Overview
FrançaisABSTRACT
This article describes the determination of the pore-size distribution of nanoporous materials by nitrogen adsorption. After presenting two basic theories (Kelvin and DFT) it presents (i) two methods suited to the study of pores smaller than 2 nm (micropores): Sing’s ?s and Horvath and Kawazoe’s method, (ii) the Barrett, Joyner and Halenda (BJH) method for pores between 2 and 50 nm (mesopores), and (iii) the application of DFT to the study of both micropores and mesopores. The merits and limits of each method are stated.
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Read the articleAUTHORS
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Françoise ROUQUEROL: Professor emeritus at Aix-Marseille Université Aix-Marseille Université-CNRS, Laboratoire MADIREL unité mixte de recherche n° 7246, France
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Jean ROUQUEROL: Emeritus Research Director at CNRS Aix-Marseille Université-CNRS, Laboratoire MADIREL Unité mixte de recherche No. 7246, France
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Isabelle BEURROIES: Senior Lecturer at Aix-Marseille Université Aix-Marseille Université-CNRS, Laboratoire MADIREL unité mixte de recherche n° 7246, France
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Philip LLEWELLYN: Director of Research at CNRS Aix-Marseille University-CNRS, MADIREL Laboratory, Joint Research Unit No. 7246, France
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Renaud DENOYEL: Director of Research at CNRS Aix-Marseille University-CNRS, MADIREL Laboratory, Joint Research Unit No. 7246, France
INTRODUCTION
This article reviews the most widely used methods for characterizing the pore size of nanoporous materials by nitrogen adsorption, in the width range from 0.1 to 50 nm.
Even when they are of natural origin (activated carbons, activated clays), these materials are most often treated to "adjust" them (in terms of pore size, specific surface area, surface chemical functions, etc.) with a view to their applications, which are numerous and include the following:
lowering natural gas storage pressure (to lighten cylinders and enable their use on natural gas-powered vehicles);
purification and recycling of aircraft atmosphere;
retention and reuse of petrol vapours from car fuel tanks;
retention and reuse of solvent vapours from paint tunnels;
remediation of soils contaminated by heavy metals;
separation of gases from air at ambient temperature, without the need for energy-intensive liquefaction and distillation;
the storage and gradual release (or "sustained release") of active drug ingredients, to ensure constant concentration in the body despite widely spaced drug doses;
the development of solar refrigeration machines exploiting the highly endothermic nature of water or alcohol vapour desorption for vaccine storage in desert environments;
recovery of hydrogen from refinery off-gases (where it costs nothing) for use as a clean fuel;
carbon dioxide sequestration to limit global warming.
It's easy to see why pore width plays such an important role in these applications. It is this width that enables us to develop both "molecular sieve" properties, allowing only a certain size of molecule to pass through, and physical adsorption energy (the narrower the pore, the higher the energy), enabling us to exploit the corresponding thermal effect, or a permeability to gases and liquids (thanks to several "hierarchical" pore sizes) capable of accelerating chemical engineering operations, or even the "useful" storage capacity of gases with sufficient adsorption energy to allow good retention but low enough to allow easy and as complete as possible recovery of the gas...
To characterize the size of nanopores, this article uses nitrogen adsorption, which is the most widely used approach, especially when the material itself is intended for an application involving adsorption.
Today's automated equipment makes it possible to carry out routine measurements, which is a definite advantage,...
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KEYWORDS
Kelvin theorie | DFT theorie | HK method | | BJH method
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Texture of divided materials
Bibliography
Software tools
Database of hundreds of adsorption isotherms, including many new adsorbents http://adsorbents.nist.gov/
NLDFT calculations http://www.NLDFT.com
Fluid properties https://www.nist.gov/srd/refprop
...Events
On a national scale: annual days of the French Adsorption Association, usually in January-February. http://www.adsorption.fr/spip.php?rubrique1
Internationally: three successive triennial congresses, one per year, usually in April-May, in the following order:
Fundamentals...
Standards and norms
- Pore size distribution and porosity of solid materials by mercury porosimetry and gas adsorption – Part 2 : Analysis of mesopores and macropores by gas adsorption - ISO 15901-2 - 2006
- Pore size distribution and porosity of solid materials by mercury porosimetry and gas adsorption – Part 3 : Analysis of micropores by gas adsorption - ISO 15901-3 - 2007
Regulations. Safety
Use of liquid nitrogen http://bip.cnrs-mrs.fr/acmo/node8.html
Handling nanomaterials and nanoparticles http://www.inrs.fr/risques/nanomateriaux/prevention-risques.html
Gas handling...
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Marketed equipment (non-exhaustive list)
The commercial adsorption units shown in Table allow a detailed study based on the nitrogen adsorption-desorption isotherm at 77 K. Generally speaking, the adsorption isotherm domain they automatically record, and the software they are equipped with, allow fairly easy access to specific surface area (BET method
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