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 Mays (2007) Studies in Surface Science and Catalysis 160 57 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

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 Colloids Surf., A: Physicochemical and Engineering Aspects, 2001, 187 -188 Ibid., 2004, 241 Adv. Colloid Interface Sci., 1998, 76-77 First Workshop 1997 Second Workshop 2000 Third Workshop 2003 Fourth Workshop 2006 Ibid., 2007, 300 Alex Neimark

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

15. 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 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

16. More Books in the COPS Area 20001998

17. 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] 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. Jean Rouquérol Current IUPAC Project in COPS Area

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 solid solid interfaces pore 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. 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. Pore Size – Definition Not straightforward and will depend on method of measurement.

23. Pore Size – Classification "… 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." Mays (2007) Studies in Surface Science and Catalysis 160 57 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. Herbst and Harting (2002), Adsorption 8, 111 CH 4 on Norit N1 steam-activated, peat-derived, extruded carbon pellets Supercritical Adsorption

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

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

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. 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