Microwave-assisted green synthesis of Ag/reduced graphene oxide nanocomposite as a surface-enhanced Raman scattering substrate with high uniformity

A nanocomposite of silver nanoparticles/reduced graphene oxide (Ag/rGO) has been fabricated as a surface-enhanced Raman scattering (SERS) substrate owing to the large surface area and two-dimensional nanosheet structure of rGO. A facile and rapid microwave-assisted green route has been used for the formation of Ag nanoparticles and the reduction of graphene oxide simultaneously with L-arginine as the reducing agent. By increasing the cycle number of microwave irradiation from 1 and 4 to 8, the mean diameters of Ag nanoparticles deposited on the surface of rGO increased from 10.3 ± 4.6 and 21.4 ± 10.5 to 41.1 ± 12.6 nm. The SERS performance of Ag/rGO nanocomposite was examined using the common Raman reporter molecule 4-aminothiophenol (4-ATP). It was found that the Raman intensity of 4-ATP could be significantly enhanced by increasing the size and content of silver nanoparticles deposited on rGO. Although the Raman intensities of D-band and G-band of rGO were also enhanced simultaneously by the deposited Ag nanoparticles which limited the further improvement of SERS detection sensitivity, the detectable concentration of 4-ATP with Ag/rGO nanocomposite as the SERS substrate still could be lowered to be 10⁻¹⁰ M and the enhancement factor could be increased to 1.27 × 10¹⁰. Furthermore, it was also achievable to lower the relative standard deviation (RSD) values of the Raman intensities to below 5%. This revealed that the Ag/rGO nanocomposite obtained in this work could be used as a SERS substrate with high sensitivity and homogeneity.     

Bifunctional ternary manganese oxide/vanadium oxide/reduced graphene oxide as electrochromic asymmetric supercapacitor

A bifunctional ternary manganese oxide/vanadium oxide/reduced graphene oxide (MnO₂/V₂O₅/rGO) was developed for asymmetric electrochromic supercapacitor (EC-SC) application. The elemental mapping revealed uniformly distributed MnO₂, V₂O₅ and rGO, depicting homogenous synthesis of the hybrid composite. The phase composition, vibration modes and valance state of the ternary composite were analyzed via X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) analysis, respectively. Interestingly, the as-prepared MnO₂/V₂O₅/rGO composite disclosed tremendous C_sp of 1403.5 F/g, which was higher compared to MnO₂/V₂O₅ (801.1 F/g), V₂O₅ (613.1 F/g), MnO₂ (126.7 F/g) and rGO (60.7 F/g). MnO₂/V₂O₅/rGO that appeared in dark green switched its visual color to orange at the charged state, confirming the electrochromic property. The bifunctional manganese oxide/vanadium oxide/reduced graphene oxide//copper-based metal-organic framework/reduced graphene oxide (MnO₂/V₂O₅/rGO//MrGO) asymmetrical EC-SC device revealed outstanding cycling stability (90.3% charge retention over 5000 cycles), tremendous specific capacitance (652.7 F/g) and maximum specific energy (60.4 Wh/kg). MnO₂/V₂O₅/rGO//MrGO asymmetrical EC-SC device demonstrated reversible color changes from dark green to orange at the discharged and charged states, respectively. The significantly great electrochromic and supercapacitive performance revealed that MnO₂/V₂O₅/rGO//MrGO is an outstanding electroactive candidate for the next generation of electrochromic supercapacitors.     

Coherent anti-Stokes Raman scattering enhancement of thymine adsorbed on graphene oxide

Coherent anti-Stokes Raman scattering (CARS) of carbon nanostructures, namely, highly oriented pyrolytic graphite, graphene nanoplatelets, graphene oxide, and multiwall carbon nanotubes as well CARS spectra of thymine (Thy) molecules adsorbed on graphene oxide were studied. The spectra of the samples were compared with spontaneous Raman scattering (RS) spectra. The CARS spectra of Thy adsorbed on graphene oxide are characterized by shifts of the main bands in comparison with RS. The CARS spectra of the initial nanocarbons are definitely different: for all investigated materials, there is a redistribution of D- and G-mode intensities, significant shift of their frequencies (more than 20 cm^-1), and appearance of new modes about 1,400 and 1,500 cm^-1. The D band in CARS spectra is less changed than the G band; there is an absence of 2D-mode at 2,600 cm^-1 for graphene and appearance of intensive modes of the second order between 2,400 and 3,000 cm^-1. Multiphonon processes in graphene under many photon excitations seem to be responsible for the features of the CARS spectra. We found an enhancement of the CARS signal from thymine adsorbed on graphene oxide with maximum enhancement factor about 10⁵. The probable mechanism of CARS enhancement is discussed.     

Spray dryer processed graphene oxide/reduced graphene oxide for high-performance supercapacitor

This study deals with the utility of mini spray dryer process to improve the dispersibility, of graphene oxide(GO) and its application for high-performance supercapacitor. Initially, the neutral solution of GO was obtained using the modified Hummer's method. After this, the prepared GO solution was processed by mini spray dryer to obtain a more purified, lighter, and dispersed form of GO which is named as spray dryer processed GO (SPGO). The SPGO thus obtained showed excellent dispersibility behavior with various solvents, which is not found in case of conventional oven drying. Furthermore, utility of SPGO and its reduced form (r-SPGO) for supercapacitor applications have been investigated. Results obtained from the cyclic voltammetry(CV) analysis, impedance, and charge-discharge behavior of supercapacitor fabricated using r-SPGO shows enhanced features. Therefore, the simple spray dried GO and its reduced form, that is, r-SPGO can be utilized as a potential candidate for the supercapacitor application. Herein, as synthesized SPGO exhibited the specific capacitance of 12.07 and 37.6 F/g with PVA-H₃PO₄ and 1 mol/L H₃PO₄, respectively, at a scan rate of 5 mV/s. On the other hand, reduced form of SPGO, that is, r-SPGO showed the specific capacitance of 27.16 and 230 F/g with PVA-H₃PO₄ and 1 mol/L H₃PO₄, respectively.     

Unusual functionalization of reduced graphene oxide for excellent chemical surface-enhanced Raman scattering by coupling with ZnO

A low-cost noble metal-free substrate comprised of annealed graphene oxide (GO)/ZnO composites is prepared to demonstrate an efficient chemical surface-enhanced Raman scattering effect. A high enhancement factor of about 10⁴, better than those reported for reduced GO (rGO)/Au and GO/Ag composites, is mainly attributed to the unusually abundant oxygen-containing groups generated on surface of rGO by coupling with ZnO nanoparticles at moderate temperature. High-resolution transmission electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy are employed to examine the evolution of ZnO as well as reduction and functionalization of GO after different heat treatments.     

MAX phase-derived woolen ball-like K2Ti8O17 with excellent surface-enhanced Raman scattering property

In surface-enhanced Raman scattering (SERS) applications, the MAX phase is typically acid etched to address deficiencies, while the more accessible alkali corrosion products are neglected. The woolen ball-like K₂Ti₈O₁₇ (KTO) nanomaterial is synthesized via an efficient hydrothermal surface corrosion reaction between KOH solution and MAX phase Ti₂AlN, which exhibits excellent SERS capabilities to the contaminating dyes. The enhancement factors are 2.33 × 10⁵, 1.04 × 10⁵ and 2.22 × 10⁵ with lowest limits of detection of 10⁻⁷ M, 10⁻⁶ M and 10⁻⁷ M for crystal violet, rhodamine 6G and methylene blue, respectively, indicating that KTO is a highly desired candidate of SERS substrate material. Meanwhile, KTO shows excellent SERS performance for chrysoidine in simulated seawater, which proves its practical application value. The excellent SERS performance of KTO is attributed to the charge transfer mechanism, which is made possible by the appropriate energy band structure and the robust adsorption capacity. In conclusion, a novel method for the synthesis of KTO is investigated and its reaction process and enhancement mechanism are exhaustively characterized and described. The woolen ball-like KTO exhibits remarkable SERS properties and potential applications.     

Flash sintering of alumina/reduced graphene oxide composites

The flash sintering behavior of Al₂O₃/reduced graphene oxide (rGO) composites was investigated. rGO was used as a composite component and a conductive additive. Under the electric fields of 250–400 V cm⁻¹, the flash event occurred at extremely low temperatures of 236–249 °C. The current density limit played a significant role in the degree of densification. A larger current density resulted in a higher density of the sample. However, current densities larger than 33.33 A cm⁻² resulted in broken samples because of the localization of high current density coupled with the formation of hot spots. Flash sintering at a furnace temperature of 800 °C, electric field of 300 V cm⁻¹ and current density limit of 33.33 A cm⁻² produced nearly completely dense Al₂O₃/rGO composites. In addition to the current limit, the furnace temperature is also a key parameter that controls the degree of densification to achieve “safe” flash sintering.     

Intensification of photocatalytic pollutant abatement in microchannel reactor using TiO2 and TiO2‐graphene

A microfluidic device was applied to the photocatalytic degradation of methylene blue as a model pollutant. Titanium dioxide nanoparticles (TiO₂–P25) and a synthesized composite TiO₂‐graphene catalyst were immobilized on the inner walls of a borosilicate glass microfluidic chip. The deposition evolution of the nanoparticles was evaluated by monitoring the optical profile of the system. It was found that a higher initial reaction rate was obtained in the microreactor containing composite catalyst (TiO₂‐GR) on the inner walls, but both systems (TiO₂ and TiO₂‐GR) achieved similar reaction rates when the steady‐state was reached. Decolorization rate of methylene blue in our microfluidic chips was found to be approximately one order of magnitude higher than equivalent macroscopic systems reported in the literature at similar experimental conditions. Additionally, computational simulations were performed to investigate the physics involved in these processes. The model was experimentally validated for further scale‐out studies. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2794–2802, 2016     

金刚烷胺/氧化石墨烯复合材料的制备及其吸附性能

以氧化石墨烯和金刚烷为原料，通过水相合成法制备了金刚烷胺功能化氧化石墨烯复合材料A/GO，以FT-IR、XRD和XPS对A/GO进行了结构表征，并考察了A/GO对有机染料的吸附性能。结果表明，与氧化石墨烯相比，A/GO对甲基蓝（AB93）表现出高效吸附性，其吸附动力学和吸附等温模型分别符合拟二级动力学和Langmuir模型，理论最大吸附容量（qm）为1250.0 mg/g。热力学分析表明，A/GO吸附AB93是自发的放热过程。A/GO吸附AB93对盐（NaCl和KCl）表现出良好的耐盐性，而CaCl2能有效地促进A/GO吸附AB93。对于刚果红和AB93等的混合染料体系，A/GO能选择性吸附AB93。     

Heteroatom-doped reduced graphene oxide/polyaniline nanocomposites with improved n-type thermoelectric performance

Polyaniline (PANI) is a potential candidate for n-type thermoelectric (TE) materials owing to its intrinsic electrical conductivity, low thermal conductivity, and facile synthesis techniques. However, its low Seebeck coefficient and power factor have limited its widespread usage. In this study, nitrogen-doped, and sulfur-nitrogen co-doped reduced graphene oxide (rGO) were used for tuning the TE properties of PANI. Doped rGO and PANI/doped-rGO nanocomposites were prepared via hydrothermal technique and chemical oxidative polymerization respectively and thereafter characterized. The TE properties of the nanocomposites were also studied and an optimized Seebeck coefficient, power factor and zT value of −1.75 mV K⁻¹, 95 μW m⁻¹ K⁻² and 0.06, respectively were reported for the PANI nanocomposite containing 1 wt% sulfur-nitrogen co-doped rGO. These results suggest that PANI/heteroatom-doped rGO can serve as promising candidates for n-type based TE applications.     

TiO2／UV／O2和TiO2／UV／N2体系降解水中对氯硝基苯

以商用TiO2P25为催化剂,分别在TiO2/UV/O2和TiO2/UV/N2两种体系下进行降解对氯硝基苯(pCNB)试验.采用ESR对两种体系下光催化反应形成的.OH进行测定,利用LC-MS对两种体系下反应形成的中间产物进行了定性和定量分析,最后对pCNB降解过程中氯和硝基的存在形式进行了研究.结果表明:TiO2/UV/O2体系的催化降解效果要明显优于TiO2/UV/N2体系;两种反应体系都有.OH产生,并且TiO2/UV/O2体系产生的.OH的量多于TiO2/UV/N2体系产生的.OH的量;TiO2/UV/O2体系形成的中间产物的种类要多于TiO2/UV/N2体系形成的,苯环上的氢、氯、硝基均可被.OH取代形成对硝基酚(pNP)、5-氯-2-硝基酚(5-C-2-PN)等酚类物质;两种体系下均有Cl-和NO2-存在,其中Cl-生成势与pCNB的去除势一致,只有TiO2/UV/O2体系中存在NO3-.     

水热合成rGO负载的MoS2催化剂及其催化蒽加氢性能

采用水热法制备了一系列还原氧化石墨烯（rGO）负载的MoS₂催化剂（MoS₂/rGO）。通过SEM、XRD、EDX、拉曼光谱、HRTEM等手段表征了不同钼源制备的MoS₂/rGO催化剂中MoS₂的堆积层数、片层尺寸、分散性等纳米结构。表征结果显示水热法可以成功地将MoS₂高分散、均匀地负载在rGO表面,且可以通过调控钼源种类调变MoS₂/rGO催化剂中MoS₂催化加氢活性位。采用蒽作为重质油模型化合物评价了MoS₂/rGO催化剂的催化加氢性能,结果表明以四硫代钼酸铵为钼源水热法制备的MoS₂/rGO-ATTM催化剂蒽加氢率和八氢蒽选择性分别是浸渍法制备IM-MoS₂/rGO催化剂的2.0倍和4.2倍。MoS₂/rGO催化剂的催化加氢活性与比表面积无关,主要取决于其上MoS₂纳米片的堆积层数和片层长度。MoS₂/rGO-ATTM催化剂的高催化加氢活性可以归结于其上MoS₂纳米片的高催化加氢活性位暴露量、催化剂的高分散性和高悬浮性。     

Synthesis of cellulose/reduced graphene oxide/polyaniline nanocomposite and its properties

A series of conductive nanocomposites cellulose/reduced graphene oxide/polyaniline (cellulose/RGO/PANi) were synthesized via in situ oxidative polymerization of aniline on cellulose/RGO with different RGO loading to study the effect of RGO on the properties of nanocomposites. The results showed that when RGO is inserted into cellulose/PANi structure, its thermal stability and conductivity are increased. So that adding of only 0.3 wt% RGO into the cellulose/PANi structure, its conductivity is increased from 1.1 × 1 10^?1 to 5.2 × 110^?1 S/cm. Scanning electron microscopy results showed that the PANi nanoparticles are formed a continuous spherical shape over the cellulose/RGO template; this increases the thermal stability of nanocomposite.     

Development of a novel smart carrier for drug delivery: Ciprofloxacin loaded vaterite/reduced graphene oxide/PCL composite coating on TiO2 nanotube coated titanium

In the field of orthopaedic implants, post-surgery infections and biocompatibility are the most challenging obstacles. Sustained and controlled antibiotic release is a key factor in novel drug delivery systems. A novel drug delivery system combined with vaterite microsphere, graphite oxide (GO), reduced graphene oxide (rGO) incorporated in a polycaprolactone (PCL) matrix on TiO₂ nanotube coated Ti (TNT-Ti) is established. Anodization was employed to develop TiO₂ nanotubular arrays on Ti. Ciprofloxacin hydrochloride (CPF–HCl) loaded vaterite microspheres were synthesized by in situ precipitation method. Deposition of vaterite/PCL, vaterite-GO/PCL and vaterite-rGO/PCL composite coating on TNT-Ti was carried out by dip coating method. The composite coatings were characterized for their phase content, morphological features and functional groups. Among the three types of composite coatings, vaterite-rGO/PCL composite coating is found to be capable of encapsulating CPF-HCl to a level of 75.14 μg. The drug release profile of CPF-HCl from the vaterite-rGO/PCL composite coating exhibits a controlled release amounting to only 35.02 % of release at the end of 120 h. The vaterite-rGO/PCL composite coating exhibits a low dissolution rate and possesses adequate bioactivity in HBSS and SBF solutions at 37 °C for 14 and 10 days, respectively. The in situ loaded CPF-HCL drug on vaterite microspheres, PCL polymer matrix and GO/rGO nanofillers does not affect the cytocompatibility and all the composite coatings supported cell viability and proliferation. The ability of vaterite-rGO/PCL composite coating to provide a slow and steady release of antibiotics with sufficient bioactivity and biocompatibility at the tissue implant interface makes it a promising for osteomyelitis infection of bone tissue implant materials.     

PAN/氧化石墨烯纳米复合材料的热性能研究

采用原位聚合的方法制备了聚丙烯腈(PAN)/氧化石墨烯(GO)纳米复合材料;利用红外光谱和紫外光谱表征了试样的组成及组分间的相互作用;使用扫描电镜和透射电镜对试样的微观形貌进行观察;从单体转化率和聚合液的黏度变化研究了GO对丙烯腈自由基聚合的影响;用热分析仪分析了GO对PAN热稳定化过程的影响。结果表明:复合体系聚合至13 h时,与空白试样(PAN)相比,聚合液的黏度和单体转化率分别降低了1.3%和2.9%,说明在聚合前期GO对自由基聚合起到一定的阻聚作用;GO的厚度由聚合前的3～4 nm剥离到聚合后的1 nm,表明GO在原位聚合过程中以单层形式分散在PAN基体中;PAN与GO之间存在较强的π-π相互作用,这种相互作用抑制了PAN在热稳定化过程中的环化反应。     

水热法制备还原氧化石墨烯及其导电性调控

导电性可调控的还原氧化石墨烯（rGO）在结构功能材料和化工新材料等领域具有重要的应用前景。本文利用水热还原法实现了rGO的绿色制备,并通过调控反应温度和时间,获得了电导率可控的rGO产品,其电导率范围为10^-4～1 S·cm^-1。采用UV-vis、FT-IR、XPS、SEM、XRD和Raman等表征方法系统研究了rGO还原过程中结构与组成的变化。发现GO还原过程中,其含氧官能团于120℃时开始明显分解,高于140℃后含量显著降低,GO片层sp2区域逐渐恢复,电导率逐渐增大到1 S·cm^-1,同时层间距从8.2 Å减少到3.6 Å（1 Å=0.1 nm）。对比热还原法,水热法有效避免了rGO片层的堆叠,产物分散性较好,有望规模化制备导电性可控的rGO产品。本研究成果对rGO生产和应用具有重要意义。     

Copper reduced defective TiO2 nanoparticles with enhanced visible light photocatalytic activity

Defective TiO₂ attracted increasing attention due to its high photocatalytic activities. Herein, we report a facile and efficient method to fabricate gray defective TiO₂ by vacuum annealing raw TiO₂ materials with copper powders. The treated TiO₂ nanoparticles exhibit significantly enhanced visible‐light‐photocatalytic performance with photo‐degradation rate increased to 400% as that of pristine commercial P25 under visible light. The performance enhancements can be attributed to the disordered structure, optimized optical and electronic properties of defective TiO₂. In addition, this facile Cu reduction method provides an effective way to generate defective sites in other metal oxides for various potential applications.