Formation of carbon nanofibers with Ni catalyst supported on a micro-mesoporous glass

The Ni/SiO2 system is one of the most interesting to produce COx-free H2 and valuable carbon nanofibers (CNFs) by the catalytic decomposition of CH4. SiO2 is one of the most effective support while Ni catalyst displays long life and high activity. We studied the catalytic chemical vapor deposition (CCVD) process of CH4 within Ni/glass system at relatively low temperature (600 °C) during long times (3 h), varying the amount of the catalyst (2.3–17.8% Ni(%)) and the carbon source (100:200 to 100:0, CH4:N2). As the amount of Ni and CH4 increases, the formation of CNFs is enhanced giving as a result CNFs/glass materials with more amount, longer and thicker CNFs. The initial microstructure of the glass support and the way of Ni catalyst is deposited play a decisive role. Pristine porous glass displays a microstructe of interconnected mesopores which are progressively filled with Ni, producing ink-bottle pores with open ends. After the CCVD process as the amount of Ni or CH4 increases, the porosity of the Ni-doped glass is reduced due to the progressively filling of the mesopores (4 nm) with CNFs. Furthermore, due to the formation of large entanglements of CNFs new pores appear (20–70 nm) depending on the processing conditions. Fish-bone with hollow core and bamboo-like CNFs are found over the surface and also inside the porous glass support. It is observed a base-growth mechanism due to the strong interaction between the catalyst and the support, which prevents the Ni deactivation enhancing its activity for long times.This work was supported by project MAT2016-78700-R financed by Spanish Research Agency and European Regional Development Fund (AEI/FEDER, EU)

Towards the understanding of the graphene oxide structure: How to control the formation of humic- and fulvic-like oxidized debris

Former structural models of graphene oxide (GO) indicated that it consists of graphene-like sheets with oxygen groups, and no attention was paid to the resulting sheet size. We now provide evidence of the complex GO structure consisting of large and small GO sheets (or oxidized debris). Different oxidation reactions were studied. KMnO4 derived GO consists of large sheets (20–30 wt.%), and oxidized debris deposits, which are formed by humic- and fulvic-like fragments. Large GO sheets contain oxygen groups, especially at the edges, such as carbonyl, lactone and carboxylic groups. Humic-like debris consists of an amorphous gel containing more oxygenated groups and trapped water molecules. The main desorbable fraction upon heating is the fulvic-like material, which contains oxygen groups and fragments with high edge/surface ratio. KClO3 in HNO3 or the Brodie method produces a highly oxidized material but at the flake level surface only; little oxidized debris and water contents are found. It is noteworthy that an efficient basal cutting of the graphitic planes in addition to an effective intercalation is caused by KMnO4, and the aid of NaNO3 makes this process even more effective, thus yielding large monolayers of GO and a large amount of humic- and fulvic-like substances.The authors thank the Government of Spain, Ministry for Economy and Competiveness, for financial support of project CTQ2013-44213-R, and Generalitat Valenciana for projects PROMETEOII/2014/007 and ISIC/2012/008. IRP thanks the Government of Spain, Ministry of Science and Education, for PhD Scholarship in the FPU program

New insights into oxygen surface coverage and the resulting two-component structure of graphene oxide

Elucidating the essential details of the structure of graphene oxide (GO) is still a challenge. There is no consensus in the increasingly abundant literature, especially relating to the epoxy groups as the main surface complexes in the basal plane, as well as the simultaneous presence of GO sheets and oxidative debris (OD), with a large difference in their oxygen content. In the present work we characterized the base-washed GO (bwGO) sheets, the OD and the humic fraction of the OD obtained by base digestion, when the parent GO was dispersed by applying sonication, a routine procedure when starting from dried graphite oxide. When sonication is not applied, the amount of OD detected is considerably lower, indicative of its formation before base digestion. The presence of lactols and carboxylic anhydrides as the dominant surface complexes at graphene edges is consistent with all the characterization results, as well as with the general knowledge of surface chemistry of carbon materials ranging from coal to graphite. These findings suggest that the Hummers-Offeman reaction produces a chemical scissor effect during the water/hydrogen peroxide quenching step, yielding a broad size distribution of GO sheets, with little in-plane oxidation and the vast majority of edges being oxidized to form oxepinone-type functionalities.The authors gratefully acknowledge the financial support of the Ministerio de Economía y Competitividad of Spain (Project CTQ2013-44213-R), and Generalitat Valenciana (project PROMETEOII/2014/007). LRR is grateful for the support of CONICYT-Chile (project Fondecyt 1160949)

Comparative study on properties of starch films obtained from potato, corn and wheat using 1-ethyl-3-methylimidazolium acetate as plasticizer

Starch films are gaining attention as substitutes of synthetic polymers due to their biodegradability and low cost. Some ionic liquids have been postulated as alternatives to glycerol, one of the best starch plasticizers, due to their great capacity to form hydrogen bonds with starch and hence great ability of preventing starch retrogradation and increasing film stability. In this work, [emim+][Ac−]-plasticized starch films were prepared from potato, corn and wheat starch. The effect of starch molecular structure in terms of granular composition (amylose and phosphate monoester contents) and molecular weight (Mw) on film properties was evaluated. Potato starch films were the most amorphous because of the higher Mw and phosphate monoester content of potato starch, both contributing to a lower rearrangement of the starch chains making the crystallization process difficult. In contrast, corn and wheat starches lead to more crystalline films because of their lower Mw, which may imply higher mobility and crystal growth rate, and lower phosphate monoester content. This more crystalline structure could be the responsible of their better mechanical properties. [emim+][Ac−] can be considered suitable for manufacturing starch films showing corn and wheat starch films similar properties to synthetic low-density polyethylene, but involving a simple and environmentally-friendly process.This work was partially supported from the European Commission, European-Union and Ministerio de Economía y Competitividad (MINECO), Spain (Ref. CTQ2016-78246-R) and Generalitat Valenciana (Project PROMETEOII/2014/007). M.G. Montalbán acknowledges support from Ministerio de Economía y Competitividad (MINECO) (Juan de la Cierva-Formación contract, Ref. FJCI-2016-28081)

The role of conductive additives on the performance of hybrid carbon xerogels as electrodes in aqueous supercapacitors

Three different hybrid carbon xerogels containing Graphene Oxide (AXGO), Micronized Graphite (AXMG) and Carbon Black (AXCB) were synthesized using an easy, fast and affordable method. These three additives were initially selected to improve the electrical conductivity of the pristine activated carbon xerogel (AX) thus expecting to improve its performance in aqueous supercapacitors. Capacitances of the corresponding devices were measured as a function of current density and results of the high and low charge transfer regime of the supercapacitors were discussed separately. In both regimes, the differences observed between the hybrid electrodes were analyzed on the basis of the concurrent influence of the micro and mesoporosity, surface chemistry and electrical conductivity of the materials. Accordingly, even though all the hybrid carbon xerogels showed higher electrical conductivities, only AXGO rendered a better performance than AX, showing the highest capacitances in the whole interval of intensities studied. Consequently, at 16 A g−1, the energy and power densities of the AXGO supercapacitors increased up to 16% and 97%, respectively, with respect to AX, and of 143% and 409%, respectively, with respect to a commercial activated carbon used as reference. The performance of AXCB and, especially AXMG was worse than AX supercapacitors due to a combination of inadequate pore size distributions and/or a poor surface chemistry. Finally, TEM analysis helped to understand the different way the three additives were affecting the nanostructure (and final properties) of the hybrid carbon xerogels.Authors gratefully acknowledge the financial support from the Ministerio de Economía, Industria y Competitividad from Spain (Project CTQ2017-87820-R). MCR also acknowledges CSIC (Project I.E. 201880E010)

Custom-Made Chemically Modified Graphene Oxide to Improve the Anti-Scratch Resistance of Urethane-Acrylate Transparent Coatings

In this work, a thermoset ultraviolet (UV)-cured polyurethane-acrylate resin was doped with different chemically-modified graphene obtained from a commercial graphene oxide (GO): as-received GO, chemically reduced GO (rGO), GO functionalized with vinyltriethoxysilane (VTES) (GOvtes), and GO functionalized with VTES and subsequently reduced with a chemical agent (rGOvtes). Modified graphene was introduced in the oligomer component via solvent-assisted process using acetone, which was recovered after completion of the process. Results indicate that the GO-doped oligomers produce cured coatings with improved anti-scratch resistance (above the resistance of conventional coatings), without surface defects and high transparency. The anti-scratch resistance was measured with atomic force microscopy (AFM). Additionally, results are presented in terms of Wolf–Wilburn scale, a straightforward method widely accepted and employed in the coating industry.This research was funded by MINISTERIO DE ECONOMÍA Y COMPETITIVIDAD (MINECO) of Spain (CTQ2014-54772-P and CTQ2013-44213-R); and GENERALITAT VALENCIANA (ROMETEOII/2014/007)

Influence of Starch Composition and Molecular Weight on Physicochemical Properties of Biodegradable Films

Thermoplastic starch (TPS) films are considered one of the most promising alternatives for replacing synthetic polymers in the packaging field due to the starch biodegradability, low cost, and abundant availability. However, starch granule composition, expressed in terms of amylose content and phosphate monoesters, and molecular weight of starch clearly affects some film properties. In this contribution, biodegradable TPS films made from potato, corn, wheat, and rice starch were prepared using the casting technique. The effect of the grain structure of each starch on microstructure, transparency, hydration properties, crystallinity, and mechanical properties of the films, was evaluated. Potato starch films were the most transparent and corn starch films the most opaque. All the films had homogeneous internal structures—highly amorphous and with no pores, both of which point to a good starch gelatinization process. The maximum tensile strength (4.48–8.14 MPa), elongation at break (35.41–100.34%), and Young’s modulus (116.42–294.98 MPa) of the TPS films were clearly influenced by the amylose content, molecular weight, and crystallinity of the film. In this respect, wheat and corn starch films, are the most resistant and least stretchable, while rice starch films are the most extensible but least resistant. These findings show that all the studied starches can be considered suitable for manufacturing resistant and flexible films with similar properties to those of synthetic low-density polyethylene (LDPE), by a simple and environmentally-friendly process.This work was partially supported by the European Commission (FEDER/ERDF), the Spanish MINECO (Ref. CTQ2016-78246-R), and Generalitat Valenciana (Project PROMETEOII/2014/007). M.G.M. acknowledges support from MINECO (Juan de la Cierva-Formación contract, Ref. FJCI-2016-28081)

Study of the behavior of biodegradable starch/polyvinyl alcohol/rosin blends

Biodegradable potato starch/PVA samples containing different concentrations of rosin were prepared by melt-mixing in order to study the enhancement of the properties of native starch films. Glycerol and polyvinyl alcohol (PVA) are commonly used as plasticizers of starch. Their relatively low molecular weight (compared with starch) contributes to a good processability. Rosin is a renewable product whose incorporation in the starch/PVA matrix induces processing aid and reinforcing effects. Its relatively high molecular weight might prevent its migration to the surface of the final product. Water content, solubility in water, mechanical properties, microstructure and dynamic mechanical analysis of the samples were studied. The addition of 8% rosin to starch/PVA blends led to tensile strength values higher than 10 MPa and elongation at break values close to 2000%, values comparable to those offered by conventional polymers used in food packaging, for example LDPE. Furthermore, starch compounds have low cost and high biodegradability.This work was partially supported from the European Commission (FEDER/ERDF) and the Spanish MINECO (Ref. CTQ2016-78246-R) and Generalitat Valenciana (Project PROMETEOII/2014/007). M.G. Montalbán acknowledges support from MINECO (Juan de la Cierva-Formación contract, Ref. FJCI-2016-28081)

Determinant influence of the electrical conductivity versus surface area on the performance of graphene oxide-doped carbon xerogel supercapacitors

A series of resorcinol formaldehyde based carbon xerogels were synthesized under identical conditions using different graphene oxide loads. The gelification reaction was carried out using a stable aqueous suspension of graphene oxide, yielding organic gels with graphene oxide concentrations ranging from 1.2–2.5%. After the carbonization, xerogels with medium surface area (650 m2/g) and a highly improved electrical conductivity were obtained. Specific capacitance of 120 F/g of one electrode at very high scan rate of 500 mV/s were achieved, as well as power densities above 30 kW/kg, which is a significant improvement of 180% with respect to the pristine xerogels. Carbonized xerogels were further steam activated to yield activated carbon xerogels with surface areas of up to 1800 m2/g. The use of activated xerogels improves slightly the specific capacitance at low scan rates only, and there is a sharp decrease above 20 mV/s, resulting in a worse performance than graphene oxide doped carbonized xerogels. The electrical conductivity of the graphene oxide-doped carbon xerogels decreases upon activation, which means that the influence of the electrical conductivity on a carbon xerogel is greater than its specific surface area, which it is the first time it is observed for porous carbons.The authors gratefully acknowledge the financial support of the Ministerio de Economía y Competitividad of Spain, MINECO (Project CTQ2014-54772-P and CTQ2013-44213-R), and Generalitat Valenciana (project PROMETEOII/2014/007)

The Effect of Different Oxygen Surface Functionalization of Carbon Nanotubes on the Electrical Resistivity and Strain Sensing Function of Cement Pastes

Different studies in the literature indicate the effectiveness of CNTs as reinforcing materials in cement–matrix composites due to their high mechanical strength. Nevertheless, their incorporation into cement presents some difficulties due to their tendency to agglomerate, yielding a non-homogeneous dispersion in the paste mix that results in a poor cement–CNTs interaction. This makes the surface modification of the CNTs by introducing functional groups on the surface necessary. In this study, three different treatments for incorporating polar oxygen functional groups onto the surface of carbon nanotubes have been carried out, with the objective of evaluating the influence of the type and oxidation degree on the mechanical and electrical properties and in strain-sensing function of cement pastes containing CNTs. One treatment is in liquid phase (surface oxidation with HNO3/H2SO4), the second is in gas phase (O3 treatment at 25 and 160 °C), and a third is a combination of gas-phase O3 treatment plus NaOH liquid phase. The electrical conductivity of cement pastes increased with O3- and O3-NaOH-treated CNTs with respect to non-treated ones. Furthermore, the oxygen functionalization treatments clearly improve the strain sensing performance of the CNT-cement pastes, particularly in terms of the accuracy of the linear correlation between the resistance and the stress, as well as the increase in the gage factor from 28 to 65. Additionally, the incorporation of either non-functionalized or functionalized CNTs did not produce any significant modification of the mechanical properties of CNTs. Therefore, the functionalization of CNTs favours the de-agglomeration of CNTs in the cement matrix and consequently, the electrical conductivity, without affecting the mechanical behaviour.This research was funded by the European Union’s Horizon 2020 Research and Innovation Programme, grant number 760940