Confrontation of various adsorption models for assessing the porous structure of activated carbons

International audienceHerein, a comprehensive analysis of DFT methods as a tool for evaluating the impact of the nature of the activating agent on the porous structure of activated carbons derived from hazelnut shells is given. The study was based on the use of NLDFT, QSDFT, and 2D-NLDFT methods applied to nitrogen adsorption isotherms, and the results were compared with those formerly obtained by using DR, BET, and LBET methods. Analyses conducted with NLDFT, QSDFT, and 2D-NLDFT revealed a very strong dependence of the results on assumptions about the specific pore model, which calls into question the reliability and credibility of these methods. However, if one takes into account the measurement errors that may during the determination of the adsorption isotherms, as well as the difficulty of selecting a representative sample in a batch of materials (most often non-homogeneous) to be analysed, some imperfections of the DFT methods become acceptable. The analyses in question revealed some limitations of the LBET method which became obvious when the analysis concerned bimodal porous materials with a considerable proportion of mesopores. In such cases, the LBET method, which was formerly designed for analysing microporous materials, may become less reliable

Enhanced resolution of ultra micropore size determination of biochars and activated carbons by dual gas analysis using N2 and CO2 with 2D-NLDFT adsorption models

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Assessment of hydrogen storage in activated carbons produced from hydrothermally treated organic materials

12 activated carbons (ACs) were prepared by KOH activation using hydrochars as precursors. These hydrochars were prepared by hydrothermal carbonisation (HTC) of sucrose solutions at concentrations ranging from 0.2 to 1.6 mol L-1. The KOH to hydrochar weight ratio (W) was varied from 1 to 5, and the activation temperature was set to 1023K. ACs texture was assessed by nitrogen and carbon dioxide adsorption at 77 and 273 K, respectively; pore size distribution was calculated by using both isotherms and the SAIEUS© software. ACs with surface areas between 790 and 2240 m2 g-1 were obtained. Hydrogen excess adsorption was determined at 298K and pressures up to 10 MPa in a volumetric device, and the isosteric heat of adsorption (Qst) was calculated for four ACs, using hydrogen isotherms obtained at 278, 298 and 308K. Potassium intercalation between graphitic planes was assumed to account for the high Qst values, 7-8 kJ mol-1. Hydrogen uptake at 2 MPa was compared with hydrogen adsorption data of 38 other ACs reported in the open literature. Hydrogen adsorption fundamentally depends on micropore volume and preliminary HTC did not enhance hydrogen storage although it could be a good strategy for doping carbon with heteroelements.The authors gratefully acknowledge the financial support of the CPER 2007-2013 “Structuration du Pôle de Compétitivité Fibres Grand’Est” (Competitiveness Fibre Cluster), through local (Conseil Général des Vosges), regional (Région Lorraine), national (DRRT and FNADT) and European (FEDER) funds. Part of this work was supported by CHEERS project (FEDER funds) and the COST Action MP1103 “Nanostructured materials for solid-state hydrogen storage”.Peer reviewe

Biochar as a catalyst for hydrogen production from methane conversion

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Hydrothermal pre-treatment, an efficient tool to improve activated carbon performances

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Short-length carbon nanotubes as building blocks for high dielectric constant materials in the terahertz range

Due to the high polarizability of finite-length carbon nanotubes (CNTs) in the quasi-static regime, they can be considered as building blocks for the fabrication of high dielectric constant material. Our theoretical estimations, based on an effective medium approach and solutions of a boundary value problem for individual CNT, predict that composite materials comprising short-length CNTs can have very high dielectric constants (up to 300) and low dielectric loss tangents (below 0.03) in the terahertz range. In order to prove this, 500–1000 nm thick films comprising single- and multi-walled CNTs of both long (0.5–2 μm) and short (0.1–0.4 μm) lengths have been fabricated. The analysis, based on the time-domain terahertz spectroscopy in the range 0.2–1.0 THz, demonstrated a decrease in the dielectric loss tangents of the CNT-based materials with a reduction in CNT length. In the terahertz range, the films comprising short-length CNTs had a relative effective permittivity with a large real part (25–136) and dielectric loss tangent (0.35–0.60)

Advances in tailoring the porosity of tannin-based carbon xerogels

Usually, carbon xerogels are obtained from resorcinol–formaldehyde organic gels. However, more cost-effective and eco-friendly carbon xerogels can be synthesised by using tannins instead of resorcinol, provided that a suitable surfactant is added to prevent the collapse of the structure. The use of tannin, a natural phenolic compound derived from wood, allows obtaining carbon xerogels with controlled porosity, as the porous properties of these materials can be tailored by an appropriate choice of the synthesis conditions. In this work, tannin–formaldehyde xerogels containing different amounts of surfactant and formaldehyde were synthesised in order to evaluate their effect on the porous structure and chemical composition. It was found that porosity and density depend greatly on the amount of surfactant. The lowest density and highest porosity values −0.34 g/cm3 and 78%, respectively-were obtained by adding 10 wt.% of surfactant. It was also found that S-doped carbon xerogels can be easily synthesized due to the strong affinity between the carbon in the structure and the sulphur from the surfactant. Furthermore, statistical analysis showed that there is interdependence between the effect of formaldehyde and the surfactant, especially in the case of volume and pore size. Hence, the choice of the appropriate surfactant-formaldehyde concentration is essential for controlling the formation of the porous polymeric structure.Financial support from the Ministerio de Economía y Competitividad of Spain MINECO (under Projects MAT2011-23733, IPT-2012-0689-420000 and CTQ2013-49433-EXP) is greatly acknowledged. NRR is also grateful to MINECO for her predoctoral research grant. The French authors also gratefully acknowledge the financial support of the CPER 2007–2013 “Structuration du Pô le de Compé titivité Fibres Grand'Est” (Competitiveness Fibre Cluster), through local (Conseil Général des Vosges), regional (Région Lorraine), national (DRRT and FNADT) and European (FEDER) funds.Peer reviewe

Graphite based heat exchangers for fouling control in dairy industry

Fouling of heat exchangers is a major problem in the dairy industry. Deposits indeed produce a thermally insulating layer over the surface of the heat exchanger that decreases the heat transfer toward fluids and increases the pressure drop. Additionally , fouling can seriously affect the quality of food products by favoring the development of harmful bacteria, and thus increase the costs and environmental impacts because thorough cleaning procedures have to be used. In this context, fouling control solut ions are thus required. The present work thus aimed at testin g graphite -based materials to heat exchangers for the dairy industry. The fouling behavior was analyzed for four commercial graphite plates, submitted to pasteurization conditions in a pilot pasteurizer

Influence of activation conditions on textural properties and performance of activated biochars for pyrolysis vapors upgrading

The main aim of the present study is to provide a comprehensive assessment of the effects of process activation conditions on the textural properties of the resulting activated carbons, which were produced from wheat straw-derived biochar through chemical activation (with K2CO3 at different pressures and mass impregnation ratios) and physical activation (with CO2 at different temperatures and pressures). For chemically activated biochars, it was found that specific surface area and pore size distribution were both only positively affected by increasing the carbonate loading. However, physically activated biochars produced at the highest pressure and lowest temperature (1.0 MPa and 700 °C) had the highest surface areas and widest pore size distributions. The materials with the most appropriate textural properties were then tested as catalysts for steam and dry reforming of the aqueous phase of pyrolysis oil. The best catalytic performance (a total gas yield of 74% and a selectivity toward H2 of almost 40%) was observed for a physically activated biochar. This good performance was ascribed to the high availability of K0 on the catalyst surface, which could effectively promote the reactions involved in the upgrading proces

Carbon Monoliths with Hierarchical Porous Structure for All-Vanadium Redox Flow Batteries

Carbon monoliths were tested as electrodes for vanadium redox batteries. The materials were synthesised by a hard-templating route, employing sucrose as carbon precursor and sodium chloride crystals as the hard template. For the preparation process, both sucrose and sodium chloride were ball-milled together and molten into a paste which was hot-pressed to achieve polycondensation of sucrose into a hard monolith. The resultant material was pyrolysed in nitrogen at 750 ◦C, and then washed to remove the salt by dissolving it in water. Once the porosity was opened, a second pyrolysis step at 900 ◦C was performed for the complete conversion of the materials into carbon. The products were next characterised in terms of textural properties and composition. Changes in porosity, obtained by varying the proportions of sucrose to sodium chloride in the initial mixture, were correlated with the electrochemical performances of the samples, and a good agreement between capacitive response and microporosity was indeed observed highlighted by an increase in the cyclic voltammetry curve area when the SBET increased. In contrast, the reversibility of vanadium redox reactions measured as a function of the difference between reduction and oxidation potentials was correlated with the accessibility of the active vanadium species to the carbon surface, i.e., was correlated with the macroporosity. The latter was a critical parameter for understanding the differences of energy and voltage efficiencies among the materials, those with larger macropore volumes having the higher efficiencies.This work was supported by ICEEL and Region Grand Est and J.F.V.-V. was hired with these fundings. This work was partly supported by a grant overseen by the French National Research Agency (Pc2TES ANR-16-CE06-0012-01), and the authors involved in it (AC, BK and VF) acknowledge the support of the project's coordinator, Mrs Fouzia Achchaq. This study was partly supported by TALiSMAN project (2019-000214), funded by European Regional Development Fund (ERDF)