A Proposal for a New IUPAC Project on the Characterisation of Porous Solids Tim Mays

2. A Proposal for a New IUPAC Project on the Characterisation of Porous Solids Tim Mays Department of Chemical Engineering University of Bath United Kingdom June 2008

3. Background • Current recommendations of the International Union of Pure and Applied Chemistry for the characterisation of porous solids were set out in 1994 • These have since proved to be invaluable to scientists and engineers with interests in porous solids • However there have been many and varied developments in the area that have been made in the intervening period • This is a proposal to establish a new IUPAC project on the characterisation of porous solids to update the 1994 recommendations in light of these developments

4. Outline • The 1994 IUPAC recommendations for the characterisation of porous solids • Significant output since 1994 • Scope of characterisation of porous solids • Some areas to consider for updating the 1994 recommendations • Process to establish a new IUPAC project • Concluding remarks

5. Outline • The 1994 IUPAC recommendations for the characterisation of porous solids • Significant output since 1994 • Scope of characterisation of porous solids • Some areas to consider for updating the 1994 recommendations • Process to establish a new IUPAC project • Concluding remarks

10. Key References D.H. Everett and F.S. Stone, eds. The Structure and Properties of Porous Materials. Proceedings of the Tenth Symposium of the Colston Research Society, University of Bristol, 1958 Mays (2007) Studies in Surface Science and Catalysis160 57

11. Outline • The 1994 IUPAC recommendations for the characterisation of porous solids • Significant output since 1994 • Scope of characterisation of porous solids • Some areas to consider for updating the 1994 recommendations • Process to establish a new IUPAC project • Concluding remarks

12. Proceedings of COPS Symposia COPS-IV Bath, 1996 COPS-V Heidelberg, 1999 COPS-VI Alicante, 2002 COPS-VII Aix-en-Provence, 2005

13. Proceedings of Workshops on the Characterization of Porous Materials: From Ångstroms to Millimeters Princeton, NJ, USA Alex Neimark First Workshop 1997 Second Workshop 2000 Third Workshop 2003 Fourth Workshop 2006 Ibid., 2007, 300 Colloids Surf., A: Physicochemical and Engineering Aspects,2001, 187 -188 Ibid.,2004, 241 Adv. Colloid Interface Sci., 1998, 76-77

14. Fundamentals of Adsorption 1995 FOA-5 USA 1998 FOA-6 France 2001 FOA-7 Japan 2004 FOA-8 USA 2007 FOA-9 Italy

15. Selected Books in the COPS Area S. Lowell, J. E. Shields, M. A. Thomas and M. Thommes, Characterization of Porous Solids and Powders: Surface Area, Pore Size and Density, Kluwer, Dordrecht, 2004 J. Rouquérol, F.Rouquérol and K. S. W. Sing, Adsorption by Powders and Porous Solids, Elsevier, Amsterdam, 1998 F. Schüth, K. S. W. Sing and J. Weitkamp, eds., Handbook of Porous Solids (Vols. 1-5), Wiley, Weinheim, 2002

16. More Books in the COPS Area 1998 2000

17. Current IUPAC Project in COPS Area Project 2006-021-2-100 Liquid Intrusion and Alternative Methods for the Characterization of Macroporous Solids http://www.iupac.org/web/ins/2006-021-2-100 [Accessed 5 June 2008] Jean Rouquérol Objective To analyse the various liquid intrusion techniques available to-day to assess the pore-size of materials (with special attention to the pores above 50 nm width), together with other alternatives, in order to provide (i) a critical and comparative appraisal and (ii) an appreciation about the ways which should be favoured and developed to solve the issue described hereafter.

18. Outline • The 1994 IUPAC recommendations for the characterisation of porous solids • Significant activities since 1994 • Scope of characterisation of porous solids • Some areas to consider for updating the 1994 recommendations • Process to establish a new IUPAC project • Concluding remarks

19. Scope pore solid solid interfaces • Characterisation involves the study of three main regions: • Solid – structure, composition, … • Solid interfaces – structure, composition, … • Pores – size, shape, orientation, location, connectivity, tortuosity, … • Link characteristics with • formation and/or processing • actual or predicted performance in applications

20. Outline • The 1994 IUPAC recommendations for the characterisation of porous solids • Significant activities since 1994 • Scope of characterisation of porous solids • Some areas to consider for updating the 1994 recommendations • Process to establish a new IUPAC project • Concluding remarks

21. Areas for Updating • Definitions, terminology, classification • Methods • Materials

22. Pore Size – Definition Not straightforward and will depend on method of measurement. P.E. Levitz, In: Handbook of Porous Solids, Vol. 1 (F. Schüth, K.S.W. Sing and J. Weitkamp, eds.), Wiley, Weinheim, 2002, pp. 37-80.

23. Pore Size – Classification Mays (2007) Studies in Surface Science and Catalysis160 57 "… pore size has, arguably, the greatest or widest influence on the properties (and hence uses) of solids, compared to other parameters such as pore shape. It is therefore unquestionably useful and convenient to use pore size (or pore size distribution) as a means to characterise and compare different porous solids." Proposed new scheme

24. Pore Size – DFT and Molecular Simulations • Local isotherms (kernels of the generalised adsorption isotherm) now commonly obtained using density functional theory or molecular simulations • Estimates of pore size distributions f(h) = f(w) depend critically on these kernels

25. Isotherm Classification

26. Supercritical Adsorption • Herbst and Harting (2002), Adsorption8, 111 • CH4 on Norit N1 steam-activated, peat-derived, extruded carbon pellets

27. Large Pores advanced separations enhanced oil recovery building materials Mays, Rigby, et al. (2007). Cement & Concrete Research, 27, 1059

28. Methods Catalyst characterisation: 3D micro-computed x-ray tomography image of a sol-gel silica pellet containing entrapped mercury following porosimetry (Rigby, 2004)

29. Outline • The 1994 IUPAC recommendations for the characterisation of porous solids • Significant activities since 1994 • Scope of characterisation of porous solids • Some areas to consider for updating the 1994 recommendations • Process to establish a new IUPAC project • Concluding remarks

30. Process to Establish a New IUPAC Project • Process established in 2000 • http://www.iupac.org/Projects • E. D. Becker, Chemistry International, 23(1), 2001 • General criteria • Projects should address one of the goals listed in the IUPAC Strategic Plan • Projects should be of international in scope and membership and be related to the role of chemistry for the needs of mankind • Key features • Ideas → Proposal → Review → Resources → Task Group → Project • Duration mormally 12-36 months • Funding typically up to US$5,000 mainly for travel, subsistence and administration costs • Consultation / activities / outcomes / dissemination

31. Outline • The 1994 IUPAC recommendations for the characterisation of porous solids • Significant activities since 1994 • Scope of characterisation of porous solids • Some areas to consider for updating the 1994 recommendations • Process to establish a new IUPAC project • Concluding remarks

32. Concluding remarks • The time may be right to consider updating the 1994 IUPAC recommendations for the characterisation of porous solids • Proposal for a new IUPAC project Recommendations for the Characterisation of Porous Solids (Phase 2?) under the Physical and Biophysical Chemistry Division (I) • Link to Project 2006-021-2-100 • Possible start date by end 2008 • Could report at CPM-4 in 2009, FOA-10 in 2010 and finally COPS-9 in 2011 • Next steps: • Determine whether idea is supported • If so then establish a Task Group and Chair • Submit proposal

33. Acknowledgements • Organisers and hosts of COPS-9 • Professor Brian McEnaney • Professor Ken Sing • Research colleagues • Engineering and Physical Sciences Research Council, UK • University of Bath Nigel Seaton