Nitrogen-Doped Porous Carbon Materials Derived from Graphene Oxide/Melamine Resin Composites for CO2 Adsorption

CO₂ adsorption in porous carbon materials has attracted great interests for alleviating emission of post-combustion CO₂. In this work, a novel nitrogen-doped porous carbon material was fabricated by carbonizing the precursor of melamine-resorcinol-formaldehyde resin/graphene oxide (MR/GO) composites with KOH as the activation agent. Detailed characterization results revealed that the fabricated MR(0.25)/GO-500 porous carbon (0.25 represented the amount of GO added in wt.% and 500 denoted activation temperature in °C) had well-defined pore size distribution, high specific surface area (1264 m²·g⁻¹) and high nitrogen content (6.92 wt.%), which was mainly composed of the pyridinic-N and pyrrolic-N species. Batch adsorption experiments demonstrated that the fabricated MR(0.25)/GO-500 porous carbon delivered excellent CO₂ adsorption ability of 5.21 mmol·g⁻¹ at 298.15 K and 500 kPa, and such porous carbon also exhibited fast adsorption kinetics, high selectivity of CO₂/N₂ and good recyclability. With the inherent microstructure features of high surface area and abundant N adsorption sites species, the MR/GO-derived porous carbon materials offer a potentially promising adsorbent for practical CO₂ capture.     

Doped-ZrO2 Aerogels: Catalysts of Controlled Structure and Properties

Doped ZrO₂ aerogels (characterised by TEM, DTA and N₂ adsorption) have been prepared and catalytically tested in CO/CO₂ hydrogenation [1] and CH₄ oxidation [2]. The primary aerogels showed cross-linked clusters of (X-ray) amorphous particles smaller than 5 nm which led to well-developed mesoporous solids with an average pore size of about 10 nm and high surface area (up to 250 m²g⁻¹) [1]. Cu/ZrO₂ aerogels (known to be very active and selective towards methanol synthesis in CO hydrogenation without predominant formation of alkanes even at higher temperatures [1]) are now seen to show these effects even more clearly in CO₂ hydrogenation. In methane oxidation, both Rh/ZrO₂ and Y₂O₃/ZrO₂ were very active. Consideration is given to the nature of the active sites, the role of CO₂ and metal/oxide interfaces and how an understanding of this reactivity can lead to better dispersed ZrO₂.     

Variation of Triterpenes in Apples Stored in a Controlled Atmosphere

Apples are seasonal fruits, and thus after harvesting apples of optimal picking maturity, it is important to prepare them properly for storage and to ensure proper storage conditions in order to minimize changes in the chemical composition and commercial quality of the apples. We studied the quantitative composition of triterpenic compounds in the whole apple, apple peel and apple flesh samples before placing them in the controlled atmosphere (CA) chambers, and at the end of the experiment, 8 months later. HPLC analysis showed that highest total amount of triterpenic compounds (1.99 ± 0.01 mg g⁻¹) was found in the whole apple samples of the ‘Spartan’ cultivar stored under variant VIII (O₂—20%, CO₂—3%, N₂—77%) conditions. Meanwhile, the highest amount of triterpenic compounds (11.66 ± 0.72 mg g⁻¹) was determined in the apple peel samples of the ‘Auksis’ cultivar stored under variant II (O₂—5%, CO₂—1%, N₂—94%) conditions. In the apple peel samples of the ‘Auksis’ cultivar stored under variant I (O₂—21%, CO₂—0.03%, N₂—78.97%) conditions, the amount of individual triterpenic compounds (ursolic, oleanolic, corosolic, and betulinic acids) significantly decreased compared with amount determined before the storage. Therefore, in the apple flesh samples determined triterpenic compounds are less stable during the storage under controlled atmosphere conditions compared with triterpenic compounds determined in the whole apple and apple peel samples.     

Ambient pressure dried tetrapropoxysilane-based silica aerogels with high specific surface area

In the present paper, we report the synthesis of tetrapropoxysilane (TPOS)-based silica aerogels with high surface area and large pore volume. The silica aerogels were prepared by a two-step sol-gel process followed by surface modification via a simple ambient pressure drying approach. In order to minimize drying shrinkage and obtain hydrophobic aerogels, the surface of the alcogels was modified using trichloromethylsilane as a silylating agent. The effect of the sol-gel compositional parameters on the polymerization of aerogels prepared by TPOS, one of the precursors belonging to the Si(OR)₄ family, was reported for the first time. The oxalic acid and NH₄OH concentrations were adjusted to achieve good-quality aerogels with high surface area, low density, and high transparency. Controlling the hydrolysis and condensation reactions of the TPOS precursor turned out to be the most important factor to determine the pore characteristics of the aerogel. Highly transparent aerogels with high specific surface area (938 m²/g) and low density (0.047 g/cm³) could be obtained using an optimized TPOS/MeOH molar ratio with appropriate concentrations of oxalic acid and NH₄OH.     

Developing Eco-Friendly and Cost-Effective Porous Adsorbent for Carbon Dioxide Capture

To address the issue of global warming and climate change issues, recent research efforts have highlighted opportunities for capturing and electrochemically converting carbon dioxide (CO₂). Despite metal doped polymers receiving widespread attention in this respect, the structures hitherto reported lack in ease of synthesis with scale up feasibility. In this study, a series of mesoporous metal-doped polymers (MRFs) with tunable metal functionality and hierarchical porosity were successfully synthesized using a one-step copolymerization of resorcinol and formaldehyde with Polyethyleneimine (PEI) under solvothermal conditions. The effect of PEI and metal doping concentrations were observed on physical properties and adsorption results. The results confirmed the role of PEI on the mesoporosity of the polymer networks and high surface area in addition to enhanced CO₂ capture capacity. The resulting Cobalt doped material shows excellent thermal stability and promising CO₂ capture performance, with equilibrium adsorption of 2.3 mmol CO₂/g at 0 °C and 1 bar for at a surface area 675.62 m²/g. This mesoporous polymer, with its ease of synthesis is a promising candidate for promising for CO₂ capture and possible subsequent electrochemical conversion.     

Characterization of Hydrophobic SiO2 Powders Prepared by Surface Modification on Wet Gel

Hydrophobic porous silica has been prepared by surface modification of TEOS (tetraethylorthosilicate) wet gel with 6 and 12 vol.% of TMCS (trimethylchlorosilane). We characterized the products by using FT-IR, TGA, DTA, N₂ adsorption/desorption, contact angle and SEM. Surface silanol groups of the gel were widely replaced by–Si(CH₃)₃ to result in a hydrophobic SiO₂ powder as confirmed by contact angle measurements with H₂O, 1-butanol and ethanol. The modified dried gels had a surface area of 950–1000 m²/g (average pore size 120 Å), compared to the non-modified surface which had a surface area of 690 m²/g (average pore size 36 Å). The adsorption/desorption isotherm curves indicated they had similar pore characteristics as aerogels prepared by the supercritical drying process.     

Influence of supercritical drying fluids on structures and properties of low-density Cu-doped SiO2 composite aerogels

The Cu-doped SiO₂ composite aerogels were successfully prepared by sol–gel process and subsequently supercritical drying with ethanol and CO₂. The Cu-doped SiO₂ composite aerogels had porous texture, low density (<100 mg cm^?3) and high specific surface area (>800 m² g^?1), which were investigated by FESEM and nitrogen adsorption desorption porosimetry. The FTIR spectra of the aerogels showed that the ethanol-dried aerogels had been modified by ethyl while the corresponding CO₂-dried aerogels had more Si–OH groups. The phase structure and thermal stability were investigated by XRD and TGA, respectively. Due to the reducibility of ethanol, the copper was crystalline in ethanol-dried sample. The Cu-doped SiO₂ composite aerogels dried with supercritical ethanol had larger pore diameter and better thermal stability under 400 °C in comparison with CO₂-dried composite aerogels. The structures and properties of Cu-doped SiO₂ composite aerogels are obviously affected by supercritical drying conditions. The effect research could instruct the synthesis of different state of Cu in composite aerogels.     

Fast CO<Subscript>2</Subscript> sequestration by aerogel composites

The increasingly evident impact of anthropogenic CO₂ emissions on climate change and associated environmental effects is stimulating the search for viable methods to remove this gas. One of the most promising strategies is the long-term storage of CO₂ in inert, insoluble and thermodynamically-stable materials. This strategy mimics the natural reactions that transform silicates into carbonates regulating the cycle of CO₂ on the surface of the Earth, operating on a geological time-scale. Consequently, the aim is to accelerate these reactions to be applicable on the timescale of human lives. We present the various technologies developed or proposed to date, based on this particular approach. The principal limiting factor is that high pressures and temperatures are required to produce appropriate materials capable of CO₂ sequestration and storage. Nevertheless, the synthetic materials known as aerogels can be modified in shape, size and chemical functionality so as to catalyse the process of CO₂ elimination through silicates (of Ca or Mg), considerably reducing the reaction time and working at atmospheric pressure and temperature.     

快速制备高掺杂CuO/SiO2复合气凝胶

通过环氧丙烷预反应法, 以乙腈为溶剂快速制备了高掺杂的氧化铜/二氧化硅复合气凝胶. 在典型的合成过程中, 将正硅酸甲酯(TMOS)、乙腈、去离子水和环氧丙烷混合进行预反应, 然后将该溶液与氯化铜的乙腈-水溶液混合并添加环氧丙烷, 在35℃烘箱中静置0.5 h 后转化为湿凝胶, 再经过CO₂超临界流体干燥和热处理即可获得黑色块状CuO/SiO₂复合气凝胶. 最终气凝胶样品密度约为180 mg·cm^-3, 比表面积高达625 m2·g^-1, 平均掺杂比为19.91%±2.42% (Cu:Si 摩尔比), 压缩模量为1.639 MPa, 具有成型性好、分散均匀等优点,是良好的背光源靶材料. 本论文还通过对比实验对凝胶化过程的机理进行分析, 结果表明, 通过改变溶剂和采用环氧丙烷预催化均衡了两种不同前驱体的反应速率, 实现了共凝胶的目的. 此外, 该方法还有望为其它金属氧化物/二氧化硅复合气凝胶的制备提供新思路.     

Fabrication of Phosphorus-Doped Cobalt Silicate with Improved Electrochemical Properties

The development of electrode materials for supercapacitors (SCs) is greatly desired, and this still poses an immense challenge for researchers. Cobalt silicate (Co₂SiO₄, denoted as CoSi) with a high theoretical capacity is deemed to be one of the sustainable electrode materials for SCs. However, its achieved electrochemical properties are still not satisfying. Herein, the phosphorus (P)-doped cobalt silicate, denoted as PCoSi, is synthesized by a calcining strategy. The PCoSi exhibits 1D nanobelts with a specific surface area of 46 m²∙g⁻¹, and it can significantly improve the electrochemical properties of CoSi. As a supercapacitor’s (SC’s) electrode, the specific capacitance of PCoSi attains 434 F∙g⁻¹ at 0.5 A∙g⁻¹, which is much higher than the value of CoSi (244 F∙g⁻¹ at 0.5 A∙g⁻¹). The synergy between the composition and structure endows PCoSi with attractive electrochemical properties. This work provides a novel strategy to improve the electrochemical performances of transition metal silicates.     

H2-induced CO adsorption and dissociation over Co/Al2O3 catalyst

The activation of adsorbed CO is an important step in CO hydrogenation. The results from TPSR of pre-adsorbed CO with H2 and syngas suggested that the presence of H2 increased the amount of CO adsorption and accelerated CO dissociation. The H2 was adsorbed first, and activated to form H＊ over metal sites, then reacted with carbonaceous species. The oxygen species for CO2 formation in the presence of hydrogen was mostly OH^＊, which reacted with adsorbed CO subsequently via CO^＊＋OH^＊ → CO2^＊＋H^＊; however, the direct CO dissociation was not excluded in CO hydrogenation. The dissociation of C-O bond in the presence of H2 proceeded by a concerted mechanism, which assisted the Boudourd reaction of adsorbed CO on the surface via CO^＊＋2H^＊ → CH^＊＋OH^＊. The formation of the surface species （CH） from adsorbed CO proceeded as indicated with the participation of surface hydrogen, was favored in the initial step of the Fischer-Tropsch synthesis.     

Robust Amino-Functionalized Mesoporous Silica Hollow Spheres Templated by CO2 Bubbles

Hollow-structured mesoporous silica has wide applications in catalysis and drug delivery due to its high surface area, large hollow space, and short diffusion mesochannels. However, the synthesis of hollow structures usually requires sacrificial templates, leading to increased production costs and environmental problems. Here, for the first time, amino-functionalized mesoporous silica hollow spheres were synthesized by using CO₂ gaseous bubbles as templates. The assembly of anionic surfactants, co-structure directing agents, and inorganic silica precursors around CO₂ bubbles formed the mesoporous silica shells. The hollow silica spheres, 200–400 nm in size with 20–30 nm spherical shell thickness, had abundant amine groups on the surface of the mesopores, indicating excellent applications for CO₂ capture, Knoevenagel condensation reaction, and the controlled release of Drugs.     

Physico-chemical properties of ambiently dried sodium silicate based aerogels catalyzed with various acids

Experimental results on the physico-chemical properties of ambiently dried sodium silicate based aerogels catalyzed with various acids are reported. The aerogels were prepared by hydrolysis and polycondensation of sodium silicate followed by subsequent washings, surface chemical modification and ambient pressure drying using 10 various acid catalysts consisting of strong and weak acids. The strength and concentration of acids have the major effect on the gelation of sol and hence the physico-chemical properties of the silica aerogels. Strong acids such as HCl, HNO₃ and H₂SO₄ resulted in shrunk (70–95%) aerogels whereas weak acids such as citric and tartaric acids resulted in less shrunk (34–50%) aerogels. The physical properties of silica aerogels were studied by measuring bulk density, volume shrinkage (%), porosity (%), pore volume, thermal conductivity, contact angle with water, Transmission Electron Microscopy (TEM), Atomic Absorption Spectroscopy (AAS), Fourier Transform Infrared Spectroscopy (FTIR), Thermo Gravimetric-Differential Thermal (TG-DT) analyses and N₂ adsorption–desorption BET surface analyzer. The best quality silica aerogels in terms of low density (0.086 g/cm³), low volume shrinkage (34%), high porosity (95%), low thermal conductivity (0.09 W/m K) and hydrophobic (148°) were obtained for molar ratio of Na₂SiO₃:H₂O:citric acid:TMCS at 1:146.67:0.72:9.46 with 20 min gelation time. The resulting aerogels exhibited the thermal stability up to around 420 °C.     

Synthesis of freestanding silica and titania-silica aerogels with ordered and disordered mesopores

Freestanding blocks of silica and titania-silica aerogels were prepared by the sol-gel method. It is possible to prepare crack-free, titania-silica aerogels with high titanium content by a careful control of the synthesis conditions. Prehydrolysis, complexation and polymer addition were used to adjust the hydrolysis and condensation rates of the silicon and titanium alkoxide precursors. Photoactive anatase TiO₂ nanocrystals with a large surface area (i.e., up to 300m²g⁻¹) were crystallized from the gel network by the high-temperature ethanol supercritical drying, and the resulting aerogel blocks were gas permeable and display a transition-regime diffusion behavior. Pore and volume shrinkages were observed in samples prepared by ethanol supercritical drying when the titanium content was increased resulting in a lower flux. Adding Pluronic P123 creates ordered mesopore domains and produces large pore aerogels even at high titanium contents. The photocatalytic oxidation reaction of trichloroethylene was performed by flowing the reactant gas mixture through the UV-irradiated aerogel blocks with excellent results.     

Effect of Precursor Nature and Sol-Gel Synthesis Conditions on TiO2 Aerogel’s Structure

The aim of this investigation was to synthesize high porosity TiO₂ aerogel by applying sol-gel and subcritical drying methods and to identify the influence of reagent’s nature and synthesis conditions on their structural and optical properties. Methods of XRD, FT-IR, BET, STA, SEM, and UV-vis were applied to investigate and compare the properties of synthesized TiO₂ aerogels and to determine the most effective synthesis route. The structural parameters of the synthesized materials can be varied by changing the precursor type (titanium (IV), isopropoxide (TIP), or tetrabutylorthotitanate (TBOT)) and the nature of the solvent used for additional exchange (n-hexane (nH), cyclohexane (CH), or diethyl ether (DE)). All of the subcritical dried samples show the amorphous structure, which tends to crystallize into the anatase phase after calcination. The number of micro and mesopores and the specific surface area depends on the synthesis conditions. The pores with the highest diameter have been found for additionally nH exchanged and aged aerogel synthesized from precursor TIP. Despite the imperfections in the structure, the produced aerogels show structural and optical properties typical of the TiO₂ structures mentioned in the literature.     

Synthesis of Silica Aerogels: Influence of the Supercritical CO2 on the Sol-Gel Process

The synthesis of silica aerogels was modified by addition of supercritical CO₂ during the sol-gel process. It was shown, that CO₂ acts as a catalyst and accelerates the gelation significantly. This effect was studied under a multitude of experimental conditions. The influence of the precursor concentration, temperature and the nature of the catalysts and solvent on the gel formation in presence of CO₂ was studied. Several gels obtained by this method were dried and transparent silica aerogels were produced.     

Zirconia‐based Aerogels via Hydrolysis of Salts and Alkoxides: The Influence of the Synthesis Procedures on the Properties of the Aerogels

This contribution aims at evaluating different synthesis procedures leading to zirconia‐based aerogels. A series of undoped and yttrium‐doped zirconia aerogels have been prepared via hydrolysis and condensation reaction of different alkoxy‐ and different inorganic salt‐based precursors followed by supercritical drying. Well‐established but deleterious zirconium n‐propoxide (TPOZ) or zirconium n‐butoxide (TBOZ) were used as metal precursors in combination with acids like nitric acid and acetic acid as auxiliary agent for the generation of non‐yttrium stabilized zirconia aerogels. Yttrium‐stabilized zirconia aerogels as well as pure zirconia aerogels were obtained by the salt route starting from ZrCl₄ and crosslinking agents like propylene oxide or acetylacetone. The characteristics of the products were analyzed by nitrogen adsorption measurements, electron microscopy, and X‐ray scattering. It turned out that with respect to all relevant properties of the aerogels as well as the practicability of the synthesis procedures, approaches based on inexpensive non‐toxic salt precursors are the methods of choice. The salt‐based approaches allow not only for low‐cost, easy‐to‐handle synthesis procedures with realizable gelation times of less than 60 seconds, but also delivered the products with the highest surface area (449 m² g^?1 for ZrCl₄) within this series of syntheses.     

Synthesis,Characterization and Application of Amine-Functionalized Hierarchically Micro-Mesoporous Silicon Composites for CO2 Capture in Flue Gas

An efficient CO₂ adsorbent with a hierarchically micro-mesoporous structure and a large number of amine groups was fabricated by a two-step synthesis technique. Its structural properties, surface groups, thermal stability and CO₂ adsorption performance were fully investigated. The analysis results show that the prepared CO₂ adsorbent has a specific hierarchically micro-mesoporous structure and highly uniformly dispersed amine groups that are favorable for the adsorption of CO₂. At the same time, the CO₂ adsorption capacity of the prepared adsorbent can reach a maximum of 3.32 mmol-CO₂/g-adsorbent in the actual flue gas temperature range of 303–343 K. In addition, the kinetic analysis results indicate that both the adsorption process and the desorption process have rapid adsorption/desorption rates. Finally, the fitting of the CO₂ adsorption/desorption experimental data by Avrami’s fractional kinetic model shows that the CO₂ adsorption rate is mainly controlled by the intra-particle diffusion rate, and the temperature has little effect on the adsorption rate.     

A Computational Analysis of the Reaction of SO2 with Amino Acid Anions: Implications for Its Chemisorption in Biobased Ionic Liquids

We report a series of calculations to elucidate one possible mechanism of SO₂ chemisorption in amino acid-based ionic liquids. Such systems have been successfully exploited as CO₂ absorbents and, since SO₂ is also a by-product of fossil fuels’ combustion, their ability in capturing SO₂ has been assessed by recent experiments. This work is exclusively focused on evaluating the efficiency of the chemical trapping of SO₂ by analyzing its reaction with the amino group of the amino acid. We have found that, overall, SO₂ is less reactive than CO₂, and that the specific amino acid side chain (either acid or basic) does not play a relevant role. We noticed that bimolecular absorption processes are quite unlikely to take place, a notable difference with CO₂. The barriers along the reaction paths are found to be non-negligible, around 7–11 kcal/mol, and the thermodynamic of the reaction appears, from our models, unfavorable.     

Synthesis of transparent silica aerogels using tetraalkylammonium fluoride catalysts

Tetraalkylammonium fluoride salts have been employed as catalysts for the synthesis of silica aerogels by a two-step, sol–gel method. Aerogel materials were characterized by N₂ physisorption and SEM. The effect of the type of catalyst on the optical transparency of obtained aerogels has been examined. It has been found that such compounds allow the synthesis of silica aerogels with the highest optical transmittance ever reported for such materials. The optimal catalysts are tetrabutyl and tetraoctyl ammonium fluoride, with which aerogels with transparency as high as 96% and extinction coefficient as low as 3.5 m⁻¹ can be prepared.