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Supercritical hydrogen adsorption in nanostructured solids with hydrogen density variation in pores

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Abstract

Experimental excess isotherms for the adsorption of gases in porous solids may be represented by mathematical models that incorporate the total amount of gas within a pore, a quantity which cannot easily be found experimentally but which is important for calculations for many applications, including adsorptive storage. A model that is currently used for hydrogen adsorption in porous solids has been improved to include a more realistic density profile of the gas within the pore, and allows calculation of the total amount of adsorbent. A comparison has been made between different Type I isotherm equations embedded in the model, by examining the quality of the fits to hydrogen isotherms for six different nanoporous materials. A new Type I isotherm equation which has not previously been reported in the literature, the Unilan-b equation, has been derived and has also been included in this comparison study. These results indicate that while some Type I isotherm equations fit certain types of materials better than others, the Tόth equation produces the best overall quality of fit and also provides realistic parameter values when used to analyse hydrogen sorption data for a model carbon adsorbent.

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Abbreviations

MOF:

Metal–organic framework

PIM:

Polymer of intrinsic microporosity

m E :

Excess mass of hydrogen

v P :

Pore volume

ρB :

Bulk density

m maxA :

Limiting maximum uptake

θA :

Fractional filling

wt %:

Weight percent

P :

Absolute pressure

b :

Affinity parameter

Q :

Enthalpic factor

b 0 :

Pre-exponential factor

R :

Molar gas constant

T :

Absolute temperature

bdc:

Benzene-1,4-dicarboxylate

MIL:

Matériaux de l’Institut Lavoisier

BET:

Brunauer, Emmett and Teller

m B(A) :

Bulk hydrogen within the adsorbate

m A :

Absolute uptake

m P :

Total uptake

ρA :

Adsorbate density

v A :

Adsorbate volume

M :

Molar mass

Z :

Compressibility factor

NIST:

National Institute of Standards and Technology

b (T) :

Tόth affinity parameter

c (T) :

Tόth heterogeneity parameter

RMSR:

Root mean square residual

b 1 :

Minimum value of b in a uniform distribution

b 2 :

Maximum value of b in a uniform distribution

Q 1 :

Minimum value of Q in a uniform distribution

Q 2 :

Maximum value of Q in a uniform distribution

θ(P,h):

Local isotherm

h :

Heterogeneity parameter

w :

Substitution variable

b (L) :

Langmuir affinity parameter

b (S) :

Sips affinity parameter

m (S) :

Sips heterogeneity parameter

b (GF) :

Generalised Freundlich affinity parameter

q :

Generalised Freundlich heterogeneity parameter

b (JF) :

Jovanović–Freundlich affinity parameter

c (JF) :

Jovanović–Freundlich heterogeneity parameter

α:

Dubinin–Astakhov enthalpic factor

β:

Dubinin–Astakhov entropic factor

m (DA) :

Adjustable parameter within the Dubinin–Astakhov equation

P 0 :

Vapour pressure

GCMC:

Grand-canonical Monte Carlo

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Acknowledgments

JES thanks the UK Engineering and Physical Sciences Research Council (EPSRC) Doctoral Training Centre in Sustainable Chemical Technologies at the University of Bath, and also to Dr Agata Godula-Jopek from the EADS Innovation Works, Munich, Germany for financial support. NB and TJM thank the EPSRC for funding via the SUPERGEN United Kingdom Sustainable Hydrogen Energy Consortium (UK-SHEC, EP/J016454/1), VPT thanks the University of Bath for funding via an EPSRC Development Fund grant and a Prize Research Fellowship, and VPT and TJM thank the EPSRC for supporting the latter stages of this work via its Delivery Fund at the University of Bath and the SUPERGEN Hydrogen and Fuel Cells Hub (EP/E040071/1). JES, NB and VPT thank the Organising Committee of the 8th International Symposium of the Effects of Surface Heterogeneity in Adsorption and Catalysis on Solids (ISSHAC-8, Aug 2012, Kraków, Poland) for the opportunity to present this work as an oral presentation and for subsidising registration for the conference. The authors thank Anne Dailly (Chemical Sciences and Materials Systems Laboratory, General Motors Global Research and Development, Warren, MI, U.S) for providing the NOTT-101 data. ADB and DJ thank the EPSRC for funding (EP/H046305/1).

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Authors and Affiliations

  1. Department of Chemical Engineering, EPSRC Doctoral Training Centre, Centre for Sustainable Chemical Technologies, University of Bath, Bath, BA27AY, UK

    Jessica E. Sharpe

  2. Department of Chemical Engineering, University of Bath, Bath, BA27AY, UK

    Nuno Bimbo, Valeska P. Ting & Timothy J. Mays

  3. Department of Chemistry, University of Bath, Bath, BA2 7AY, UK

    Andrew D. Burrows & Dongmei Jiang

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  1. Jessica E. Sharpe
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Correspondence to Timothy J. Mays.

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Sharpe, J.E., Bimbo, N., Ting, V.P. et al. Supercritical hydrogen adsorption in nanostructured solids with hydrogen density variation in pores. Adsorption 19, 643–652 (2013). https://doi.org/10.1007/s10450-013-9487-6

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