Fabrication of 3D Polypyrrole/Graphene Oxide Composite Hydrogels with High Performance Swelling Properties

The polypyrrole (PPy)/graphene oxide (GO) composite hydrogels with hierarchical porous structures were fabricated by one-step self-assembly method. The static oxidation polymerization of pyrrole monomer in GO aqueous solution resulted in the formation of three-dimensional (3D) PPy/GO composite hydrogels, which consisted of one-dimensional PPy nanofibers and two-dimensional GO nanosheets. The as-prepared composite hydrogels exhibited shrinking–swelling behavior with cycles of suction and water-supplying. The effects of GO nanosheets content on the swelling properties were investigated. Results showed that the well-dispersed GO nanosheets in the hydrogel networks resulted in a significant improvement in water absorbencies of the hydrogels. PPy/GO composite hydrogels exhibited unobvious variation in the water absorbency even in saline solutions. Such excellent properties in water absorbencies endow the conducting 3D PPy/GO composite hydrogels with great potential applications in electrochemical sensors or controlled release.     

二氧化钛/氧化石墨烯复合光催化剂的合成

采用水热法,以钛酸四正丁酯及氧化石墨烯（GO）为原料,在水性体系中合成了一系列具有不同GO质量分数的TiO2/GO复合光催化剂。FE-SEM分析结果表明,分散的钛酸四正丁酯以多分子层的形式吸附到氧化石墨烯的表面,最后在水热过程中转化为锐钛型TiO2粒子。当氧化石墨烯的质量分数低于3%时,产物中含有纯TiO2微球及TiO2/GO复合物;当氧化石墨烯质量分数大于5%时,产物为单纯的TiO2/GO复合物。电化学性能测试结果表明,GO复合后,TiO2电极中载流子的传输效率提高。氧化石墨烯复合量为10%时,复合光催化剂显示了对亚甲基蓝最佳的光催化活性。当复合氧化石墨烯转化为石墨烯后,其光催化活性可得到进一步大幅度的提高。     

Graphene‐based composite with microwave absorption property prepared by in situ reduction

Binary composite of graphene/poly(ethylene oxide) (PEO) with microwave absorption property is prepared by in situ reduction process. Graphite oxide (GO) is prepared from flake graphite by modified Hummers' method and further dispersed in distilled water to get GO solution. Then, PEO powder is slowly added into GO solution to get GO/PEO solution, and graphene/PEO composites is prepared via a facile and quick reduction process in GO/PEO solution. PEO and graphene/PEO composites are characterized by scanning electron microscopy, atomic force microscopy, thermo gravimetric analysis, and vector network analyzer. The results show that graphene is uniformly dispersed in PEO matrix because GO and PEO can be uniformly dispersed at molecular level due to their water‐solubility and the agglomeration of graphene can be prevented by PEO macromolecular chains during in situ reduction process. Graphene/PEO composite has better thermal stability than PEO, which can be explained by the graphene restoration of sp² bonded carbon structure. Meanwhile, graphene/PEO composite shows excellent microwave absorption property at low grapheme content. The minimum reflection loss of graphene/PEO composite is up to −20.0 dB when the content of graphene is only 1 wt%. POLYM. COMPOS., 35:461–467, 2014. © 2013 Society of Plastics Engineers     

Friction and wear behavior of alumina-based graphene and CNFs composites

Alumina – carbon nanofibers (CNF) and alumina – graphene oxide (GO) composites were prepared by spark plasma sintering using freeze-dried powders prepared from optimized suspensions of the mixtures. The tribological behavior was studied using the ball-on-disk technique in dry sliding at ambient conditions and compared to a monolithic alumina used as a reference. At low loads there was little difference between friction and wear behavior, whereas at moderate loads the composites showed a noticeable reduction in wear rate over monolithic alumina, five and 2.5 times for the GO and the CNF composite respectively; the friction coefficient slightly decreased for the alumina – GO material. This behavior is related to the presence of a carbon-rich protecting tribofilm. The film present in the alumina – GO showed better tribological performance due to the absence of coalescence of cracks that led to delamination events in the case of the alumina – CNF composite.     

Polymer-derived ceramic/graphene oxide architected composite with high electrical conductivity and enhanced thermal resistance

A low temperature method for the fabrication of architected ceramic composites contining graphene is developed based on the infiltration of lightweight graphene oxide (GO) micro-lattices with a preceramic polymer. Self-supported highly porous three-dimensional (3D) GO structures fabricated by direct ink writing are infiltrated with a liquid organic-polysilazane (a compound of Si, C, H, N), and subsequently pyrolyzed at temperatures of 800–1000?ºC to activate the ceramic conversion. These ceramic composites replicate the patterned GO skeleton and, whereas the graphene network provides the conductive path for the composite (electrical conductivity in the range 0.2–4?S?cm^?1), the ceramic wrapping serves as a protective barrier against atmosphere, temperature (up to 900?°C in air) and even direct flame. These structured composites also show hydrophobicity (wetting angle above 120°) and better load bearing capacity than the corresponding 3D GO lattice. The process is very versatile, being applicable to different liquid precursors.     

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。     

Versatile photoluminescence from graphene and its derivatives

Graphene and its derivatives exhibit many interesting photoluminescence (PL) properties because of their unique electronic structures. In spite of the absence of the bandgap, graphene shows PL due to hot electrons. Graphene oxide (GO) fluorescence is different from that of a single organic fluorophore, for which the spectral properties and emission lifetime are independent of wavelength. Single-layered GO sheets are made of a large number of covalently connected independent fluorophores of varying sizes. These fluorophores are aromatic π-conjugated sp²-hybridized subsystems of carbon atoms surrounded by sp³ regions. The PL of GO is pH dependent because of the presence of many oxygen-containing groups in GO sheets. Reduced graphene oxide (rGO) PL is somewhat different from GO because the number and size of sp² fragments are increased in rGO due to the elimination of the functional groups containing oxygen via reduction. Nanosized graphene/GO possesses a strong quantum confinement effect and hence emits intense excitation wavelength-dependent PL. Moreover, graphene quantum dots show upconversion PL due to anti-Stokes transition. The diverse PL properties including the effect of reduction, pH, and solvent have been reported in many recent studies. Here, the versatile PL features of graphene derivatives are reviewed to elucidate the mechanism of PL.     

Scalable preparation of three-dimensional porous structures of reduced graphene oxide/cellulose composites and their application in supercapacitors

Controlling the assembled structures of graphene has recently attracted enormous attention due to intriguing properties of the resultant structures. In this study, three-dimensional (3D) porous structures of reduced graphene oxide (RGO) with various ratios of RGO to cellulose have been fabricated by a scalable, but simple and efficient, approach that consists of ball milling assisted chemical reduction of GO, template shaping, coagulating, and lyophilization. The efficient mechanical shearing of ball milling and the hydrogen bond interactions between RGO and cellulose molecules contribute to the formation of a homogeneous RGO/cellulose hydrogel, improved thermal stability of the resultant composites, and enhanced crystallinity of the cellulose in the composites. The coagulation effect of cellulose maintains the RGO sheets in the 3D structures of cellulose; on the other hand, the RGO sheets facilitate the preservation of the 3D structures during freeze-drying, leading to the formation of 3D porous structures of RGO/cellulose composites. Benefiting from the continuous RGO network in the composites, the 3D porous structures of RGO(70)/cellulose(100) (GO:cellulose = 70:100 in weight) show an electrical conductivity of 15.28 S m⁻¹. Moreover, the 3D porous structures show potential application in supercapacitors due to the fact that they provide high specific surface area and fast charge propagation.     

Radiation synthesis of graphene oxide/composite hydrogels and their ability for potential dye adsorption from wastewater

A high yield of graphene oxide (GO) was chemically synthesized from graphite powder utilizing adjusted Hummer's method. The contents of acidic functional groups in GO were determined using potentiometric titration. Composite hydrogels dependent on graphene oxide/poly(2-acrylamido-2-methylpropanesulfonic acid)/polyvinyl alcohol (GO/PAMPS/PVA) were synthesized utilizing a ⁶⁰Co gamma irradiation source at different doses. The synthesized graphene oxide and composite hydrogels were portrayed via X-ray diffraction, thermogravimetric analysis, and Fourier transform infrared analysis. The morphology of composite hydrogels was characterized by scanning electron microscope. The gel % and swelling % for the prepared hydrogel demonstrated that the swelling % of hydrogel increased with raising AMPS content. Whereas the increment of GO and increasing the irradiation dose lead to a reduction in the swelling %. The influences of pH, GO percentage, initial dye concentration, the adsorbent dosage, contact time, and temperature on the adsorption of basic blue 3 dye were evaluated and the adsorption capacity was 194.6 mg/g at optimum conditions; pH = 6, GO/PAMPS/PVA composite hydrogels with 5 wt% of GO, initial dye concentration = 200 mg/L, adsorbent dose = 0.1 g, solution volume = 50 mL after 360 min at room temperature (25°C). The adsorption of dye onto the GO/PAMPS/PVA composite hydrogels follows Pseudo-second-order adsorption kinetics, fits the Freundlich adsorption isotherm model.     

Preparation and derivation mechanism of methyl methacrylate/nitrile butadiene rubber/graphene oxide composites by ball-milling

Methyl methacrylate/nitrile butadiene rubber/graphene oxide (MMA/NBR/GO) composite materials were prepared by ball-milling based on the mechano-chemical principle. The effects of some key process parameters, such as graphene oxide (GO) content, ball-to-powder ratio (BPR), and ball-milling time on textures and structures of MMA/NBR/GO composite materials were studied systematically by Zeta potentials, Raman spectroscopy, Thermogravimetric analysis, Fourier transform infrared spectrometry, and the derivation mechanism was examined. The results indicated composite materials with excellent dispersion stability at GO content of 0.3%, BPR of 3.87, and ball-milling time of 5 h, the value of sedimentation rate is only 1.0%, the Zeta potential is −41.5 mV, and the mass loss ratio is 40.36%. FT-IR result shows that the intensity of the characteristic peak all decreases after ball milling, and carboxyl group of GO and hydroxyl group connected to the benzene ring is broken. The graft position is  CN and CH₂ of NBR, and  CH₃ of MMA. Under these conditions, the oxygen-containing functional groups of GO were successfully grafted onto the MMA and NBR.     

纳米粒子/氧化石墨烯改性复合膜制备及其分离性能研究

采用真空抽滤-压力喷涂的方法，以聚酰胺纳滤膜为基膜，制备了氧化石墨烯和二氧化钛纳米粒子质量比为1∶1、2∶1、3∶1和4∶1的复合膜GOT1、GOT2、GOT3和GOT4以及氧化石墨烯和二氧化硅纳米粒子质量比为1∶1、2∶1、3∶1和4∶1的复合膜GOS1、GOS2、GOS3和GOS4。通过SEM、EDS、XPS和GIWAXS方法对GOT复合膜和GOS复合膜进行了分析表征，结果表明，氧化石墨烯和纳米粒子均匀负载在聚酰胺纳滤膜表面。研究了复合膜的性能，并推测了复合膜的净水机理。其中GOT复合膜在0.75 MPa下水通量可达50 L·m^-2·h^-1,相较于原始基膜提高了25%,显示出了最佳的水通量性能，并且在保持较高通量的同时，对盐溶液和重金属离子的截留率仍能维持在90%左右。真空抽滤-压力喷涂的方法为氧化石墨烯复合膜的制备提供一种新的工艺思路，为废水处理提供了一种更高净化效率的复合膜。     

Additive Manufacturing of Graphene–Hydroxyapatite Nanocomposite Structures

In this article, a powder‐bed class of additive manufacturing (AM) is incorporated into the manufacturing of graphene nanocomposite 3D structures. For AM of graphene‐based 3D structures, graphene oxide (GO)/hydroxyapatite (Hap) nanocomposite (GHN) was synthesized at different GO to Hap percentage (wt.%), including 0.2% and 0.4% to develop a printable powder. The synthesized powder was utilized in a powder‐bed AM system to fabricate 3D porous structures of GHN powder. It was shown that at layer thickness of 125 μm and core binder saturation level of 400%, the compressive mechanical strength of the samples with higher content of graphene was improved significantly.     

Fabrication of free-standing graphene composite films as electrochemical biosensors

We report a simple fabrication method for large-scale free-standing graphene–gold nanoparticle and graphene-single wall carbon nanotube composite films by using a centrifugal vacuum evaporation followed by a thermal reduction process. The homogeneous mixture of a graphene oxide (GO) suspension with gold nanoparticle (Au NP) or single wall carbon nanotube (SWCNT) is self-assembled at the air/liquid interface, resulting in the multilayered GO–Au NP and GO–SWCNT composite films. The cross-sectional image reveals that the graphene layers are orderly stacked in the reduced GO–Au NP film, while the reduced GO–SWCNT film shows a randomly packed morphology due to the dominant π–π interaction between the side wall of SWCNTs and the GO surfaces. In particular, the reduced GO–Au NP film shows an increased electrode kinetics and cyclic voltammetric response in proportion to the amount of Au NPs, and 3-fold enhancement of anodic peak current was observed compared with that of the reduced GO films. We employed the reduced GO–Au NP film as a matrix to immobilize tyrosinase enzyme for phenol detection, and the phenol-induced electrochemical catalytic reaction can be monitored with 3-fold higher sensitivity than the reduced GO film, demonstrating great potential of graphene composite as an electrochemical enzyme biosensor for environmental pollutant screening.     

Mixed Matrix PVDF/Graphene and Composite‐Skin PVDF/Graphene Oxide Membranes Applied in Membrane Distillation

This work elucidates the influence of graphene (G) and graphene oxide (GO) content on the desalination performance and scaling characteristics of G/polyvinylidene fluoride (G/PVDF) mixed matrix and GO/PVDF composite‐skin membranes, applied in a direct contact membrane distillation process (DCMD). Inclusion of high quality, nonoxidized, monolayered graphene sheets as polymer membrane filler, and application of a novel GO/water‐bath coagulation method for the preparation of the GO/PVDF composite films, took place. Water permeability and desalination tests via DCMD, revealed that the optimal G content was 0.87 wt%. At such concentration the water vapor flux of the G/PVDF membrane was 1.7 times that of the nonmodified reference, while the salt rejection efficiency was significantly improved (99.8%) as compared to the neat PVDF. Similarly the GO/PVDF surface‐modified membrane, prepared using a GO dispersion with low concentration (0.5 g/L), exhibited twofold higher water vapor permeate flux as compared to the neat PVDF, but however, its salt rejection efficiency was moderate (80%), probably due to pore wetting during DCMD. The relatively low scaling tendency observed for both G and GO modified membranes is primarily attributed to their smoother surface texture as compared to neat PVDF, while scaling is caused by the deposition of calcite crystals, identified by XRPD analysis. POLYM. ENG. SCI., 59:E262–E278, 2019. © 2018 Society of Plastics Engineers     

Effect of graphene oxide size and structure on synthesis and optoelectronic properties of hybrid graphene oxide‐poly(3‐hexylthiophene) nanocomposites

Conjugated polymer‐layered filler nanocomposites have received extensive interest as multifunctional materials in various futuristic applications. In this study, the effect of graphene oxide (GO) particle size on the synthesis, optical, and electrochemical properties of in situ prepared graphene oxide (GO)‐poly(3‐hexylthiophene) (P3HT) nanocomposites have been studied. The intercalation of GO with P3HT is inferred from shifting and broadening of the characteristic D‐ and G‐bands of GO in Raman spectra and also the vibrational frequencies in FTIR. This interaction is further confirmed from increase of the optical band gap and the ellipsometry data. The UV–visible absorption maximum (λ _max) of P3HT decreases from 438 to 418 nm in the nanocomposite owing to ionic interactions between GO and the polymer causing a decrease of the polymer conjugation length. Compared to the homopolymer, the emission maximum of the composite is broadened and enhanced in intensity with 10 wt% GO but emission quenching is observed with GO nanoparticles. The evidence of polymer intercalation was also deduced from the determination of the basal spacing and unit cell dimensions of GO, using X‐ray diffraction data. Morphological studies using field emission scanning electron microscopy suggest that the crystalline rod‐like structures observed in the homopolymer have changed to more amorphous, flaky, and porous structures. The cyclic voltammetry studies show an increase in current with increasing GO content in the porous nanocomposites. POLYM. COMPOS., 38:852–862, 2017. © 2015 Society of Plastics Engineers     

Preparation of polyimide/siloxane‐functionalized graphene oxide composite films with high mechanical properties and thermal stability via in situ polymerization

An effective approach to prepare polyimide/siloxane‐functionalized graphene oxide composite films is reported. The siloxane‐functionalized graphene oxide was obtained by treating graphene oxide (GO) with 1,3‐bis(3‐aminopropyl)‐1,1,3,3‐tetra‐methyldisiloxane (DSX) to obtain DSX‐GO nanosheets, which provided a starting platform for in situ fabrication of the composites by grafting polyimide (PI) chains at the reactive sites of functional DSX‐GO nanosheets. DSX‐GO bonded with the PI matrix through amide linkage to form PI‐DSX‐GO films, in which DSX‐GO exhibited excellent dispersibility and compatibility. It is demonstrated that the obvious reinforcing effect of GO to PI in mechanical properties and thermal stability for PI‐DSX‐GO is obtained. The tensile strength of a composite film containing 1.0 wt% DSX‐GO was 2.8 times greater than that of neat PI films, and Young's modulus was 6.3 times than that of neat PI films. Furthermore, the decomposition temperature of the composite for 5% weight loss was approximately 30 °C higher than that of neat PI films. © 2015 Society of Chemical Industry     

GO表面原位生长CNTs改善聚丙烯导热复合材料分散与界面形态

二维结构氧化石墨烯(GO)纳米片在高分子导热复合材料领域有良好应用前景,但常受限于片层间相互作用过大导致的局部团聚,不利于力学性能和导热性能的提高。借助GO纳米片表面和边缘提供的大量活性位点以吸附铁基催化剂,进而通过微波辅助合成方法在GO表面原位生长碳纳米管(CNTs)的策略,在数分钟内合成具有三维多层次结构的纳米杂化体(GO-CNT)。通过常规熔融共混方法,可获得GO-CNT在聚丙烯(PP)基体中良好剥离与均匀分散形态,明显不同于GO/PP复合体系中严重的局部团聚现象。均匀分散的GO-CNT对PP复合材料的力学性能和导热性能提升效果显著：在3%(质量分数)含量下,复合材料的屈服强度和热导率分别达到了38.0 MPa和0.76 W/(m·K),较纯PP增幅分别为20%和230%,明显优于传统GO改性复合材料。本研究为解决纳米片状填料在导热复合材料中的应用瓶颈提供了可行的结构设计策略和复合材料制备方法。     

氧化石墨烯-壳聚糖纤维制备及其对染料吸附性能

选取壳聚糖和聚乙烯醇与氧化石墨烯共混复合,通过湿法纺丝工艺技术,制备不同氧化石墨烯含量的氧化石墨烯-壳聚糖复合纤维。利用扫描电镜和红外光谱表征了复合纤维的微观结构和化学组成,结果表明:复合纤维成形较好,氧化石墨烯与壳聚糖之间形成了稳定的氢键。通过染料吸附试验可知:氧化石墨烯可明显提高复合纤维对染料的吸附能力,当氧化石墨烯质量分数为1%时,吸附效果最理想,吸附量可达407 mg/g,有望用于印染废水的综合处理。     

Graphene Oxide/ Polyacrylic acid-based double network skeleton for enhanced cationic dye adsorption

ABSTRACT

A three-dimensional (3D) porous graphene oxide/polyacrylic acid (GO/PAA) aerogel with double network skeleton was assembled by in situ solution polymerization method toward removing multi-cationic dyes from wastewater, such as methylene blue (MB), crystal violet (CV), methyl orange (MO), and rhodamine B (RhB), in which the adsorption capacities for CV and MB were 851.31 and 771.14 mg g^?1, respectively. This composite showed outstanding adsorption capacity due to the structure of 3D double network skeleton, large specific surface area, and remarkable carboxyl group content.     

燃料电池用纳米改性聚苯并咪唑阴离子交换膜的制备

以环氧氯丙烷和1–甲基咪唑为原料制备新型离子液体(IL),以IL为原料对氧化石墨烯(GO)进行表面修饰制备离子液体功能化氧化石墨烯(IL–GO),以IL–GO为添加剂制备基于含氟聚苯并咪唑(FPBI)复合膜。研究了IL–GO的含量对复合膜的热稳定性、力学强度、离子电导率、离子交换容量(IEC)、吸水率、溶胀度和耐碱性等性能的影响。研究结果表明,复合膜的IEC、离子电导率和拉伸性能都随着IL–GO含量的增加而增大,当IL–GO含量为30%时其拉伸应力和拉伸弹性模量分别达到77.5 MPa和1.95 GPa,在80℃下,其最大离子电导率可达72.3 m S/cm,然而复合膜的热稳定性并没随着IL–GO含量的增加而改变。FPBI/IL–GO复合膜具有良好的稳定性,该系列阴离子交换膜有望在碱性阴离子交换膜燃料电池中得到应用。