膜光电化学（PEC）性能的影响。结果表明：通过在电解液中添加适量的空穴吞噬剂Na₂SO₃,或对表面进行Co-Pi改性均能有效改善BiVO₄薄膜的PEC活性。这些措施均能有效抑制固液界面处的载流子复合反应。经Co-Pi改性的BiVO₄薄膜在0.6 V（vs SCE）偏压下,0.1 mol·L^-1 Na₂SO₄+0.1 mol·L^-1 Na₂SO₃的电解液中展现出最高的光电流密度（4.3 mA·cm^-2）。此外,选用一个代表性BiVO₄薄膜作为光阳极制备了一个PEC生物传感器,在检测谷胱甘肽（GSH）上表现出比较高的灵敏度。本研究证实了BiVO₄薄膜的PEC性能严重依赖着光俘获效率和载流子输运过程。