Carbon Xerogels Research Articles

Kraft lignin-based carbon xerogel/zinc oxide composite for 4-chlorophenol solar-light photocatalytic degradation: effect of pH, salinity, and simultaneous Cr(VI) reduction.

Considering the ever-increasing need for efficient wastewater treatment, this study focused on the development of new kraft lignin-based carbon xerogel/zinc oxide (XCL/ZnO w) photocatalysts. The inclusion of the carbon xerogel is expected to cause an improvement in charge transfer throughout the photoactivation process, consequently enhancing its overall photocatalytic efficiency. Characterization shows that the materials developed are composed of both zinc oxide and carbon xerogel. The addition of the lignin-based carbon xerogel caused a significant morphological modification to the composite materials, resulting in a greater specific surface area. Regarding the photocatalytic efficiency, the optimized composite (XCL/ZnO 1.0) displayed superior efficiency to the pure zinc oxide, especially when calcined at 700°C, with an increase of 20% in the overall photodegradation capacity for the 4-chlorophenol (4CP) molecule. The XCL/ZnO 1.0 also displayed better performance than its tannin counterpart, previously reported in the literature, obtaining a 60% increase in the apparent reaction rate constant. The XCL/ZnO 1.0 also displayed better performance for the simultaneous hexavalent chrome (Cr (VI)) reduction/4CP oxidation reaction. Salinity and system pH had a significant influence on the efficiency of the 4CP photodegradation, as higher values of salinity and lower pHs caused a decrease in the overall efficiency of the process. At last, chronoamperometry and open-circuit potential tests confirmed the superiority of the XCL/ZnO 1.0 over the pure ZnO, highlighting the beneficial impact of the carbon xerogel on the charge transport dynamics of the composite.

Amine-Modified Carbon Xerogels as Effective Carbon-Based Adsorbents of Anionic Dye from Aqueous Solutions.

Carbon xerogels were obtained by polycondensation of resorcinol and formaldehyde in a water medium. Their surface was oxidized by ammonium persulfate and then modified with amine groups. Four amines were used: methylamine, ethylamine, propylamine, and ethylenediamine, differing in carbon chain length and number of amine groups. The materials were characterized by low-temperature nitrogen sorption, elemental analysis, thermal analysis, X-ray diffraction, infrared spectroscopy, and determination of the surface oxygen group content with the use of the Boehm method. The final carbon adsorbents had surface areas ranging from 172–663 m2/g and acid–base nature. They were applied for adsorption of thymol blue from water solution. The sorption capacities of the studied adsorbents ranged from 83 to 140 mg/g. The presence of amine groups on the xerogel surface was found to increase its sorption capacity towards the dye studied. The dye adsorption process is endothermic and spontaneous, as indicated by the positive values of ΔH and the negative values of ΔG, respectively. The kinetics of adsorption of thymol blue was established to be described by the pseudo-second-order model. The equilibrium data were analyzed by the Langmuir and Freundlich models. The character of thymol blue adsorption is much better described by the Langmuir isotherm.

3D Nanohybrid of MoS2 nanocoils functionalized carbon xerogels for methanol electro-oxidation

Searching for suitable low-cost electro-catalysts for methanol oxidation with high stability is a big challenge. Here, we report the successful preparations of carbon xerogels (CX) derived from resorcinol and formaldehyde monomors. Carbon xerogel was further functionalized with transition metals and transition metal dichalcogenides namely; Mo, W, MoS2 and WS2 through the hydrothermal process in presence of nickel foam (NF). These binder free nanocomposites were employed as electro-catalysts for methanol oxidation reaction (MOR). An outstanding electrochemical activity for MoS2/CX/NF electro-catalyst for MOR was observed that delivered high current density of about 550 mA‧cm−2 and long-term stability. This outstanding electro-catalytic performance towards MOR for MoS2/CX are due to the unique nanocoil structure of MoS2, which increases mesoporosity and active surface area, allowing for sufficient electrical conductive channels and pathways for electrons. This work could introduce a promising electro-catalyst for large scale commercial fuel cell applications.

Facile in Situ Fabrication of a Co-Fe Bimetallic N-doped Carbon Xerogel as an Efficient Electrocatalyst for Oxygen Reduction Reaction in Acidic and Alkaline Media

Facile in Situ Fabrication of a Co-Fe Bimetallic N-doped Carbon Xerogel as an Efficient Electrocatalyst for Oxygen Reduction Reaction in Acidic and Alkaline Media

Synthesis of composite membranes from polyacrylonitrile/carbon resorcinol/formaldehyde xerogels: gamma effect study, characterization and ultrafiltration of salted oily wastewater

Abstract The subsequent activated carbons of resorcinol-formaldehyde xerogels are synthesized and exposed to wide range of gamma irradiation dose. Xerogels and their subsequent activated carbons are characterized by diverse techniques; FTIR, Raman, porosity analysis, SEM, EDX and AFM. The composite membranes are fabricated from polyacrylonitrile and activated carbon xerogels as composite membranes to be utilized in ultrafiltration process of salted oily wastewater. The soybean oil is exploited as organic feeding solution. The results declared that values of flux and rejection reach 157 (L m−2 h−1) and 99.8 (%), respectively. Overall, the best performing composite membrane is conducted by maximizing pure water flux. The optimally synthesized membrane performs well for purification of salted oily wastewater, and a significant increment in permeate flux is obtained with soybean oil rejection is at ∼99.8% and with maximum flux is at 32 (L m−2 h−1). Further, the composite membranes showed good promise for ultrafiltration of salted oily wastewater.

Resorcinol-based carbon xerogel/ZnO composite for solar-light-induced photodegradation of sulfamerazine

Recently, the release of antibiotics, such as sulfonamides, into the environment has raised significant concern due to the potential creation of antibiotic-resistant bacteria. Thus, the development of remediation technologies for effluents containing such compounds is of utmost urgency. In this context, this work evaluated the creation of a resorcinol-based carbon xerogel/zinc oxide photocatalyst (XC/ZnO) to efficiently promote the photodegradation of the antibiotic known as sulfamerazine in aqueous media. The employment of this carbonaceous structure as a co-catalyst is justified by its high surface area and electrical conductivity. The methodology used in the synthesis of the composites was a simple one-pot reaction, combining the simultaneous precipitation of zinc oxide and polycondensation of the resorcinol-based carbon gel. Regarding the composites' characterization, X-ray diffractometry confirms that the composites have the Wurtzite structure of the zinc oxide, whereas the carbon xerogel formation is evidenced by the infrared, diffuse reflectance, and X-ray photoelectron spectroscopies. Morphology-wise, the XC/ZnO is arranged as nodular particle agglomerates, with particles between 500 nm and 50 nm. The photocatalytic tests under simulated solar radiation show that the composites developed are superior to the pure oxide in the photodegradation of sulfamerazine, as all XC/ZnO materials developed achieved higher apparent reaction rate constants (kapp) than pure zinc oxide, with the XC/ZnO 0.5 material obtaining a kapp 75% higher than the one observed for the ZnO sample. Furthermore, the chronoamperometry tests confirmed that the optimized composite (XC/ZnO 0.5) has a greater capacity for photocurrent generation when compared to pure zinc oxide. Therefore, the modification proposed was successful to enhance the photodegradation of sulfamerazine in aqueous media, highlighting the viability of the composites developed for photocatalytic applications.

Pore-scale investigation on the multi-component gas adsorption and diffusion in carbon xerogel microporous structure using molecular simulation methods

The atomic model of carbon xerogel microporous structure is reconstructed by a modified virtual porous carbon (VPC) model. The physical parameters of the reconstructed model, especially the predicted nitrogen adsorption isotherm, agree well with the experimental data. Then, the adsorption and diffusion of the gas in carbon xerogel microporous structure are investigated at the pore-scale. The results show that decreases of isosteric adsorption heat and the excess adsorption in carbon xerogel microporous structure are majorly contributed by the desorption of adsorbates in ultramicropores with the temperature increasing. The microporous structure appears a strong selectivity for oxygen in the air, due to the molecular sieving effect and the strong solid-fluid interaction between the pore wall and oxygen. As the desorption of oxygen in ultramicropores due to its increasing steric repulsion with the temperature rising from 298 K to 573 K, the selectivity of microporous structure for oxygen decreases, and the gap between isosteric adsorption heat for nitrogen and oxygen is narrowed. The systemic migration of gas molecules from the ultramicropores to the wider area is observed by the pore-scale analysis, and it makes the gas diffusivity appear an approximately linear relationship with the temperature.

Immobilization and Characterization of L-Asparaginase over Carbon Xerogels.

L-asparaginase (ASNase) is an aminohydrolase currently used in the pharmaceutical and food industries. Enzyme immobilization is an exciting option for both applications, allowing for a more straightforward recovery and increased stability. High surface area and customizable porosity make carbon xerogels (CXs) promising materials for ASNase immobilization. This work describes the influence of contact time, pH, and ASNase concentration on the immobilization yield (IY) and relative recovered activity (RRA) using the Central Composite Design methodology. The most promising results were obtained using CX with an average pore size of 4 nm (CX-4), reaching IY and RRA of 100%. At the optimal conditions (contact time 49 min, pH 6.73, and [ASNase] 0.26 mg·mL−1), the ASNase-CXs biocomposite was characterized and evaluated in terms of kinetic properties and operational, thermal, and pH stabilities. The immobilized ASNase onto CX-4 retained 71% of its original activity after six continuous reaction cycles, showed good thermal stability at 37 °C (RRA of 91% after 90 min), and was able to adapt to both acidic and alkaline environments. Finally, the results indicated a 3.9-fold increase in the immobilized ASNase affinity for the substrate, confirming the potential of CXs as a support for ASNase and as a cost-effective tool for subsequent use in the therapeutic and food sectors.

Influence of Resorcinol to Sodium Carbonate Ratio on Carbon Xerogel Properties for Aluminium Ion Battery.

Carbon xerogels were synthesized using a soft-template route with resorcinol as the carbon source and sodium carbonate as the catalyst. The influence of the resorcinol to catalyst ratio in the range of 500–20,000 on pore structure, graphitic domains, and electronic conductivity of as-prepared carbon xerogels, as well as their performance in an aluminium ion battery (AIB), was investigated. After carbonization steps of the polymers up to 800 °C, all carbon samples exhibited similar specific volumes of micropores (0.7–0.8 cm³ g−1), while samples obtained from mixtures with R/C ratios lower than 2000 led to carbon xerogels with significantly higher mesopore diameters up to 6 nm. The best results, in terms of specific surface (1000 m² g−1), average pore size (6 nm) and reversible capacity in AIB cell (28 mAh g−1 @ 0.1 A g−1), were obtained with a carbon xerogel sample synthetized at a resorcinol to catalyst ratio of R/C = 500 (CXG500). Though cyclic voltammograms of carbon xerogel samples did not exhibit any sharp peaks in the applied potential window, the presence of both oxidation and a quite wide reduction peak in CXG500–2000 cyclic voltammograms indicated pseudocapacitance behaviour induced by diffusion-controlled intercalation/de-intercalation of AlCl4− ions into/from the carbon xerogel matrix. This was confirmed by shifting of the (002) peak towards lower 2θ angle values in the XRD pattern of the CXG500 electrode after the charging step in AIB, whereas the contribution of pseudocapacitance, calculated from half-cell measurements, was limited to only 6% of overall capacitance.

Carbon-based nanohybrid fabricated in-situ and boosted the adsorption of anionic reactive yellow dye

The purpose of this research is to report a unique manipulation of producing carbon nanotubes/carbon xerogel (CNTs/CX) hybrid loaded with bimetallic catalysts of Fe–Ni via one-step chemical vapor deposition (CVD) of camphor. Active bimetallic catalysts were formed during carbonization of resorcinol–formaldehyde xerogel at 800 °C to form carbon xerogel (CX); meanwhile, the carbon gas was librated from camphor at 220 °C for 45 min. CX and CNTs/CX samples were analyzed using measurements of transmission electron microscope (TEM), X-ray diffraction tool (XRD) and Fourier transform infrared spectroscopy (FTIR). Further, the liquid-phase adsorption of a reactive yellow 160 (RY160) dye on CX and CNTs/CX samples and thermodynamic studies were investigated. TEM and XRD results revealed the formation of carbon nodules in CX combined with bundles of CNTs having outer diameters ranged from 40 to 80 nm in CNTs/CX. Adsorption of RY160 dye was highly relied on pH, temperature, initial dye concentration and contact time. Through kinetic modeling, pseudo-second-order kinetic model expressed closely the experimental data of RY160 adsorption. Equilibrium adsorption studies declared that the Freundlich model is the better with adsorption of RY160 on CNTs/CX due to it has heterogeneous surface character resulting from combination of CX and CNTs. Langmuir adsorption capacity (qL, mg/g) values exhibited that CNTs/CX sample have a superior adsorption of RY160 dye which were reached to 167 mg/g than that by CX (qL = 125 mg/g). Thereof, the produced CX and CNTs/CX samples present higher removal capacity and can be employed successfully for RY160 dye removal from a textile wastewater.

Revisiting the Effect of Pyrolysis Temperature and Type of Activation on the Performance of Carbon Electrodes in an Electrochemical Capacitor.

Hierarchical porous carbons are known to enhance the electrochemical features of electrodes in electrochemical capacitors. However, the contribution of surface oxygen and the resulting functionalities and wettability, along with the role of electrical conductivity and degree of amorphous or crystalline nature in the micro-mesoporous carbons, are not yet clear. This article considers the effect of carbonisation temperature (500–900 °C) and the type of activation (CO2, KOH) on the properties mentioned above in case of carbon xerogels (CXs) to understand the resulting electrochemical performances. Depending on the carbonisation temperature, CX materials differ in micropore surface area (722–1078 m2 g−1) while retaining a mesopore surface area ~300 m2 g−1, oxygen content (3–15%, surface oxygen 0–7%), surface functionalities, electrical conductivity (7 × 10−6–8 S m−1), and degree of amorphous or crystalline nature. Based on the results, electrochemical performances depend primarily on electrical conductivity, followed by surface oxygen content and meso-micropore connectivity. The way of activation using a varied extent of CO2 exposure and KOH concentrations played differently in CX in terms of pore connectivity from meso- to micropores and their contributions and degree of oxidation, and resulted in different electrochemical behaviours. Such performances of activated CXs depend solely on micro-mesopore features.

Thermal Evolution of C-Fe-Bi Nanocomposite System: From Nanoparticle Formation to Heterogeneous Graphitization Stage.

Carbon xerogel nanocomposites with integrated Bi and Fe particles (C–Bi–Fe) represent an interesting model of carbon nanostructures decorated with multifunctional nanoparticles (NPs) with applicability for electrochemical sensors and catalysts. The present study addresses the fundamental aspects of the catalyzed growth of nano-graphites in C–Bi–Fe systems, relevant in charge transport and thermo-chemical processes. The thermal evolution of a C–Bi–Fe xerogel is investigated using different pyrolysis treatments. At lower temperatures (~750°C), hybrid bismuth iron oxide (BFO) NPs are frequently observed, while graphitization manifests under more specific conditions such as higher temperatures (~1,050°C) and reduction yields. An in situ heating TEM experiment reveals graphitization activity between 800 and 900°C. NP motion is directly correlated with textural changes of the carbon support due to the catalyzed growth of graphitic nanoshells and nanofibers as confirmed by HR-TEM and electron tomography (ET) for the graphitized sample. An exponential growth model for the catalyst dynamics enables the approximation of activation energies as 0.68 and 0.29–0.34 eV during reduction and graphitization stages. The results suggest some similarities with the tip growth mechanism, while oxygen interference and the limited catalyst–feed gas interactions are considered as the main constraints to enhanced growth.

Influence of Nitrogen and Sulfur Doping of Carbon Xerogels on the Performance and Stability of Counter Electrodes in Dye Sensitized Solar Cells

In this work, carbon xerogels (CXGs) doped with nitrogen or sulfur have been investigated as DSSC counter electrodes. CXGs have been prepared by a sol–gel method from resorcinol and formaldehyde and subsequent carbonization. Nitrogen doping has been carried out by introducing melamine into the synthesis process along with resorcinol and formaldehyde, while sulfur has been incorporated by direct reaction of the carbon material with elemental sulfur. The counter electrodes for DSSCs have been prepared by airbrushing on conductive glass (fluorine-doped tin oxide, FTO), and their electrochemical behavior has been evaluated, observing that the introduction of heteroatoms such as nitrogen or sulfur leads to an improvement in efficiency compared to the undoped material thanks to a decrease in charge transfer resistance.

Commercial Gold Complexes Supported on Functionalised Carbon Materials as Efficient Catalysts for the Direct Oxidation of Ethane to Acetic Acid

The single-pot efficient oxidation of ethane to acetic acid catalysed by Au(I) or Au(III) compounds, chlorotriphenylphosphinegold(I) (1), chlorotrimethylphosphinegold(I) (2), 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidenegold(I) chloride (3), dichloro(2-pyridinecarboxylato)gold(III) (4), homogenous and supported on different carbon materials: activated carbon (AC), multi-walled carbon nanotubes (CNT) and carbon xerogel (CX), oxidised with nitric acid followed by treatment with NaOH (-ox-Na), is reported. The reactions were performed in water/acetonitrile. The materials were selective for the production of acetic acid, with no trace of by-products being detected. The best homogenous catalysts were complexes 2 and 3 which showed the highest ethane conversion and an acetic acid yield of ca. 21%, followed by 4 and 1. The heterogenised materials showed much better activity than the homogenous counterparts, with acetic acid yields up to 41.4% for 4@CNT-ox-Na, and remarkable selectivity (with acetic acid being the only product detected). The heterogenised catalysts with the best results were reused up to five cycles, with no significant loss of activity, and maintaining high selectivity for acetic acid. 4@CNT-ox-Na showed not only the best catalytic activity but also the best stability during the recycling runs.

Copper Supported on Mesoporous Structured Catalysts for NO Reduction

Nitrogen oxides (NOx) are one of the pollutants of greatest concern in terms of atmospheric contamination and, consequently, human health. The main objective of this work, is the synthesis of structured carbon catalysts, introducing on their surface metals and nitrogen groups, catalytically active in NO reduction. Structured catalysts represent an attractive alternative to powder catalysts because they have better thermal stability and lower pressure drop. The catalysts were synthesized by coating a melamine foam using precursor solutions of carbon xerogels with and without nitrogen (using melamine and urea as precursors), and impregnated with transition metals (Fe, Ni and Cu). The introduction of nitrogen and metals modified the textural properties of the materials. Samples synthesized with melamine presented the highest amount of nitrogen, while the highest content of copper, found to be the most active transition metal for NO reduction, was found in structured catalysts impregnated with urea. The presence of transition metals in catalysts is essential for the reduction of NO to N2 and the introduction of nitrogenous precursors makes this evident. The synthesis and application of carbon-supported structured catalysts containing transition metals for NO reduction is demonstrated in this work for the first time, as well as the study of the factors influencing their performance.

Magnetite Nanoparticle/Copper Phosphate Nanoflower Composites for Fenton-like Organic Dye Degradation

A fast and sustainable technique in catalytically degrading organic dyes under flow is reported. It involves the use of three different applications of the high-shear and intense micro-mixing vortex fluidic device (VFD), including material fabrication, reactor coating, and material “banding”. The active catalytic material is a composite of magnetite nanoparticles and Cu3(PO4)2 nanoflowers (MNPCuNFs), 8–10 μm in diameter, which are generated in the VFD within 30 min. MNPCuNFs magnetically and centrifugally held against the surface of the rapidly rotating tube in the VFD have enhanced catalytic activity in degrading four different organic dyes under real-time monitoring with at least a fivefold increase in the degradation efficiency compared to that in the batch processing. To further improve the platform performance, the VFD tube reactor was chemically modified, incorporating a thin layer of silica-activated carbon xerogel coating which behaves synergistically with the nanoflowers. This coated tube is highly stable and reusable, dramatically increasing the degradation efficiency by about 30-fold relative to using batch processing. Integrating an ultraviolet–visible spectroscopy-based probe allows real-time monitoring of the reaction and also provides a direct tool to evaluate the coating layer post reaction. This study provides a rational design of hybrid materials and the use of a modified VFD tube reactor toward efficient degradation of organic dyes in real time.

Ruthenium-based catalysts supported on carbon xerogels for hydrogen production via ammonia decomposition

Carbon xerogels were synthesised and used as support of ruthenium-based catalysts for the ammonia decomposition reaction. To improve their physical-chemical properties, carbon xerogels were either activated in carbon dioxide atmosphere (for 1 and 5 h), or doped with nitrogen via co-precursor method, using urea as nitrogen source. Un-promoted and sodium-promoted ruthenium catalysts were prepared by incipient wetness impregnation. All catalysts were tested during the ammonia decomposition reaction (1 atm, 100–600 °C), showing high catalytic activity. The 5 h carbon dioxide activation treatment resulted in a decrease in oxygen surface groups (i.e. by 11 wt%) on carbon xerogels surface, and in an increase in the structure crystallinity (i.e. by 15% in the TBurn) of carbon xerogels, resulting in a higher ammonia decomposition reaction rate (i.e. 3.5-fold at 450 °C). Similarly, nitrogen addition to carbon xerogels had a positive effect on the catalysts basicity, enhancing their catalytic performance (i.e. triple reaction rate at 450 °C). The addition of sodium conferred an enhancement in the performance of each catalyst (i.e. reaction rate up to 9 times higher at 450 °C). Two ammonia decomposition reaction runs were performed for all catalysts, to test the performance reproducibility of the catalysts. It was found that un-promoted catalysts exhibited higher reaction rates (i.e. up to 3.5 times at 450 °C) during the second run of reaction due to the larger ruthenium particle size, whereas sodium-promoted catalysts exhibited similar catalytic activity in both reaction runs due to the presence of sodium oxide avoiding the sintering of ruthenium particles.

Sustainable Carbon Xerogel in the Production of Electromagnetic Radar Absorbing Composites in the Ku-Band

Carbonaceous porous materials are strong candidates for producing low-cost, lightweight, and sustainable electromagnetic (EM) absorbing materials. This work investigates the production of radar-absorbing materials (RAM) by a simple method. Sustainable carbon xerogel (CX) was synthesized from tannin, a biosourced molecule. CX and commercial carbon nanotube (CNT) were embedded in a silicone matrix at proportions of 10 and 15 wt.% of CX and 0.1 wt.% of CNT to produce flexible composites. The morphology and structure of the carbonaceous materials were evaluated by field-emission scanning electron microscopy (FEG-SEM), Raman spectroscopy, X-ray diffraction (XRD), textural properties by N2 adsorption-desorption isotherms, and mercury porosimetry. The electromagnetic characterization of the composites was analyzed by a vector network analyzer (VNA) in the Ku-band. The results demonstrated that an increased concentration of CX in the composite improved reflection loss reaching -43.19 dB at 13.79 GHz.

Enhanced electrocatalytic performance of N-doped carbon xerogels obtained through dual nitrogen doping for the oxygen reduction reaction.

The development of high efficiency and low-cost electrocatalysts for the oxygen reduction reaction (ORR) is urgently desired for many energy storage and conversion systems. Nitrogen-doped carbon xerogels (NCXs) which have been successfully applied as effective electrocatalysts for the ORR have continued to attract attention due to their competitive price and tunable surface chemistry. A new dual N-doped NCX (NCoNC) electrocatalyst is fabricated as a carbon based catalyst though a facile impregnation of peptone in a precursor and ammonia etching pyrolysis method. XPS analysis demonstrates that the NCoNC electrocatalyst not only has a high N doping amount, but also has an optimized chemical state composition of N doping, which play an important role in improving the microstructure and catalytic performance of the catalysts. XRD and HRTEM results show that the doped metal nano-particles are coated with a double carbon layer of graphene carbon (inner layer) and amorphous carbon (outer layer) forming serrated edges that facilitate the ORR process. The as-obtained NCoNC catalyst exhibits good electrocatalytic performance and excellent stability for the ORR in both acidic and alkaline environments. In particular, in alkaline electrolyte, the decrements of both the limiting current density and the half-wave potential of the NCoNC catalyst were significantly lower than those of a commercial Pt/C catalyst during accelerated aging tests. When serving as an air electrode in Zn–air batteries, the catalyst also exhibits superior catalytic performance with a peak power density of 78.2 mW cm−2 and a stable open-circuit voltage of 1.37–1.43 V. This work presents a novel tactic to regulate the microstructure and composition of carbon-based electrocatalysts by the facile and scalable dual-effect nitrogen doping method which may be conducive to promoting and developing highly efficient and promising electrocatalysts for the ORR.

Highly Graphitic Fe-Doped Carbon Xerogels as Dual-Functional Electro-Fenton Catalysts for Wastewater Decontamination

Highly Graphitic Fe-Doped Carbon Xerogels as Dual-Functional Electro-Fenton Catalysts for Wastewater Decontamination