Porous materials play a vital role in science and technology. The ability to control their pore structures at the atomic, molecular, and nanometer scales enable interactions with atoms, ions and molecules to occur throughout the bulk of the material, for practical applications. Three-dimensional (3D) porous carbon-based materials (e.g., graphene aerogels/hydrogels, sponges and foams) made of graphene or graphene oxide-based networks have attracted considerable attention because they offer low density, high porosity, large surface area, excellent electrical conductivity and stable mechanical properties. Water pollution and associated environmental issues have become a hot topic in recent years. Rapid industrialization has led to a massive increase in the amount of wastewater that industries discharge into the environment. Water pollution is caused by oil spills, heavy metals, dyes, and organic compounds released by industry, as well as via unpredictable accidents. In addition, water pollution is also caused by radionuclides released by nuclear disasters or leakage. This review presents an overview of the state-of-the-art synthesis methodologies of 3D porous graphene materials and highlights their synthesis for environmental applications. The various synthetic methods used to prepare these 3D materials are discussed, particularly template-free self-assembly methods, and template-directed methods. Some key results are summarized, where 3D graphene materials have been used for the adsorption of dyes, heavy metals, and radioactive materials from polluted environments.
Carboxylated multi-wall carbon nanotubes (MWCNTs-COOH) have been used as efficient adsorbents for the removal of picric acid from aqueous solutions under stirring and ultrasound conditions. Batch experiments were conducted to study the influence of the different parameters such as pH, amount of adsorbents, contact time and concentration of picric acid on the adsorption process. The kinetic data were fitted with pseudo-first order, pseudo-secondorder, Elovich and intra-particle diffusion models. The kinetic studies were well described by the pseudo-second-order kinetic model for both methods. In addition, the adsorption isotherms of picric acid from aqueous solutions on the MWCNTs were investigated using six two-parameter models (Langmuir, Freundlich, Tempkin, Halsey, Harkins-Jura, Fowler- Guggenheim), four three-parameter models (Redlich-Peterson, Khan, Radke-Prausnitz, and Toth), two four-parameter equations (Fritz-Schlunder and Baudu) and one five-parameter equation (Fritz-Schlunder). Three error analysis methods, correlation coefficient, chi-square test and average relative errors, were applied to determine the best fit isotherm. The error analysis showed that the models with more than two parameters better described the picric acid sorption data compared to the two-parameter models. In particular, the Baudu equation provided the best model for the picric acid sorption data for both methods.
The aim of the work was to investigate the thermo-electrical properties of low cost and rapidly produced randomly oriented carbon/carbon (C/C) composite. The composite body was fabricated by combining the high-pressure hot-pressing (HP) method with the lowpressure impregnation thermosetting carbonization (ITC) method. After the ITC method step selected samples were graphitized at 3000°C. Detailed characterization of the samples’ physical properties and thermal properties, including thermal diffusivity, thermal conductivity, specific heat and coefficient of thermal expansion, was carried out. Additionally, direct current (DC) electrical conductivity in both the in-plane and through-plane directions was evaluated. The results indicated that after graphitization the specimens had excellent carbon purity (99.9 %) as compared to that after carbonization (98.1). The results further showed an increasing trend in thermal conductivity with temperature for the carbonized samples and a decreasing trend in thermal conductivity with temperature for graphitized samples. The influence of the thickness of the test specimen on the thermal conductivity was found to be negligible. Further, all of the specimens after graphitization displayed an enormous increase in electrical conductivity (from 190 to 565 and 595 to 1180 S/cm in the through-plane and in-plane directions, respectively).
Biodegradable epoxy (B-epoxy) was prepared from diglycidyl ether of bisphenol A and epoxidized linseed oil. The mechanical properties of B-epoxy composites reinforced with multi-walled carbon nanotubes (MWCNTs/B-epoxy) were examined by employing dynamic mechanical analysis, critical stress intensity factor (KIC) tests, and impact strength tests. The electromagnetic interference shielding effectiveness (EMI-SE) of the composites was evaluated using reflection and absorption methods. Mechanical properties of MWCNTs/B-epoxy were enhanced with an increase in the MWCNT content, whereas they deteriorated when the MWCNT content was >5 parts per hundred resin (phr). This can likely be attributed to the entanglement of MWCNTs with each other in the B-epoxy due to the presence of an excess amount of MWCNTs. The highest EMI-SE obtained was ~16 dB for the MWCNTs/B-epoxy composites with a MWCNT content of 13 phr at 1.4 GHz. The composites (13 phr) exhibited the minimum EMI-SE (90%) when used as shielding materials at 1.4 GHz. The EMI-SE of the MWCNTs/B-epoxy also increased with an increase in the MWCNT content, which is a key factor affecting the EMI-SE.
In this paper, the in vitro biocompatibility of graphene film (GF) with osteoblasts was evaluated through cell adhesion, viability, alkaline phosphatase activity, F-actin and vinculin expressions, versus graphite paper as a reference material. The results showed that MG-63 cells exhibited stronger cell adhesion, better proliferation and viability on GF, and osteoblasts cultured on GF exhibited vinculin expression throughout the cell body. The rougher and wrinkled surface morphology, higher elastic modulus and easy out-of-plane deformation associated with GF were considered to promote cell adhesion. Also, the biomineralization of GF was assessed by soaking in simulated body fluid, and the GF exhibited enhanced mineralization ability in terms of mineral deposition, which almost pervaded the entire GF surface. Our results suggest that graphene promotes cell adhesion, activity and the formation of bonelike apatite. This research is expected to facilitate a better understanding of graphene-cell interactions and potential applications of graphene as a promising toughening nanofiller in bioceramics used in load-bearing implants.
This study synthesized pure anatase carbon doped TiO2 photocatalysts supported on a stainless steel mesh using a sol-gel solution of 8% polyacrylonitrile (PAN)/dimethylformamide (DMF)/TiCl4. The influence of the pyrolysis temperature and holding time on the morphological characteristics, particle sizes and surface area of the prepared catalyst was investigated. The prepared catalysts were characterized by several analytical methods: high resolution scanning electron microscopy (HRSEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), and X-ray photoelectron spectroscopy (XPS). The XRD patterns showed that the supported TiO2 nanocrystals are typically anatase, polycrystalline and body-centered tetragonal in structure. The EDS and XPS results complemented one another and confirmed the presence of carbon species in or on the TiO2 layer, and the XPS data suggested the substitution of titanium in TiO2 by carbon. Instead of using calcination, PAN pyrolysis was used to control the carbon content, and the mesoporosity was tailored by the applied temperature. The supported TiO2 nanocrystals prepared by pyrolysis at 300, 350, and 400ºC for 3 h on a stainless steel mesh were actual supported carbon doped TiO2 nanocrystals. Thus, PAN/DMF/TiCl4 offers a facile, robust sol-gel related route for preparing supported carbon doped TiO2 nanocomposites.
Nitrogen-doped carbon nanosheets with a developed porous structure were prepared from polyurethane foams by hydrothermal carbonization following ZnCl2 chemical activation. Scanning electron microscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, solid state 13C nuclear magnetic resonance (NMR) spectra and X-ray photoelectron spectroscopy were used to characterize the nitrogen-doped carbon nanosheet structure and composition. The removal of Cr(VI) by the N-doped carbon nanosheets was investigated. The results showed that the maximum removal capacity for chromium of 188 mg/g was found at pH=2.0 with PHC-Z-3. pH had an important effect on Cr(VI) removal and the optimal pH was 2.0. Moreover, amino groups and carboxyl groups in the nitrogen-doped carbon nanosheet played important roles in Cr(VI) removal, and promoted the reduction of Cr(VI) to Cr(III).
Activated carbons (ACs) have been used as electrode materials of electric double-layer capacitors (EDLC) due to their high specific surface areas (SSA), stability, and ecological advantages. In order to make high-energy-density ACs for EDLC, petroleum pitch (PP) precarbonized at 500–1000°C in N2 gas for 1 h was used as the electrode material of the EDLC after KOH activation. As the pre-carbonization temperature increased, the SSA, pore volume and gravimetric capacitance tended to decrease, but the crystallinity and electrode density tended to increase, showing a maximum volumetric capacitance at a medium carbonization temperature. Therefore, it was possible to control the crystalline structure, SSA, and pore structure of AC by changing the pre-carbonization temperature. Because the electrode density increased with increasing of the pre-carbonization temperature, the highest volumetric capacitance of 28.4 F/cc was obtained from the PP pre-carbonized at 700°C, exhibiting a value over 150% of that of a commercial AC (MSP-20) for EDLC. Electrochemical activation was observed from the electrodes of PP as they were pre-carbonized at high temperatures above 700°C and then activated by KOH. This process was found to have a significant effect on the specific capacitance and it was demonstrated that the higher charging voltage of EDLC was, the greater the electrochemical activation effect was.
In the present study, biomass-based lignin was extracted from industrial waste black liquor and the extracted lignin was characterized by means of attenuated total reflectance- Fourier transform infrared spectroscopy and 1H-nuclear magnetic resonance spectroscopy. The extracted lignin was carbonized at different temperatures and then activated with steam at 850oC. The extracted lignin in powder state was transformed into a bulky carbonized lignin due to possible fusion between the lignin particles occurring upon carbonization. The carbonized and then pulverized lignin exhibits brittle surfaces, the increased thermal stability, and the carbon assay with increasing the carbonization temperature. The scanning electron microscopic images and the Brunauer-Emmett-Teller result indicate that the steam-activated carbon has the specific surface area of 1718 m2/g, which is markedly greater than the carbonized lignin. This study reveals that biomassbased activated carbon with highly porous structure can be produced from costless black liquor via steam-activation process.