Towards the valorisation of glycerol by designing the surface chemistry of carbon xerogels by doping and oxygen functionalization.

Research on innovative approaches to the valorisation of glycerol as a subproduct of biodiesel production has acquired an increasing demand in the development of a circular economy around energy generation, especially, in the line of improvement of the heterogeneous metallic catalysts used. In this regard, carbon xerogels have gained importance due to their stability and modifiability, while transition metals such as copper stand out as a cost-effective alternative, resulting in a technology where surface engineering plays a crucial role in achieving competitive catalytic activity. Building upon this, current research evaluates doped xerogels (Si, N, or GO) as supports of Cu and catalysts by themselves for glycerol oxidation. Benefits from the incorporation of oxygenated functional groups (OFG) were also evaluated. Results showed a consistently higher selectivity towards lactic acid (LA) across all catalysts and competitive catalytic conversion. In this performance, dopants played a crucial role in surface acid-base characteristics, while oxygenated functional groups (OFG) influenced copper adsorption, dispersion, and reducibility. Notably, the Cu/CXN-f catalyst demonstrated the highest LA yield by combining the effect of N as a doping species, with the presence of OFG and the formation of appropriated metallic Cu domains. This research underscores the potential of carbon xerogels in the tailored catalyst design, contributing to sustainable chemical production through their customizable textural and chemical properties.

Highly graphitic Fe-doped carbon xerogels as dual-functional electro-Fenton catalysts for the degradation of tetracycline in wastewater.

Fe-doped carbon xerogels with a highly developed graphitic structure were synthesized by a one-step sol-gel polymerization. These highly graphitic Fe-doped carbons are presented as promising dual-functional electro-Fenton catalysts to perform both the electro-reduction of O2 to H2O2 and H2O2 catalytic decomposition (Fenton) for wastewater decontamination. The amount of Fe is key to the development of this electrode material, since affects the textural properties; catalyzes the development of graphitic clusters improving the electrode conductivity; and influences the O2-catalyst interaction controlling the H2O2 selectivity but, at the same time is the catalyst for the decomposition of the electrogenerated H2O2 to OH• radicals for the organic pollutants oxidation. All materials achieve the development of ORR via the 2-electron route. The presence of Fe considerably improves the electro-catalytic activity. However, a mechanism change seems to occur at around -0.5 V in highly Fe-doped samples. At potential lower than -0.5 eV, the present of Feδ+ species or even Fe-O-C active sites favour the selectivity to 2e-pathway, however at higher potentials, Feδ+ species are reduced favoring a O-O strong interaction enhancing the 4e-pathway. The Electro-Fenton degradation of tetracycline was analyzed. The TTC degradation is almost complete (95.13%) after 7 h of reaction without using any external Fenton-catalysts.

Synthesis of Nitrogen and Phosphorus/Sulfur Co-Doped Carbon Xerogels for the Efficient Electrocatalytic Reduction of p-Nitrophenol.

Carbon xerogels co-doped with nitrogen (N) and phosphorus (P) or sulfur (S) were synthesized and employed as catalysts for the electrocatalytic reduction of p-nitrophenol (p-NP). The materials were prepared by first synthesizing N-doped carbon xerogels (NDCX) via the pyrolysis of organic gels, and then introducing P or S atoms to the NDCX by a vapor deposition method. The materials were characterized by various measurements including X-ray diffraction, N2 physisorption, Transmission electron microscopy, Fourier Infrared spectrometer, and X-ray photoelectron spectra, which showed that N atoms were successfully doped to the carbon xerogels, and the co-doping of P or S atoms affected the existing status of N atoms. Cyclic voltammetry (CV) scanning manifested that the N and P co-doped materials, i.e., P-NDCX-1.0, was the most suitable catalyst for the reaction, showing an overpotential of -0.569 V (vs. Ag/AgCl) and a peak slop of 695.90 µA/V. The material was also stable in the reaction and only a 14 mV shift in the reduction peak overpotential was observed after running for 100 cycles.

Structure and Properties of the Xerogels Based on Potassium Silicate Liquid Glass and Urea.

The xerogels based on the aqueous solutions of urea in potassium silicate liquid glass (PSLG) were produced by CO2 bubbling and investigated. The structure and chemical composition of the obtained materials were analyzed. Using the SEM, XRD, IR-FT, DSC, and low energy local EDS analysis, it was recognized that the dried gels (xerogels) contained three forms of urea: oval crystals of regular shape appeared onto the surface of xerogel particles; fibrous crystals were located in the silicate matrix; and molecules/ions were incorporated into the silicate matrix. It was shown that an increase in [(NH2)2CO] in the gel-forming system promoted increased contents in crystalline forms of urea as well as the diameter of the fiber-shaped urea crystals. A rate of the urea release in water from the granulated xerogels containing 5.8, 12.6, and 17.9 wt.% of urea was determined by the photometric method. It was determined that the obtained urea-containing xerogels were characterized with a slow release of urea, which continued up to 120 days, and could be used as controlled release fertilizers containing useful nutrients (N, K).

In-Situ Silica Xerogel Assisted Facile Synthesis of Fe-N-C Catalysts with Dense Fe-Nx Active Sites for Efficient Oxygen Reduction.

In the past decade, atomically dispersed Fe active sites (coordinated with nitrogen) on carbon materials (FeNC) have emerged rapidly as promising single-atom catalysts (SACs) for the oxygen reduction reaction (ORR) to substitute precious group metal (PGM) catalysts, owing to their earth abundance and low cost. Nonetheless, the production of highly active FeNC SACs is largely restricted by material cost, low product yield and difficulty of microstructure design. Herein, the authors demonstrate a facile in-situ xerogel (ISG) assisted synthetic strategy, using cheap materials, to construct FeNC SACs (ISG FeNC). The porous silica xerogel, formed in-situ with the FeNC precursors, encourages the emergence of enormous micropores/mesopores and homogeneous confinement/protection to the precursors during pyrolysis, benefiting to the formation of abundant accessible active sites (27.6 × 1019 sites g-1 ). Correspondingly, the ISG FeNC exhibits excellent ORR activity with a half-wave potential (E1/2  = 0.91 V) in alkaline medium. The Zn-air battery assembled using the ISG FeNC SACs as the bifunctional catalyst of air cathode, demonstrates commendable performance with high peak power density of 249.1 mW cm-2 and superior long-term stability (660 cycles with 220 h). This work offers an economic and efficient way to fabricate PGM-free SACs for diverse applications.

Enhanced anaerobic treatment of synthetic protein-rich wastewater promoted by organic xerogels.

Carbon-based materials have been shown to enhance anaerobic digestion processes by promoting direct interspecies electron transfer in methanogenic consortia. However, little is known on their effects during the treatment of complex substrates, such as those derived from protein-rich wastewaters. Here, organic xerogels (OX) are tested, for the first time, as accelerators of the methanogenic activity of an anaerobic consortium treating a synthetic protein-rich wastewater. Three OX with distinct pore size distribution (10 and 1000 nm for OX-10 and OX-1000, respectively) and structural conformation (graphene oxide integration into OX-10-GO polymeric matrix) were synthesized. OX-1000 promoted the highest methane production rate (5.21 mL/g*h, 13.5% increase with respect to the control incubated without OX) among the synthesized OX. Additionally, batch bioreactors amended with OX achieved higher chemical oxygen demand (COD) removal (up to 88%) as compared to the control, which only showed 50% of COD removal. Interestingly, amendment of bioreactors with OX also triggered the production of medium-chain fatty acids, including caprylate and caproate. Moreover, OX decreased the accumulation of ammonium, derived from proteins hydrolysis, partly explained by their adsorption capacities, and probably involving their electron-accepting capacity promoting anaerobic ammonium oxidation. This is the first time that OX were successfully applied as methanogenic accelerators for the anaerobic treatment of synthetic protein-rich wastewater, increasing the methane production rate and COD removal as well as triggering the production of medium chain fatty acids and attenuating the accumulation of ammonium. Therefore, OX are proposed as suitable materials to boost the efficiency of anaerobic systems to treat complex industrial wastewaters.

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

Carbon xerogel nanocomposites with integrated Bi and Fe particles (C­Bi­Fe) 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 C­Bi­Fe systems, relevant in charge transport and thermo-chemical processes. The thermal evolution of a C­Bi­Fe 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 0.29­0.34 eV during reduction and graphitization stages. The results suggest some similarities with the tip growth mechanism, while oxygen interference and the limited catalyst­feed gas interactions are considered as the main constraints to enhanced growth.

Effect of Washing Treatment on the Textural Properties and Bioactivity of Silica/Chitosan/TCP Xerogels for Bone Regeneration.

Silica/biopolymer hydrogel-based materials constitute very attractive platforms for various emerging biomedical applications, particularly for bone repair. The incorporation of calcium phosphates in the hybrid network allows for designing implants with interesting biological properties. Here, we introduce a synthesis procedure for obtaining silica-chitosan (CS)-tricalcium phosphate (TCP) xerogels, with CS nominal content varying from 4 to 40 wt.% and 10 to 20 wt.% TCP. Samples were obtained using the sol-gel process assisted with ultrasound probe, and the influence of ethanol or water as washing solvents on surface area, micro- and mesopore volume, and average pore size were examined in order to optimize their textural properties. Three washing solutions with different soaking conditions were tested: 1 or 7 days in absolute ethanol and 30 days in distilled water, resulting in E1, E7, and W30 washing series, respectively. Soaked samples were eventually dried by evaporative drying at air ambient pressure, and the formation of interpenetrated hybrid structures was suggested by Fourier transformed infrared (FTIR) spectroscopy. In addition the impact that both washing solvent and TCP content have on the biodegradation, in vitro bioactivity and osteoconduction of xerogels were explored. It was found that calcium and phosphate-containing ethanol-washed xerogels presented in vitro release of calcium (2-12 mg/L) and silicon ions (~60-75 mg/L) after one week of soaking in phosphate-buffered saline (PBS), as revealed by inductive coupled plasma (ICP) spectroscopy analysis. However, only the release of silicon was detected for water-washed samples. Besides, all the samples exhibited in vitro bioactivity in simulated body fluid (SBF), as well as enhanced in vitro cell growth and also significant focal adhesion development and maturation.

Designing silica xerogels containing RTIL for CO2 capture and CO2/CH4 separation: Influence of ILs anion, cation and cation side alkyl chain length and ramification.

CO2 separation from natural gas is considered to be a crucial strategy to mitigate global warming problems, meet product specification, pipeline specs and other application specific requirements. Silica xerogels (SX) are considered to be potential materials for CO2 capture due to their high specific surface area. Thus, a series of silica xerogels functionalized with imidazolium, phosphonium, ammonium and pyridinium-based room-temperature ionic liquids (RTILs) were synthesized. The synthesized silica xerogels were characterized by NMR, helium pycnometry, DTA-TG, BET, SEM and TEM. CO2 sorption, reusability and CO2/CH4 selectivity were assessed by the pressure-decay technique. Silica xerogels containing IL demonstrated advantages compared to RTILs used as separation solvents in CO2 capture processes including higher CO2 sorption capacity and faster sorption/desorption. Using fluorinated anion for functionalization of silica xerogels leads to a higher affinity for CO2 over CH4. The best performance was obtained by SX- [bmim] [TF2N] (223.4 mg CO2/g mg/g at 298.15 K and 20 bar). Moreover, SX- [bmim] [TF2N] showed higher CO2 sorption capacity as compared to other reported sorbents. CO2 sorption and CO2/CH4 selectivity results were submitted to an analysis of variance and the means compared using Tukey's test (5%).

Technologies and Formulation Design of Polysaccharide-Based Hydrogels for Drug Delivery.

Polysaccharide-based hydrogel particles (PbHPs) are very promising carriers aiming to control and target the release of drugs with different physico-chemical properties. Such delivery systems can offer benefits through the proper encapsulation of many drugs (non-steroidal and steroidal anti-inflammatory drugs, antibiotics, etc) ensuring their proper release and targeting. This review discusses the different phases involved in the production of PbHPs in pharmaceutical technology, such as droplet formation (SOL phase), sol-gel transition of the droplets (GEL phase) and drying, as well as the different methods available for droplet production with a special focus on prilling technique. In addition, an overview of the various droplet gelation methods with particular emphasis on ionic cross-linking of several polysaccharides enabling the formation of particles with inner highly porous network or nanofibrillar structure is given. Moreover, a detailed survey of the different inner texture, in xerogels, cryogels or aerogels, each with specific arrangement and properties, which can be obtained with different drying methods, is presented. Various case studies are reported to highlight the most appropriate application of such systems in pharmaceutical field. We also describe the challenges to be faced for the breakthrough towards clinic studies and, finally, the market, focusing on the useful approach of safety-by-design (SbD).

Patterning of Nanoparticle-Based Aerogels and Xerogels by Inkjet Printing.

Nanoparticle-based voluminous 3D networks with low densities are a unique class of materials and are commonly known as aerogels. Due to the high surface-to-volume ratio, aerogels and xerogels might be suitable materials for applications in different fields, e.g. photocatalysis, catalysis, or sensing. One major difficulty in the handling of nanoparticle-based aerogels and xerogels is the defined patterning of these structures on different substrates and surfaces. The automated manufacturing of nanoparticle-based aerogel- or xerogel-coated electrodes can easily be realized via inkjet printing. The main focus of this work is the implementation of the standard nanoparticle-based gelation process in a commercial inkjet printing system. By simultaneously printing semiconductor nanoparticles and a destabilization agent, a 3D network on a conducting and transparent surface is obtained. First spectro-electrochemical measurements are recorded to investigate the charge-carrier mobility within these 3D semiconductor-based xerogel networks.

Combinational Hydrogel and Xerogel Actuators Showing NIR Manipulating Complex Actions.

Near-infrared (NIR)-driven shape memory hydrogels are synthesized with a one-pot polymerization of N,N-dimethylacrylamide in the inorganic clay and graphene oxide (GO) suspension. The hydrogel consists of only a physically crosslinked network, which is partially thermoreversible. With the efficient photothermal energy transformation of GO in the hydrogels, the shape recovery from the temporal shape is achieved by NIR irradiation. The optimal shape fixing percentage and recovery rate are found at moderate monomer and crosslinker contents. Meanwhile, the xerogel dried from the hydrogel also shows a fast NIR response shape change. The NIR manipulating combinational hydrogel-xerogel actuators are prepared by combining the wet and soft hydrogel and its dry and rigid xerogel together. The actuators achieve complex actions of turning and lifting under sequential NIR irradiation to carry an object up- and downward and around obstacles, or to transfer an object to a target position. This work provides a new idea for designing combinational actuators to fulfil complex actions.

A Polycarboxyl-Decorated FeIII -Based Xerogel-Derived Multifunctional Composite (Fe3 O4 /Fe/C) as an Efficient Electrode Material towards Oxygen Reduction Reaction and Supercapacitor Application.

Low cost, non-noble metal catalysts with a good oxygen reduction reaction (ORR) activity comparable to that of platinum and also having good energy storage properties are highly desirable but challenging. Several challenges are associated with the development of such materials. Herein, we demonstrate a new polycarboxyl-functionalised FeIII -based gel material, synthesised following a solvothermal method and the development of its composite (Fe3 O4 /Fe/C) by annealing at optimised temperature. The developed composite displayed excellent electrocatalytic activity for the oxygen reduction reaction with an onset potential of 0.87 V (vs. RHE) and a current density value of -5 mA cm-2 , which are comparable with commercial 20 wt % Pt/C. In addition, as one of the most desirable properties, the composite exhibits a better methanol tolerance and greater durability than Pt/C. The same material was explored as an energy storage material for supercapacitors, which showed a specific capacitance of 245 F g-1 at a current density of 1 A g-1 . It is expected that this Fe3 O4 /Fe/C composite with a disordered graphitised carbon matrix will pave a horizon for developing energy conversion and energy storage devices.

Lanthanum-doped silica xerogels for the removal of fluorides from waters.

The objective of this study was to determine the influence of different operational variables on fluoride (F-) removal from waters using lanthanum (La)-doped silica xerogels and the mechanisms involved in this process. Accordingly, four xerogels were synthesized, one acting as blank (X-B), two doped with LaCl3 and dried at different temperatures (X-LaCl and X-LaCl-M), and a fourth doped with La2O3 (X-LaO). The results show that fluorides are only removed when La-doped xerogels are utilized. In addition, X-LaCl yielded the highest adsorption capacity, removing 28.44% of the initial fluoride concentration at a solution pH of 7. Chemical characterization of materials confirmed that fluoride removal from waters is due to the precipitation of LaF3 on the surface of La-doped xerogels. The presence of dissolved organic matter on the aqueous solution also reduce the removal capacity of La xerogels. Finally, analysis of the influence of solution pH revealed that the adsorption capacity of all xerogels was highest at a solution pH of 7.

The performance of hybrid titania/silica-derived xerogels as active antifouling/fouling-release surfaces against the marine alga Ulva linza: in situ generation of hypohalous acids.

Mixed titania/silica xerogels were prepared using titanium tetraisopropoxide (TTIP) and tetraethoxy orthosilicate (TEOS). Xerogel properties were modified by incorporating n-octyltriethoxysilane (C8). The xerogels catalyze the oxidation of bromide and chloride with hydrogen peroxide (H2O2) to produce hypohalous acids at pH 7 and pH 8. The antifouling/ fouling-release performance of a TTIP/C8/TEOS xerogel in the presence and absence of H2O2 was evaluated for the settlement of zoospores of the marine alga Ulva linza and for the removal of sporelings (young plants). In the absence of H2O2, differences in the settlement of zoospores and removal of sporelings were not significant relative to a titanium-free C8/TEOS xerogel. Addition of H2O2 gave a significant reduction in zoospore settlement and sporeling removal relative to the C8/TEOS xerogel and relative to peroxide-free conditions. The impact of TTIP on xerogel characteristics was evaluated by comprehensive contact angle analysis, scanning electron microscopy, and X-ray photoelectron spectroscopy.

Molecular Dynamics Simulation Study of the Selectivity of a Silica Polymer for Ibuprofen.

In the past few years, the sol-gel polycondensation technique has been increasingly employed with great success as an alternative approach to the preparation of molecularly imprinted materials (MIMs). The main aim of this study was to study, through a series of molecular dynamics (MD) simulations, the selectivity of an imprinted silica xerogel towards a new template-the (±)-2-(P-Isobutylphenyl) propionic acid (Ibuprofen, IBU). We have previously demonstrated the affinity of this silica xerogel toward a similar molecule. In the present study, we simulated the imprinting process occurring in a sol-gel mixture using the Optimized Potentials for Liquid Simulations-All Atom (OPLS-AA) force field, in order to evaluate the selectivity of this xerogel for a template molecule. In addition, for the first time, we have developed and verified a new parameterisation for the Ibuprofen(®) based on the OPLS-AA framework. To evaluate the selectivity of the polymer, we have employed both the radial distribution functions, interaction energies and cluster analyses.

Resorcinol-formaldehyde xerogel as a micro-solid-phase extraction sorbent for the determination of herbicides in aquatic environmental samples.

In this study, organic aerogels were synthesized by the sol-gel polycondensation of mixed cresol with formaldehyde in a slightly basic aqueous solution. Carbon aerogels and xerogels are generated by pyrolysis of organic aerogels. The novel sol-gel-based micro-solid-phase extraction sorbent, resorcinol-formaldehyde xerogel, was employed for preconcentration of some selected herbicides. Three herbicides of the aryloxyphenoxypropionate group, clodinafop-propargyl, haloxyfop-etotyl, and fenoxaprop-P-ethyl, were extracted from aqueous samples by micro-solid-phase extraction and subsequently determined by gas chromatography with mass spectrometry. The effect of different parameters influencing the extraction efficiency of these herbicides including sample flow rate, sample volume, and extraction time were investigated and optimized. Under optimum conditions, linear calibration curves in the range of 0.10-500 ng/L with R(2) > 0.99 were obtained. The relative standard deviation at 50 µg/L concentration level was lower than 10% (n = 5) and detection limits were between 0.05 and 0.20 µg/L. The proposed method was successfully applied to the sampling and extraction of herbicides from Zayanderood and paddy water samples.

Advances in Carbon Xerogels: Structural Optimization for Enhanced EDLC Performance.

This review explores the recent progress on carbon xerogels (CXs) and highlights their development and use as efficient electrodes in organic electric double-layer capacitors (EDLCs). In addition, this work examines how the adjustment of synthesis parameters, such as pH, polymerization duration, and the reactant-to-catalyst ratio, crucially affects the structure and electrochemical properties of xerogels. The adaptability of xerogels in terms of modification of their porosity and structure plays a vital role in the improvement of EDLC applications as it directly influences the interaction between electrolyte ions and the electrode surface, which is a key factor in determining EDLC performance. The review further discusses the substantial effects of chemical activation with KOH on the improvement of the porous structure and specific surface area, which leads to notable electrochemical enhancements. This structural control facilitates improvement in ion transport and storage, which are essential for efficient EDLC charge-discharge (C-D) cycles. Compared with commercial activated carbons for EDLC electrodes, CXs attract interest for their superior surface area, lower electrical resistance, and stable performance across diverse C-D rates, which underscore their promising potential in EDLC applications. This in-depth review not only summarizes the advancements in CX research but also highlights their potential to expand and improve EDLC applications and demonstrate the critical role of their tunable porosity and structure in the evolution of next-generation energy storage systems.

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.

Improved L-Asparaginase Properties and Reusability by Immobilization onto Functionalized Carbon Xerogels.

Enzyme immobilization can offer a range of significant advantages, including reusability, and increased selectivity, stability, and activity. In this work, a central composite design (CCD) of experiments and response surface methodology (RSM) were used to study, for the first time, the L-asparaginase (ASNase) immobilization onto functionalized carbon xerogels (CXs). The best results were achieved using CXs obtained by hydrothermal oxidation with nitric acid and subsequent heat treatment in a nitrogen flow at 600 °C (CX-OX-600). Under the optimal conditions (81 min of contact time, pH 6.2 and 0.36 g/L of ASNase), an immobilization yield (IY) of 100 % and relative recovered activity (RRA) of 103 % were achieved. The kinetic parameters obtained also indicate a 1.25-fold increase in the affinity of ASNase towards the substrate after immobilization. Moreover, the immobilized enzyme retained 97 % of its initial activity after 6 consecutive reaction cycles. All these outcomes confirm the promising properties of functionalized CXs as support for ASNase, bringing new insights into the development of an efficient and stable immobilization platform for use in the pharmaceutical industry, food industry, and biosensors.