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

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

Prodromal symptoms and the duration of untreated psychosis in first episode of psychosis patients: what differences are there between early vs. adult onset and between schizophrenia vs. bipolar disorder?

To assess the role of age (early onset psychosis-EOP < 18 years vs. adult onset psychosis-AOP) and diagnosis (schizophrenia spectrum disorders-SSD vs. bipolar disorders-BD) on the duration of untreated psychosis (DUP) and prodromal symptoms in a sample of patients with a first episode of psychosis. 331 patients with a first episode of psychosis (7–35 years old) were recruited and 174 (52.6%) diagnosed with SSD or BD at one-year follow-up through a multicenter longitudinal study. The Symptom Onset in Schizophrenia (SOS) inventory, the Positive and Negative Syndrome Scale and the structured clinical interviews for DSM-IV diagnoses were administered. Generalized linear models compared the main effects and group interaction. 273 AOP (25.2 ± 5.1 years; 66.5% male) and 58 EOP patients (15.5 ± 1.8 years; 70.7% male) were included. EOP patients had significantly more prodromal symptoms with a higher frequency of trouble with thinking, avolition and hallucinations than AOP patients, and significantly different median DUP (91 [33–177] vs. 58 [21–140] days; Z = − 2.006, p = 0.045). This was also significantly longer in SSD vs. BD patients (90 [31–155] vs. 30 [7–66] days; Z = − 2.916, p = 0.004) who, moreover had different profiles of prodromal symptoms. When assessing the interaction between age at onset (EOP/AOP) and type of diagnosis (SSD/BD), avolition was significantly higher (Wald statistic = 3.945; p = 0.047), in AOP patients with SSD compared to AOP BD patients (p = 0.004). Awareness of differences in length of DUP and prodromal symptoms in EOP vs. AOP and SSD vs. BD patients could help improve the early detection of psychosis among minors

Negative symptoms and sex differences in first episode schizophrenia: What's their role in the functional outcome? A longitudinal study

Introduction: Negative symptoms (NS) include asociality, avolition, anhedonia, alogia, and blunted affect and are linked to poor prognosis. It has been suggested that they reflect two different factors: diminished expression (EXP) (blunted affect and alogia) and amotivation/pleasure (MAP) (anhedonia, avolition, asociality). The aim of this article was to examine potential sex differences among first-episode schizophrenia (FES) patients and analyze sex-related predictors of two NS symptoms factors (EXP and MAP) and functional outcome. Material and methods: Two hundred and twenty-three FES (71 females and 152 males) were included and evaluated at baseline, six-months and one-year. Repeated measures ANOVA was used to examine the effects of time and sex on NS and a multiple linear regression backward elimination was performed to predict NS factors (MAP-EXP) and functioning. Results: Females showed fewer NS (p = 0.031; Cohen's d = −0.312), especially those related to EXP (p = 0.024; Cohen's d = −0.326) rather than MAP (p = 0.086), than males. In both male and female group, worse premorbid adjustment and higher depressive symptoms made a significant contribution to the presence of higher deficits in EXP at one-year follow-up, while positive and depressive symptoms predicted alterations in MAP. Finally, in females, lower deficits in MAP and better premorbid adjustment predicted better functioning at one-year follow-up (R2 = 0.494; p < 0.001), while only higher deficits in MAP predicted worse functioning in males (R2 = 0.088; p = 0.012). Conclusions: Slightly sex differences have been found in this study. Our results lead us to consider that early interventions of NS, especially those focusing on motivation and pleasure symptoms, could improve functional outcomes

Ice-Prevention and De-Icing Capacity of Epoxy Resin Filled with Hybrid Carbon-Nanostructured Forms: Self-Heating by Joule Effect

In this study, CNTs and graphite have been incorporated to provide electrical conductivity and self-heating capacity by Joule effect to an epoxy matrix. Additionally, both types of fillers, with different morphology, surface area and aspect ratio, were simultaneously incorporated (hybrid CNTs and graphite addition) into the same epoxy matrix to evaluate the effect of the self-heating capacity of carbon materials-based resins on de-icing and ice-prevention capacity. The self-heating capacity by Joule effect and the thermal conductivity of the differently filled epoxy resin were evaluated for heating applications at room temperature and at low temperatures for de-icing and ice-prevention applications. The results show that the higher aspect ratio of the CNTs determined the higher electrical conductivity of the epoxy resin compared to that of the epoxy resin filled with graphite, but the 2D morphology of graphite produced the higher thermal conductivity of the filled epoxy resin. The presence of graphite enhanced the thermal stability of the filled epoxy resin, helping avoid its deformation produced by the softening of the epoxy resin (the higher the thermal conductivity, the higher the heat dissipation), but did not contribute to the self-heating by Joule effect. On the other hand, the feasibility of electrically conductive epoxy resins for de-icing and ice-prevention applications by Joule effect was demonstrated.This research was funded by the European Commission by the financial support of the MASTRO project, H2020 R&I programme. Contract no. 760940

Role of graphene oxide surface chemistry on the improvement of the interlaminar mechanical properties of resin infusion processed epoxy‐carbon fiber composites

The present study deals with the influence of graphene oxide functional groups on their ability to reinforce an epoxy resin when forming carbon fiber composites. Composites were processed through the direct vacuum infusion of the doped resin into carbon fiber fabrics. We used graphene oxide nanosheets with two different chemical characters: as‐produced graphene oxide, with a high oxygen content and acid character, and a simple ammonia base‐washed graphene oxide, which to a great extent removes the oxidative debris or highly oxidized fulvic‐like entities, resulting in an average lower oxygen content and cleaner surface sheets than as‐produced graphene oxide. Base‐washed graphene oxide performed considerably better in both tensile and mode‐I interlaminar properties of carbon fiber composites. The fracture energy required for the onset of mode I interlaminar fracture toughness was enhanced 31% when using as‐produced graphene oxide and 60% when using base‐washed graphene oxide by adding 0.2 wt% only. More interestingly, base‐washed graphene oxide produces a higher delamination resistance along the entire range of crack growth. The effect of adding graphene oxide with a cleaner surface and lower oxygen surface chemistry allows direct chemical bonding matrix‐graphene when the resin is curing, promoting a better interface fiber‐resin and consequently, improving the reinforcement efficiency.Government of Spain and the Ministry of Economy and Competitiveness; contract grant number: CTQ2013-44213-R; contract grant sponsor: Generalitat Valenciana; contract grant number: PROMETEOII/2014/007

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 carbonsThe 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)Peer reviewe

Effective method for a graphene oxide with impressive selectivity in carboxyl groups

The development of new applications of graphene oxide in the biomedical field requires the covalent bonding of bioactive molecules to a sheet skeleton. Obtaining a large carboxyl group population over the surface is one of the main targets, as carboxyl group concentration in conventional graphene oxide is low among a majority of non-useful sp3-C-based functionalities. In the present work, we propose a selective method that yields an impressive increase in carboxyl group population using single-layer, thermally reduced graphene oxide as a precursor in a conventional Hummers–Offemann reaction. When starting with a reduced graphene oxide with no interlayer registry, sulfuric acid cannot form a graphite intercalated compound. Then, potassium permanganate attacks in in-plane (vacancies or holes) structural defects, which are numerous over a thermally reduced graphene oxide, as well as in edges, yielding majorly carboxyl groups without sheet cutting and unzipping, as no carbon dot formation was observed. A single-layer precursor with no ordered stacking prevents the formation of an intercalated compound, and it is this mechanism of the potassium permanganate that results in carboxyl group formation and the hydrophilic character of the compound