Molten salt activation for synthesis of porous carbon nanostructures and carbon sheets

We report here a molten salt (MS) process for the synthesis of nanoporous carbon structures and carbon sheets. Using glucose as the model carbon precursor, the process yields different porous carbon structures with specific surface area up to near 2000 m²/g in molten LiCl/KCl containing different dissolved oxysalts KNmO_x, where Nm are nonmetal elements of H, B, C, N, P, S, and Cl. These oxysalts dissolved in LiCl/KCl exert a dominating influence on the pore formation as well as two-dimensional growth of the carbons in MS. Based on the energetics of the redox reaction between carbon and the above oxysalts, a general mechanistic explanation for the pore formation and the activation process in MS is presented. The process reported here not only provides an easy route to convert biomass molecules to carbon-based functional nanomaterials, but also opens up a new direction towards carbonization and two-dimensional growth in high temperature ionic solvent systems.     

Oxidation of hydrogen sulfide over microporous carbons

Microporous carbon of high purity was produced by the carbonization of Saran at 900° followed by activation in either CO₂ at 900°, O₂ at 300°, or air at 425°. The activated carbons were characterized using N₂ adsorption at ?195° CO₂ adsorption at 25°, and mercury and helium displacements. Hydrogen sulfide oxidation (at H₂S pressures between 0.4–3.8 Torr) by O₂ (in excess of stoichiometric amount) was studied between 100–160° using a microbalance, that is by weighing the build-up of sulfur on the carbon. The predominant reaction, $\text{H}{}_2\text{S +}\text{1}\text{2}\text{O}{}_2\text{→}\text{1}\text{2}\text{S}{}_2\text{+ H}{}_2\text{O}$ was first order in H₂S concentration and independent of O₂ concentration. The rate was only slightly reduced by sulfur build-up to at least 36%, by weight, on the carbon. The oxidation rate was significantly higher over the O₂-activated carbon than over the CO₂-activated carbon. Throughout the studies, oxidation rates could be correlated with area active to O₂ chemisorption. It is concluded that H₂S oxidation proceeds via rapid dissociative chemisorption of oxygen on carbon sites followed by reaction with H₂S. Rates of H₂S oxidation were also studies over commercial, granular activated carbons of significant ash contents.     

珊瑚状氮掺杂多孔碳的制备及其超电容性能

在三聚氰胺为氮源、碳酸钾为活化剂的条件下,由菜籽饼制得了珊瑚状氮掺杂分级多孔碳(CNPCs)。采用场发射扫描电子显微镜、透射电子显微镜、X射线光电子能谱、氮吸脱附等表征手段,研究了三聚氰胺的用量对CNPCs微观形貌、组成及孔隙结构的影响。结果表明,当三聚氰胺的用量为2 g时,所得CNPC2的比表面积达2050 m2·g-1。以6 mol·L-1KOH为电解液,在0.05 A·g-1的电流密度下,CNPCs的比容可达274 F·g-1;当电流密度为50 A·g-1时,CNPCs的比容为169 F·g-1,显示了优异的倍率性能。经过10000次充放电测试后,比容保持率达96%,展现了良好的循环稳定性。此工作为从生物质大规模生产高性能储能用多孔碳材料提供了一种简单、绿色的方法。     

可脱除硫化氢的液体脱硫剂研究进展

一种可通过直接注入法注入管线中的三嗪类可脱除H2S液体脱硫剂,由于具有高效、价格低廉、易制备、抗菌、可减少低碳钢的腐蚀等特点,弥补了海上脱硫空间和成本的限制,近些年在国外海上石油辅助产品中发展迅猛,前景广阔.详细介绍了1,3,5-三(2-羟乙基)-六氢均三嗪的结构、性质、机理、工艺特点、国外应用现况,最后对其发展前景进行了展望.     

Chemically activated fungi-based porous carbons for hydrogen storage

A set of porous carbons has been prepared by chemical activation of various fungi-based chars with KOH. The resulting carbon materials have high surface areas (1600–2500 m²/g) and pore volumes (0.80–1.56 cm³/g), regardless of the char precursors. The porosities mainly derived from micropores in activated carbons strongly depend on the activation parameters (temperature and KOH amount). All activated carbons have uniform micropores with pore size of 0.8–0.9 nm, but some have a second set of micropores (1.3–1.4 nm pore size), further broadened to 1.9–2.1 nm as a result of increasing either the activation temperature to 750 °C or KOH/char mass ratio to 5/1. These fungi-based porous carbons achieve an excellent H₂ uptake of up to 2.4 wt% at 1 bar and −196 °C, being in agreement with results from other porous carbonaceous adsorbents reported in the literature. At high pressure (ca. 35 bar), the saturated H₂ uptake reaches 4.2–4.7 wt% at −196 °C for these fungi-based porous carbons. The results imply a great potential of these fungi-based porous carbons as H₂ on-board storage media.     

Green synthesis of templated porous carbons

Porous carbon materials such as activated carbons are widely used industrially for the purposes of purification, decolourization, deodorization, and gas storage, among others. Routes for the synthesis of these materials employing templates have increasingly attracted attention due to the ease of manipulating the characteristics of the final product. In the present work, a simple synthesis method was applied for the production of highly porous carbon materials using commercial sugar as the carbon source, Aerosil silica as a template, and deionized water. The synthesis procedure was as follows: (I) Gel formation; (II) carbonization of the gels; (III) removal of the silica template; (IV) activation. The materials were characterized by N₂ and CO₂ physisorption, Raman spectroscopy, X-ray diffraction, Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy, and thermogravimetric analysis. The aging time had an important influence on the specific area and porosity of the material, with physisorption analysis revealing a high specific area and pore volume. The activation procedures further contributed to significantly increasing the specific area (up to 1158 m² g⁻¹) and pore volume (up to 1.65 cm³ g⁻¹). The X-ray diffractograms and Raman spectra identified the formation of semi-crystalline structures in the material, with the presence of a random distribution of graphite and graphene oxide, in addition to amorphous carbon. FTIR analysis showed the presence of bands corresponding to aromatic groups. The results demonstrated that it was possible to obtain materials with excellent potential for use in different industrial sectors using simple raw materials and a technique that is easy to reproduce.     

Electrochemical removal of hydrogen sulfide from polluted brines using porous flow through electrodes

Carbon felt was used in porous electrodes to achieve electrochemical oxidation of sulfide ions from flowing chloride brines. Using X-ray photoelectron spectroscopy (XPS) and Energy Dispersive Spectroscopy (EDS), sulfur was identified as the final reaction product under various potentials and temperatures. While some of the resulting sulfur flows out with the electrolyte, the rest remains adsorbed on the graphite surface. The rate of the process and the removal efficiency increase with potential, temperature, flow rate and sulfide concentration. The measured limiting currents are substantially lower than those predicted from mass transfer correlations. This was attributed to the passivating effects of the sulfur deposited on the internal surface of the porous electrode. Potentiostatic current transients show that the carbon felt electrodes have higher capacity for removing sulfide ions than planar electrodes, which is attributed to the large internal surface area of the carbon felt.     

High hydrogen uptake capacity of mesoporous nitrogen-doped carbons activated using potassium hydroxide

Mesoporous nitrogen-doped carbons activated using potassium hydroxide have large surface areas and high pore volumes, are studied for their hydrogen storage properties. The activated material can store 6.84 wt.% of hydrogen at 77 K under a pressure of 20 bar, which is estimated to correspond to a maximum capacity of 8.24 wt.% based on the Langmuir simulation. The hydrogen adsorption values show linear relationships with the volumes of micropores and small mesopores under those conditions, which indicates that the small mesopores between the sizes 2 and 3 nm also make contributions to the hydrogen adsorption at high pressure.     

Molten salt synthesis of zinc aluminate powder

ZnAl₂O₄ powder was synthesised by reacting equimolar ZnO and Al₂O₃ powders in alkaline chlorides (LiCl, NaCl or KCl). Formation of ZnAl₂O₄ started at about 700 °C in LiCl and 800 °C in NaCl and KCl. With increasing temperature, the amounts of ZnAl₂O₄ in the resultant powders increased with a concomitant decrease of ZnO and Al₂O₃. ZnAl₂O₄ powder was obtained by water-washing the samples heated for 3 h at 1000 °C (LiCl) or 1050 °C (NaCl and KCl). ZnAl₂O₄ formed in situ on Al₂O₃ grains from the surface inwards. The synthesised ZnAl₂O₄ grains retained the size and morphology of the original Al₂O₃ powders, indicating that a template formation mechanism dominated formation of ZnAl₂O₄ by molten salt synthesis.     

Molten salt synthesis of titanate pyrochlore waste-forms

Actinide chlorides, such as those arising from pyrochemical reprocessing operations can be problematic to immobilise, as the high chloride content often makes their solubilities in melts very low, and even in small quantities can seriously affect the properties of the waste-form. Rather than attempt to immobilise the chlorine, one potential approach is to utilise the chloride salt as a reaction medium from which the An(III) cations can be extracted and immobilised. To this end, lanthanide titanate pyrochlores have been prepared by molten salt synthesis in CaCl₂:MgCl₂, CaCl₂:NaCl and MgCl₂:NaCl eutectics. Single-phase pyrochlore is found to be formed at temperatures as low as 650 °C in the CaCl₂:NaCl system, whereas in the CaCl₂:MgCl₂ and MgCl₂:NaCl eutectics reaction with Mg produces a magnesium titanate secondary phase. Compositions of Yb₂Ti₂O₇ doped with Sm³⁺ as an actinide surrogate have been synthesised, and cold-pressing and sintering at 1500 °C yields fully dense pellets.     

One-pot hydrothermal synthesis of nitrogen-doped hierarchically porous carbon monoliths for supercapacitors

The nitrogen-doped hierarchically porous carbon monoliths (N-HPCMs) were successfully synthesized by using dicyandiamide (DCDA) as nitrogen source, phenolic resol as carbon precursor and mixed triblock copolymers as templates via a one-pot hydrothermal approach. The obtained carbon monoliths possess tunable mesopore size (4.3–11.4 nm), large surface area (552–660 m²/g), and high nitrogen content (up to 12.1 wt%). Ascribed to the nitrogen-doped frameworks and hierarchical porosity, N-HPCMs exhibit good electrochemical performance as the supercapacitor electrode with specific capacitance of 268.9 F/g (in 6 M KOH) at a current density of 1 A/g, and a 4.1 % loss of the specific capacitance after 5,000 charge–discharge cycles, indicating a long-term cycling stability. Such unique features make N-HPCMs promising electrode materials for high performance supercapacitors.     

Efficient CO2 adsorption and mechanism on nitrogen-doped porous carbons

In this work, nitrogen-doped porous carbons (NACs) were fabricated as an adsorbent by urea modification and KOH activation. The CO₂ adsorption mechanism for the NACs was then explored. The NACs are found to present a large specific surface area (1920.72– 3078.99 m²·g⁻¹) and high micropore percentage (61.60%–76.23%). Under a pressure of 1 bar, sample NAC-650-650 shows the highest CO₂ adsorption capacity up to 5.96 and 3.92 mmol·g⁻¹ at 0 and 25 °C, respectively. In addition, the CO₂/N₂ selectivity of NAC-650-650 is 79.93, much higher than the value of 49.77 obtained for the nonnitrogen-doped carbon AC-650-650. The CO₂ adsorption capacity of the NAC-650-650 sample maintains over 97% after ten cycles. Analysis of the results show that the CO₂ capacity of the NACs has a linear correlation (R² = 0.9633) with the cumulative pore volume for a pore size less than 1.02 nm. The presence of nitrogen and oxygen enhances the CO₂/N₂ selectivity, and pyrrole-N and hydroxy groups contribute more to the CO₂ adsorption. In situ Fourier transform infrared spectra analysis indicates that CO₂ is adsorbed onto the NACs as a gas. Furthermore, the physical adsorption mechanism is confirmed by adsorption kinetic models and the isosteric heat, and it is found to be controlled by CO₂ diffusion. The CO₂ adsorption kinetics for NACs at room temperature and in pure CO₂ is in accordance with the pseudo-first-order model and Avramís fractional-order kinetic model.     

Molten salt synthesis of PZT powder for direct write inks

The preparation of lead zirconate titanate (PZT) powder by molten salt synthesis (MSS) is described and a mechanism proposed. The effect of process parameters, such as reaction time and temperature and heating rate, on particle size and shape was investigated. A reaction mechanism for the synthesis of PZT by molten salt method is proposed, where dissolved Pb initially reacts with insoluble TiO₂ to form intermediate PbTiO₃. Subsequently Zr diffuses into and reacts with PbTiO₃ to form PZT. Spherical particles, ～340 nm in size, were obtained, using a NaCl/KCl salt, by heating the starting materials at 850 °C for 60 min, with a ramp rate of 3.3 °C min^?1.     

空间位阻胺脱硫化氢研究进展

综述了空间位阻胺选择性脱硫化氢的机理,其优势在于比普通醇胺更快的脱硫速率、更高的选择性和更低的腐蚀性及发泡性,重点论述了国内外空间位阻胺脱硫剂的发展现状,如以空间位阻胺为主的复合脱硫剂SHA、空间位阻胺脱硫配方溶剂CT8-16等,并基于空间位阻胺脱硫剂特点与过程强化技术相结合的应用情况,展望了未来发展的趋势是研发性能更优的空间位阻胺脱硫剂,或与新工艺技术相结合。     

Designed synthesis of porous carbons for the separation of light hydrocarbons

The separation of light hydrocarbon mixtures (C₁-C₃) generated from petrochemical industry is vital and challenging process for obtaining valuable pure chemical feedstocks. In comparison to the energy intensive conventional separation technologies (cryogenic distillation, absorption and hydrogenation), the adsorptive separation is considered as a low energy cost and high efficiency process. Porous carbons have been demonstrated as excellent adsorbents for the separation of light hydrocarbons, owing to their designable structure and tailorable properties. This review summarizes the recent advances of using porous carbons as adsorbents for the separation of light hydrocarbons, including methane/nitrogen, methane/alkane, methane/carbon dioxide, ethylene/ethane and propylene/propane. We discuss the separation mechanisms and highlight the material features including pore structure, surface chemistry and target molecular properties that determine the separation performance. Furthermore, the challenges and development direction associated with carbonaceous adsorbents for light hydrocarbon separation are discussed, meanwhile the guidelines for the design of porous carbons are proposed.     

Fabrication of nitrogen-doped hierarchically porous carbons through a hybrid dual-template route for CO2 capture and haemoperfusion

Hierarchically porous carbon materials have many important technological applications; however, most of them were fabricated using either expensive materials or complicated procedures. Based on a general chelate-assisted multi-component co-assembly strategy, nitrogen-doped hierarchically porous carbon materials were fabricated by using Al-based composite and commercial triblock copolymer Pluronic F127 as co-templates, and natural banana peel as precursor. This versatile strategy allowed to easily achieve tunable surface area (700–2100 m² g⁻¹), pore volume (0.38–1.65 cm³ g⁻¹) and a narrow average mesoporous size of ca. 2.72–4.03 nm by simply varying the dosages of Al³⁺ and F127, and to attain high N content (4.54 wt%) in a large-scale fabrication system (2 L). X-ray photoelectron spectroscope characterization of the as-prepared sample revealed nitrogen atoms are mainly in the form of pyridinic nitrogen, quaternary nitrogen and pyridine-N-oxide. Importantly, these as-obtained carbon materials showed excellent performance in CO₂ capture and bilirubin removal with high adsorption capacities and selectivities. The present fabrication strategy is also applicable to the design of porous carbons doped with other elements by choosing appropriate biomass precursors.     

Hydrothermal synthesis of V2O5 nanospheres as catalyst for hydrogen sulfide removal from sour water

Vanadium pentoxide (V₂O₅) nanospheres were synthesized hydrothermally for the first time with high specific surface area. The effect of different parameters including pH level, H₂O₂/H₂O volume ratio and reaction temperature on the precipitate yield was investigated, and the highest yield was attained at the pH level of 3, H₂O₂/H₂O volume ratio of 0.01 and the reaction temperature of 160 °C. Freeze drying, oven drying and vacuum drying methods along with auxiliary processes were employed to improve the drying process and minimize the aggregation of the synthesized nanoparticles (NPs). Two auxiliary processes were used prior to drying in the oven to improve the performance of drying. Firstly, precipitates were immersed in ethanol to get replaced in place of water molecules in a week. The precipitates were then dried at room temperature for a week to evaporate their moisture. In vacuum drying method, only the second auxiliary process was employed. In freeze drying technique, the segregate and uniform nanospheres of V₂O₅ were produced with an average diameter of 37 nm. Generally, the employed additional treatments cause the drying techniques to enhance and the extent of particles aggregation to reduce. Finally, the application of the synthesized NPs as catalyst was investigated for the elimination of H₂S from sour water with the initial concentration of 1300 ppm. The sour water was provided from Shiraz Oil Refinery Company. Results revealed that the synthesized NPs enable to completely eliminate hydrogen sulfide from sour water with 20% greater conversion at early contact seconds as compared to commercial V₂O₅ powder.     

离子液体吸收分离硫化氢进展

针对近年来离子液体在吸收分离硫化氢(H₂S)气体方面的研究进展, 重点论述了H₂S在离子液体中的溶解度及对其他气体的选择性、H₂S-离子液体体系的热力学性质及模型。对离子液体吸收H₂S的机理进行了分析, 阐述了离子液体阴阳离子种类、结构以及取代基等对H₂S分离性能的影响规律, 简要提出了该领域存在的研究难点和未来的发展方向。     

Activated carbons with metal containing bentonite binders as adsorbents of hydrogen sulfide

Wood-based activated carbon was ground and mixed with 10% bentonite binders containing either iron, zinc or copper cations adsorbed within the interlayer space and/or on the external surface of bentonite flakes. To better understand the role of transition metals, carbon was also impregnated with iron, zinc and copper salts. The structure of materials after modification was determined using nitrogen adsorption. The modification resulted in a decrease in porosity, especially in micropore volume, as a result of combined mass dilution effect and adsorption/re-adsorption of metals in small pores. Introduction of bentonite binders containing adsorbed metal increased the capacity of carbon for hydrogen sulfide only in the case of material containing copper. Copper also significantly increases the performance of carbon as an H₂S adsorbent when impregnation is applied whereas the effects of other metals used in this study are much less pronounced. It is likely that copper present in the small pores acts as a catalyst for oxygen activation causing hydrogen sulfide oxidation. As a result of this process, elemental sulfur is formed which, when present in small pores, is oxidized to weakly adsorbed SO₂. The SO₂ is removed from the surface when continuous reaction with hydrogen sulfide occurs. Thus, even though binding carbon with spent bentonites after copper adsorption increases the capacity of carbon toward H₂S removal, the formation of SO₂, another undesirable pollutant, does detract somewhat from the procedure.