Size Control of Carbon Xerogel Spheres as Key Factor Governing the H2O2 Selectivity in Metal-Free Bifunctional Electro-Fenton Catalysts for Tetracycline Degradation.

Carbon xerogel spheres co-doped with nitrogen and eco-graphene were synthesized using a typical solvothermal method. The results indicate that the incorporation of eco-graphene enhances the electrochemical properties, such as the current density (JK) and the selectivity for the four transferred electrons (n). Additionally, nitrogen doping has a significant effect on the degradation efficiency, varying with the size of the carbon xerogel spheres, which could be attributed to the type of nitrogenous group doped in the carbon material. The degradation efficiency improved in the nanometric spheres (48.3% to 61.6%) but decreased in the micrometric-scale spheres (58.6% to 53.4%). This effect was attributed to the N-functional groups present in each sample, with N-CNS-5 exhibiting a higher percentage of graphitic nitrogen (35.7%) compared to N-CMS-5 (15.3%). These findings highlight the critical role of sphere size in determining the type of N-functional groups present in the sample. leading to enhanced degradation of pollutants as a result of the electro-Fenton process.

Cellulose-based materials in tailoring a novel defective titanium­carbon­phosphorus hybrid composites for highly efficient photocatalytic activity.

Until now, black titania has attracted much interest as a potential photocatalyst. In this contribution, we report the first demonstration of the effective strategy to fundamentally improve the photocatalytic performance using a novel sustainable defective titanium­carbon-phosphorous (TCPH) hybrid nanocomposite. The prepared TCPH was used for photocatalytic degradation of the main organic pollutants, which is methyl orange (MO) dye. The physico-chemical properties of as-prepared samples were characterized by various techniques to observe the transformations after carbonization and the interaction between different composite phases. The existence of Ti+3 and oxygen vacancies at the surface, and a notable increase in surface area, are all demonstrated by TCPH, together with the distinct core-shell structure. These unique properties exhibit excellent photocatalytic performance due to the boosted charge transport and separation. The highest degradation efficiency of methyl orange (MO) was attained in the case of TCPH when compared with titanium-cellulose-phosphorous (TCeP) and titanium­carbon-phosphorous (TCPN). Accordingly, the highest degradation efficiency was achieved by applying the optimal operational conditions of 1 g/L of TCPH catalyst, 10 mg/L of MO, pH of 7 and the temperature at 25 ± 3 °C after 3 min under LED lamp (365 nm) with light intensity 100 mW/cm2. The degradation mechanism was investigated, and the trapping tests showed the dominance of hydroxyl radicals in the degradation of MO. TCPH showed high stability under a long period of operation in five consecutive cycles, which renders the highly promising on an industrial scale. The fabrication of highly active defective titanium­carbon-phosphorous opens new opportunities in various areas, including water splitting, and CO2 reduction.

Carbon Gels-Green Graphene Composites as Metal-Free Bifunctional Electro-Fenton Catalysts.

The Electro-Fenton (EF) process has emerged as a promising technology for pollutant removal. However, the EF process requires the use of two catalysts: one acting as an electrocatalyst for the reduction of oxygen to H2O2 and another Fenton-type catalyst for the generation of ·OH radicals from H2O2. Thus, the search for materials with bifunctionality for both processes is required for a practical and real application of the EF process. Thus, in this work, bifunctional electrocatalysts were obtained via doping carbon microspheres with Eco-graphene, a form of graphene produced using eco-friendly methods. The incorporation of Eco-graphene offers numerous advantages to the catalysts, including enhanced conductivity, leading to more efficient electron transfer during the Electro-Fenton process. Additionally, the synthesis induced structural defects that serve as active sites, promoting the direct production of hydroxyl radicals via a 3-electron pathway. Furthermore, the spherical morphology of carbon xerogels enhances the accessibility of the reagents to the active sites. This combination of factors results in the effective degradation of Tetracycline (TTC) using metal-free catalysts in the Electro-Fenton process, achieving up to an impressive 83% degradation without requiring any other external or additional catalyst.

Growing Tungsten Nanophases on Carbon Spheres Doped with Nitrogen. Behaviour as Electro-Catalysts for Oxygen Reduction Reaction.

This work shows the preparation of carbon nanospheres with a high superficial nitrogen content (7 wt.%), obtained by a simple hydrothermal method, from pyrocatechol and formaldehyde, around which tungsten nanophases have been formed. One of these nanophases is tungsten carbide, whose electro-catalytic behavior in the ORR has been evaluated together with the presence of nitrogen surface groups. Both current and potential kinetic density values improve considerably with the presence of tungsten, despite the significant nitrogen loss detected during the carbonization treatment. However, the synergetic effect that the WC has with other electro-catalytic metals in this reaction cannot be easily evaluated with the nitrogen in these materials, since both contents vary in opposite ways. Nevertheless, all the prepared materials carried out oxygen electro-reduction by a mixed pathway of two and four electrons, showing remarkable electro-catalytic behavior.

Synthesis of Magnetic Adsorbents Based Carbon Highly Efficient and Stable for Use in the Removal of Pb(II) and Cd(II) in Aqueous Solution.

In this study, two alternative synthesis routes for magnetic adsorbents were evaluated to remove Pb(II) and Cd(II) in an aqueous solution. First, activated carbon was prepared from argan shells (C). One portion was doped with magnetite (Fe3O4+C) and the other with cobalt ferrite (CoFe2O4+C). Characterization studies showed that C has a high surface area (1635 m2 g-1) due to the development of microporosity. For Fe3O4+C the magnetic particles were nano-sized and penetrated the material's texture, saturating the micropores. In contrast, CoFe2O4+C conserves the mesoporosity developed because most of the cobalt ferrite particles adhered to the exposed surface of the material. The adsorption capacity for Pb(II) was 389 mg g-1 (1.88 mmol g-1) and 249 mg g-1 (1.20 mmol g-1); while for Cd(II) was 269 mg g-1 (2.39 mmol g-1) and 264 mg g-1 (2.35 mmol g-1) for the Fe3O4+C and CoFe2O4+C, respectively. The predominant adsorption mechanism is the interaction between -FeOH groups with the cations in the solution, which are the main reason these adsorption capacities remain high in repeated adsorption cycles after regeneration with HNO3. The results obtained are superior to studies previously reported in the literature, making these new materials a promising alternative for large-scale wastewater treatment processes using batch-type reactors.

Design of Self-Supported Flexible Nanostars MFe-LDH@ Carbon Xerogel-Modified Electrode for Methanol Oxidation.

Layered double hydroxides (LDHs) have emerged as promising electrodes materials for the methanol oxidation reaction. Here, we report on the preparation of different LDHs with the hydrothermal process. The effect of the divalent cation (i.e., Ni, Co, and Zn) on the electrochemical performance of methanol oxidation was investigated. Moreover, nanocomposites of LDHs and carbon xerogels (CX) supported on nickel foam (NF) substrate were prepared to investigate the role of carbon xerogel. The results show that NiFe-LDH/CX/NF is an efficient electrocatalyst for methanol oxidation with a current density that reaches 400 mA·m-2 compared to 250 and 90 mA·cm-2 for NiFe-LDH/NF and NF, respectively. In addition, all LDH/CX/NF nanocomposites show excellent stability for methanol oxidation. A clear relationship is observed between the electrodes crystallite size and their activity to methanol oxidation. The smaller the crystallite size, the higher the current density delivered. Additionally, the presence of carbon xerogel in the nanocomposites offer 3D interconnected micro/mesopores, which facilitate both mass and electron transport.

Nickel Cobaltite Functionalized Silver Doped Carbon Xerogels as Efficient Electrode Materials for High Performance Symmetric Supercapacitor.

Introducing new inexpensive materials for supercapacitors application with high energy density and stability, is the current research challenge. In this work, Silver doped carbon xerogels have been synthesized via a simple sol-gel method. The silver doped carbon xerogels are further surface functionalized with different loadings of nickel cobaltite (1 wt.%, 5 wt.%, and 10 wt.%) using a facile impregnation process. The morphology and textural properties of the obtained composites are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and nitrogen physisorption analysis. The silver doped carbon xerogels display a higher surface area and larger mesopore volume compared to the un-doped carbon xerogels and hierarchically porous structure is obtained for all materials. The hybrid composites have been utilized as electrode materials for symmetric supercapacitors in 6 M KOH electrolyte. Among all the hybrid composites, silver doped carbon xerogel functionalized with 1 wt.% nickel cobaltite (NiCo1/Ag-CX) shows the best supercapacitor performance: high specific capacitance (368 F g-1 at 0.1 A g-1), low equivalent series resistance (1.9 Ω), high rate capability (99% capacitance retention after 2000 cycles at 1 A g-1), and high energy and power densities (50 Wh/Kg, 200 W/Kg at 0.1 A g-1). It is found that the specific capacitance does not only depend on surface area, but also on others factors such as particle size, uniform particle distribution, micro-mesoporous structure, which contribute to abundant active sites and fast charge, and ion transfer rates between the electrolyte and the active sites.

Binary and Ternary 3D Nanobundles Metal Oxides Functionalized Carbon Xerogels as Electrocatalysts toward Oxygen Reduction Reaction.

A series of carbon xerogels doped with cobalt, nickel, and iron have been prepared through the sol-gel method. The doped carbon xerogels were further functionalized with binary and ternary transition metal oxides containing Co, Ni, and Zn oxides by the hydrothermal method. A development in the mesopore volume is achieved for functionalized carbon xerogel doped with iron. However, in the functionalization of carbon xerogel with ternary metal oxides, a reduction in pore diameter and mesopore volume is found. In addition, all functionalized metal oxides/carbon are in the form of 3D nanobundles with different lengths and widths. The prepared samples have been tested as electrocatalysts for oxygen reduction reaction (ORR) in basic medium. All composites showed excellent oxygen reduction reaction activity; the low equivalent series resistance of the Zn-Ni-Co/Co-CX composite was especially remarkable, indicating high electronic conductivity. It has been established that the role of Zn in this type of metal oxides nanobundles-based ORR catalyst is not only positive, but its effect could be enhanced by the presence of Ni.

Biomass-Derived Carbon Molecular Sieves Applied to an Enhanced Carbon Capture and Storage Process (e-CCS) for Flue Gas Streams in Shallow Reservoirs.

It is possible to take advantage of shallow reservoirs (<300 m) for CO2 capture and storage in the post-combustion process. This process is called enhanced carbon capture and storage (e-CCS). In this process, it is necessary to use a nano-modifying agent to improve the chemical-physical properties of geological media, which allows the performance of CO2 selective adsorption to be enhanced. Therefore, this study presents the development and evaluation of carbon sphere molecular nano-sieves (CSMNS) from cane molasses for e-CSS. This is the first report in the scientific literature on CSMNS, due to their size and structure. In this study, sandstone was used as geological media, and was functionalized using a nanofluid, which was composed of CNMNS dispersed in deionized water. Finally, CO2 or N2 streams were used for evaluating the adsorption process at different conditions of pressure and temperature. As the main result, the nanomaterial allowed a natural selectivity towards CO2, and the sandstone enhanced the adsorption capacity by an incremental factor of 730 at reservoir conditions (50 °C and 2.5 MPa) using a nanoparticle mass fraction of 20%. These nanofluids applied to a new concept of carbon capture and storage for shallow reservoirs present a novel landscape for the control of industrial CO2 emissions.

Functionalized Cellulose for the Controlled Synthesis of Novel Carbon-Ti Nanocomposites: Physicochemical and Photocatalytic Properties.

Carbon-Ti nanocomposites were prepared by a controlled two-step method using microcrystalline cellulose as a raw material. The synthesis procedure involves the solubilization of cellulose by an acid treatment (H3PO4 or HNO3) and the impregnation with the Ti precursor followed of a carbonization step at 500 or 800 °C. The type of acid treatment leads to a different functionalization of cellulose with phosphorus- or oxygen-containing surface groups, which are able to control the load, dispersion and crystalline phase of Ti during the composite preparation. Thus, phosphorus functionalities lead to amorphous carbon-Ti composites at 500 °C, while TiP2O7 crystals are formed when prepared at 800 °C. On the contrary, oxygenated groups induce the formation of TiO2 rutile at an unusually low temperature (500 °C), while an increase of carbonization temperature promotes a progressive crystal growth. The removal of Orange G (OG) azo dye in aqueous solution, as target pollutant, was used to determine the adsorptive and photocatalytic efficiencies, with all composites being more active than the benchmark TiO2 material (Degussa P25). Carbon-Ti nanocomposites with a developed micro-mesoporosity, reduced band gap and TiO2 rutile phase were the most active in the photodegradation of OG under ultraviolet irradiation.

Removal of emerging pollutants present in water using an E-coli biofilm supported onto activated carbons prepared from argan wastes: Adsorption studies in batch and fixed bed.

In order to improve the removal rates of paracetamol and amoxicillin present in water, activated carbons prepared from argan waste were designed as a support for a biofilm-based on E. coli yielding microporous materials with high surface areas, in such a way that the biofilm support could be made homogeneously on the internal and external surface of the material. Adsorption studies without the presence of the biofilm showed rapid kinetics with adsorption constants kPCT = 0.06 and kAMX = 0.007 min-1. The adsorption isotherms could be described by the Langmuir isotherm model reaching a maximum adsorption capacity of qPCT = 502 and qAMX = 319 mg g-1. In contrast, the results obtained for the materials that support the biofilm showed slow kinetics (kPCT = 0.007 and kAMX = 0.003 min-1) and a remarkable change in the shape of the adsorption isotherms, since the experimental data are better represented by a combined Langmuir-Freundlich model, in which three important stages are observed: (i) In a first stage, adsorption is carried out in those spaces available after supporting the biofilm in the surface of the ACs. Once these spaces have been saturated, a second stage (ii) is present with an exponential behavior typical of the Freundlich isotherm, attributed to the adsorption of the pharmaceutical compounds in the biofilm, Finally a third stage is observed (iii) where the asymptotic behavior typical of the saturation of the adsorbent according to the Langmuir model is already appreciated (qPCT = 504 and qAMX = 465 mg g-1).

Element-Doped Functional Carbon-Based Materials.

Carbon materials are one of the most fascinating materials because of their unique properties and potential use in several applications. They can be obtained from agricultural waste, organic polymers, or by using advanced synthesizing technologies. The carbon family is very wide, it includes classical activated carbons to more advanced types like carbon gels, graphene, and so on. The surface chemistry of these materials is one of the most interesting aspects to be studied. The incorporation of different types of chemical functionalities and/or heteroatoms such as O, N, B, S, or P on the carbon surface enables the modification of the acidic-basic character, hydrophilicity-hydrophobicity, and the electron properties of these materials, which in turn determines the final application. This book collects original research articles focused on the synthesis, properties, and applications of heteroatom-doped functional carbon materials.

Carbon Xerogels Hydrothermally Doped with Bimetal Oxides for Oxygen Reduction Reaction.

A total of two carbon xerogels doped with cobalt and nickel were prepared by the sol-gel method. The obtained carbon xerogels underwent further surface modification with three binary metal oxides namely: nickel cobaltite, nickel ferrite, and cobalt ferrite through the hydrothermal method. The mesopore volumes of these materials ranged between 0.24 and 0.40 cm3/g. Moreover, there was a morphology transformation for the carbon xerogels doped with nickel cobaltite, which is in the form of nano-needles after the hydrothermal process. Whereas the carbon xerogels doped with nickel ferrite and cobalt ferrite maintained the normal carbon xerogel structure after the hydrothermal process. The prepared materials were tested as electrocatalysts for oxygen reduction reaction using 0.1 M KOH. Among the prepared carbon xerogels cobalt-doped carbon xerogel had better electrocatalytic performance than the nickel-doped ones. Moreover, the carbon xerogels doped with nickel cobaltite showed excellent activity for oxygen reduction reaction due to mesoporosity development. NiCo2O4/Co-CX showed to be the best electrocatalyst of all the prepared electrocatalysts for oxygen reduction reaction application, exhibiting the highest electrocatalytic activity, lowest onset potential Eonset of -0.06 V, and the lowest equivalent series resistance (ESR) of 2.74 Ω.

Influence of Surface Chemistry on the Electrochemical Performance of Biomass-Derived Carbon Electrodes for its Use as Supercapacitors.

Activated carbons prepared by chemical activation from three different types of waste woods were treated with four agents: melamine, ammonium carbamate, nitric acid, and ammonium persulfate, for the introduction of nitrogen and oxygen groups on the surface of materials. The results indicate that the presence of the heteroatoms enhances the capacitance, energy density, and power density of all samples. The samples treated with ammonium persulfate show the maximum of capacitance of 290 F g-1 while for the melamine, ammonium carbamate, and nitric acid treatments, the samples reached the maximum capacitances values of 283, 280, and 455 F g-1 respectively. This remarkable electro-chemical performance, as the high specific capacitances can be due to several reasons: i) The excellent and adequate textural characteristics makes possible a large adsorption interface for electrolyte to form the electrical double layer, leading to a great electrochemical double layer capacitance. ii) The doping with hetero-atoms enhances the surface interaction of these materials with the aqueous electrolyte, increasing the accessibility of electrolyte ions. iii) The hetero-atoms groups can also provide considerable pseudo-capacitance improving the overall capacitance.

An Enhanced Carbon Capture and Storage Process (e-CCS) Applied to Shallow Reservoirs Using Nanofluids Based on Nitrogen-Rich Carbon Nanospheres.

The implementation of carbon capture and storage process (CCS) has been unsuccessful to date, mainly due to the technical issues and high costs associated with two main stages: (1) CO2 separation from flue gas and (2) CO2 injection in deep geological deposits, more than 300 m, where CO2 is in supercritical conditions. This study proposes, for the first time, an enhanced CCS process (e-CCS), in which the stage of CO2 separation is removed and the flue gas is injected directly in shallow reservoirs located at less than 300 m, where the adsorptive phenomena control CO2 storage. Nitrogen-rich carbon nanospheres were used as modifying agents of the reservoir porous texture to improve both the CO2 adsorption capacity and selectivity. For this purpose, sandstone was impregnated with a nanofluid and CO2 adsorption was evaluated at different pressures (atmospheric pressure and from 3 × 10-3 MPa to 3.0 MPa) and temperatures (0, 25, and 50 °C). As a main result, a mass fraction of only 20% of nanomaterials increased both the surface area and the molecular interactions, so that the increase of adsorption capacity at shallow reservoir conditions (50 °C and 3.0 MPa) was more than 677 times (from 0.00125 to 0.9 mmol g-1).

The use of functionalized carbon xerogels in cells growth.

In the present study carbon xerogels are used for the first time to study the fibroblast cell growth. For that, carbon xerogel microspheres are synthesized and thereafter functionalized with carbon nanofibers followed by the 1,3-dipolar cycloaddition of azomethine ylides (the so called "Prato reaction") or the addition of aryl diazonium salts (the so called "Tour reaction") to improve its wettability. The presence of nanofibers produces a huge improvement of the functionalization degree (59 versus 372 µmol/g for pristine carbon spheres and carbon spheres with 30% of carbon nanofibers, respectively) in spite of the blockage of the carbon spheres porosity caused after the nanofibers growth. This improvement was explained on the base of the increase of the number of probable active sites for the addition reactions (CC bonds) and the accessibility to these active sites (accessible surface area) by the presence of nanofibers. These high functionalization degrees reflect a promising potential of these materials in biomedical applications. Toxicity results obtained using a fibroblast cell line showed that samples are biocompatible for this kind of cells and that the presence of carbon fibers on the surface of the spheres increases the cells proliferation in a high extend reaching in some case values around 150% regarding the control. This study evidences that carbon aerogels could be interesting materials in biological applications, an unexplored field for this type of materials, being biocompatible, favouring the proliferation of cells and achieving high functionalization degrees.

From Polyethylene to Highly Graphitic and Magnetic Carbon Spheres Nanocomposites: Carbonization under Pressure.

Carbon nanocomposites microspheres were synthesized from Low-Density Polyethylene (LDPE) by a facile one-step strategy under solvent-free conditions. The synthesis of these materials was carried out in a closed Hastelloy® reactor at 700 °C. The treatment, during which autogenic pressure was generated, leads to highly graphitic materials with stunning properties, particularly concerning the oxidation resistance (compared to the graphite stability). The metallic doping triggers the growth of nanostructures with diverse morphologies around the spheres, obtaining samples with magnetic properties.

On the Interactions and Synergism between Phases of Carbon⁻Phosphorus⁻Titanium Composites Synthetized from Cellulose for the Removal of the Orange-G Dye.

Carbon⁻phosphorus⁻titanium composites (CPT) were synthesized by Ti-impregnation and carbonization of cellulose. Microcrystalline cellulose used as carbon precursor was initially dissolved by phosphoric acid (H3PO4) to favor the Ti-dispersion and the simultaneous functionalization of the cellulose chains with phosphorus-containing groups, namely phosphates and polyphosphates. These groups interacted with the Ti-precursor during impregnation and determined the interface transformations during carbonization as a function of the Ti-content and carbonization temperature. Amorphous composites with high surface area and mesoporosity were obtained at low Ti-content (Ti:cellulose ratio = 1) and carbonization temperature (500 °C), while in composites with Ti:cellulose ratio = 12 and 800 °C, Ti-particles reacted with the cellulose groups leading to different Ti-crystalline polyphosphates and a marked loss of the porosity. The efficiency of composites in the removal of the Orange G dye in solution by adsorption and photocatalysis was discussed based on their physicochemical properties. These materials were more active than the benchmark TiO2 material (Degussa P25), showing a clear synergism between phases.

Electrodes Based on Carbon Aerogels Partially Graphitized by Doping with Transition Metals for Oxygen Reduction Reaction.

A series of carbon aerogels doped with iron, cobalt and nickel have been prepared. Metal nanoparticles very well dispersed into the carbon matrix catalyze the formation of graphitic clusters around them. Samples with different Ni content are obtained to test the influence of the metal loading. All aerogels have been characterized to analyze their textural properties, surface chemistry and crystal structures. These metal-doped aerogels have a very well-developed porosity, making their mesoporosity remarkable. Ni-doped aerogels are the ones with the largest surface area and the smallest graphitization. They also present larger mesopore volumes than Co- and Fe-doped aerogels. These materials are tested as electro-catalysts for the oxygen reduction reaction. Results show a clear and strong influence of the carbonaceous structure on the whole electro-catalytic behavior of the aerogels. Regarding the type of metal doping, aerogel doped with Co is the most active one, followed by Ni- and Fe-doped aerogels, respectively. As the Ni content is larger, the kinetic current densities increase. Comparatively, among the different doping metals, the results obtained with Ni are especially remarkable.

Surface chemistry, porous texture, and morphology of N-doped carbon xerogels.

N-doped carbon xerogels were obtained from organic xerogels prepared using different N-containing organic compounds, including 3-hydroxy aniline, melamine, and 3-hydroxy pyridine. Carbonization was carried out between 500 and 900 degreeC. The surface chemistry of samples was determined by elemental analysis and X-ray photoelectron spectroscopy, their porous texture was determined by N2 and CO2 adsorption at (-)196 and 0degreeC, respectively, and their morphology was determined by scanning electron microscopy. N-doped carbon xerogels with a wide variety of N contents and functionalities were obtained according to the ingredients and carbonization temperature used. Carbon xerogels contained, in different proportions, three/four N functionalities: pyridinic, pyrrolic and/or pyridonic, and quaternary N functionalities. They were microporous carbons with narrow micropores that had constrictions at their entrances, producing higher CO2(-) than N2-determined micropore surface areas. Morphology studies showed samples to be constituted by isolated microspheres or microsphere clusters. Microsphere diameters depended on the recipe and carbonization temperature used.