How reproducible are surface areas calculated from the BET equation?

Johannes W.M. Osterrieth; James Rampersad; David Madden; Nakul Rampal; Luka Skoric; Bethany Connolly; Mark D. Allendorf; Vitalie Stavila; Jonathan L. Snider; Rob Ameloot; João Marreiros; Conchi Ania; Diana Azevedo; Enrique Vilarrasa-Garcia; Bianca F. Santos; Xian He Bu; Ze Chang; Hana Bunzen; Neil R. Champness; Sarah L. Griffin; Banglin Chen; Rui Biao Lin; Benoit Coasne; Seth Cohen; Jessica C. Moreton; Yamil J. Colón; Linjiang Chen; Rob Clowes; François Xavier Coudert; Yong Cui; Bang Hou; Deanna M. D'Alessandro; Patrick W. Doheny; Mircea Dincă; Chenyue Sun; Christian Doonan; Michael Thomas Huxley; Jack D. Evans; Paolo Falcaro; Raffaele Ricco; Omar Farha; Karam B. Idrees; Timur Islamoglu; Pingyun Feng; Huajun Yang; Ross S. Forgan; Dominic Bara; Shuhei Furukawa; Eli Sanchez; Jorge Gascon; Selvedin Telalović; Sujit K. Ghosh; Soumya Mukherjee; Matthew R. Hill; Muhammed Munir Sadiq; Patricia Horcajada; Pablo Salcedo-Abraira; Katsumi Kaneko; Radovan Kukobat; Jeff Kenvin; Seda Keskin; Susumu Kitagawa; Ken ichi Otake; Ryan P. Lively; Stephen J.A. DeWitt; Phillip Llewellyn; Bettina V. Lotsch; Sebastian T. Emmerling; Alexander M. Pütz; Carlos Martí-Gastaldo; Natalia M. Padial; Javier García-Martínez; Noemi Linares; Daniel Maspoch; Jose A. Suárez del Pino; Peyman Moghadam; Rama Oktavian; Russel E. Morris; Paul S. Wheatley; Jorge Navarro; Camille Petit; David Danaci; Matthew J. Rosseinsky; Alexandros P. Katsoulidis; Martin Schröder; Xue Han; Sihai Yang; Christian Serre; Georges Mouchaham; David S. Sholl; Raghuram Thyagarajan; Daniel Siderius; Randall Q. Snurr; Rebecca B. Goncalves; Shane Telfer; Seok J. Lee; Valeska P. Ting; Jemma L. Rowlandson; Takashi Uemura; Tomoya Iiyuka; Monique A. van der Veen; Davide Rega; Veronique Van Speybroeck; Sven M.J. Rogge; Aran Lamaire; Krista S. Walton; Lukas W. Bingel; Stefan Wuttke; Jacopo Andreo; Omar Yaghi; Bing Zhang; Cafer T. Yavuz; Thien S. Nguyen; Felix Zamora; Carmen Montoro; Hongcai Zhou; Angelo Kirchon; David Fairen-Jimenez

doi:10.1002/adma.202201502

How reproducible are surface areas calculated from the BET equation?

Johannes W.M. Osterrieth, James Rampersad, David Madden, Nakul Rampal, Luka Skoric, Bethany Connolly, Mark D. Allendorf, Vitalie Stavila, Jonathan L. Snider, Rob Ameloot, João Marreiros, Conchi Ania, Diana Azevedo, Enrique Vilarrasa-Garcia, Bianca F. Santos, Xian He Bu, Ze Chang, Hana Bunzen, Neil R. Champness, Sarah L. GriffinBanglin Chen, Rui Biao Lin, Benoit Coasne, Seth Cohen, Jessica C. Moreton, Yamil J. Colón, Linjiang Chen, Rob Clowes, François Xavier Coudert, Yong Cui, Bang Hou, Deanna M. D'Alessandro, Patrick W. Doheny, Mircea Dincă, Chenyue Sun, Christian Doonan, Michael Thomas Huxley, Jack D. Evans, Paolo Falcaro, Raffaele Ricco, Omar Farha, Karam B. Idrees, Timur Islamoglu, Pingyun Feng, Huajun Yang, Ross S. Forgan, Dominic Bara, Shuhei Furukawa, Eli Sanchez, Jorge Gascon, Selvedin Telalović, Sujit K. Ghosh, Soumya Mukherjee, Matthew R. Hill, Muhammed Munir Sadiq, Patricia Horcajada, Pablo Salcedo-Abraira, Katsumi Kaneko, Radovan Kukobat, Jeff Kenvin, Seda Keskin, Susumu Kitagawa, Ken ichi Otake, Ryan P. Lively, Stephen J.A. DeWitt, Phillip Llewellyn, Bettina V. Lotsch, Sebastian T. Emmerling, Alexander M. Pütz, Carlos Martí-Gastaldo, Natalia M. Padial, Javier García-Martínez, Noemi Linares, Daniel Maspoch, Jose A. Suárez del Pino, Peyman Moghadam, Rama Oktavian, Russel E. Morris, Paul S. Wheatley, Jorge Navarro, Camille Petit, David Danaci, Matthew J. Rosseinsky, Alexandros P. Katsoulidis, Martin Schröder, Xue Han, Sihai Yang, Christian Serre, Georges Mouchaham, David S. Sholl, Raghuram Thyagarajan, Daniel Siderius, Randall Q. Snurr, Rebecca B. Goncalves, Shane Telfer, Seok J. Lee, Valeska P. Ting, Jemma L. Rowlandson, Takashi Uemura, Tomoya Iiyuka, Monique A. van der Veen, Davide Rega, Veronique Van Speybroeck, Sven M.J. Rogge, Aran Lamaire, Krista S. Walton, Lukas W. Bingel, Stefan Wuttke, Jacopo Andreo, Omar Yaghi, Bing Zhang, Cafer T. Yavuz, Thien S. Nguyen, Felix Zamora, Carmen Montoro, Hongcai Zhou, Angelo Kirchon, David Fairen-Jimenez^*

^*Corresponding author for this work

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Abstract

Porosity and surface area analysis play a prominent role in modern materials science. At the heart of this sits the Brunauer–Emmett–Teller (BET) theory, which has been a remarkably successful contribution to the field of materials science. The BET method was developed in the 1930s for open surfaces but is now the most widely used metric for the estimation of surface areas of micro- and mesoporous materials. Despite its widespread use, the calculation of BET surface areas causes a spread in reported areas, resulting in reproducibility problems in both academia and industry. To prove this, for this analysis, 18 already-measured raw adsorption isotherms were provided to sixty-one labs, who were asked to calculate the corresponding BET areas. This round-robin exercise resulted in a wide range of values. Here, the reproducibility of BET area determination from identical isotherms is demonstrated to be a largely ignored issue, raising critical concerns over the reliability of reported BET areas. To solve this major issue, a new computational approach to accurately and systematically determine the BET area of nanoporous materials is developed. The software, called “BET surface identification” (BETSI), expands on the well-known Rouquerol criteria and makes an unambiguous BET area assignment possible.

Original language	English
Article number	2201502
Number of pages	12
Journal	Advanced Materials
Volume	34
Issue number	27
Early online date	23 May 2022
DOIs	https://doi.org/10.1002/adma.202201502
Publication status	Published - 7 Jul 2022

Bibliographical note

Funding Information:
This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (NanoMOFdeli), ERC‐2016‐COG 726380, Innovate UK (104384) and EPSRC IAA (IAA/RG85685). N.R. acknowledges the support of the Cambridge International Scholarship and the Trinity‐Henry Barlow Scholarship (Honorary). O.K.F. and R.Q.S. acknowledge funding from the U.S. Department of Energy (DE‐FG02‐08ER15967). R.S.F. and D.B. acknowledge funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (SCoTMOF), ERC‐2015‐StG 677289. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy's National Nuclear Security Administration under contract DE‐NA‐0003525. The authors gratefully acknowledge funding from the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office, through the Hydrogen Storage Materials Advanced Research Consortium (HyMARC). This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government. J.D.E. acknowledges the support of the Alexander von Humboldt Foundation and the Center for Information Services and High Performance Computing (ZIH) at TU Dresden. S.K.G. and S.M. acknowledge SERB (Project No. CRG/2019/000906), India for financial support. K.K. and R.K. acknowledge Active Co. Research Grant for funding. S.K. acknowledges funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (COSMOS), ERC‐2017‐StG 756489. N.L. and J.G.M acknowledge funding from the European Commission through the H2020‐MSCA‐RISE‐2019 program (ZEOBIOCHEM – 872102) and the Spanish MICINN and AEI/FEDER (RTI2018‐099504‐B‐C21). N.L. thanks the University of Alicante for funding (UATALENTO17‐05). ICN2 is supported by the Severo Ochoa program from the Spanish MINECO (Grant No. SEV‐2017‐0706) S.M.J.R. and A.L. wish to thank the Fund for Scientific Research Flanders (FWO), under grant nos. 12T3519N and 11D2220N. L.S. was supported by the EPSRC Cambridge NanoDTC EP/L015978/1. C.T.Y. and T.S.N. acknowledges funds from the National Research Foundation of Korea, NRF‐2017M3A7B4042140 and NRF‐2017M3A7B4042235. P.F. and H. Y. acknowledge US Department of Energy, Office of Basic Energy Sciences, Materials Sciences and Engineering Division under Award No. DE‐SC0010596 (P.F.). R.O. would like to acknowledge funding support during his Ph.D. study from Indonesian Endowment Fund for Education‐LPDP with the contract No. 202002220216006. Daniel Siderius: Official contribution of the National Institute of Standards and Technology (NIST), not subject to copyright in the United States of America. Daniel Siderius: Certain commercially available items may be identified in this paper. This identification does not imply recommendation by NIST, nor does it imply that it is the best available for the purposes described. B.V.L, S.T.E and A.M.P acknowledge funding from the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Program (Grant agreement no. 639233, COFLeaf).

Publisher Copyright:
© 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.

Keywords

adsorption
BET theory
porosimetry
porous materials
surface area

ASJC Scopus subject areas

General Materials Science
Mechanics of Materials
Mechanical Engineering

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Cite this

Osterrieth, J. W. M., Rampersad, J., Madden, D., Rampal, N., Skoric, L., Connolly, B., Allendorf, M. D., Stavila, V., Snider, J. L., Ameloot, R., Marreiros, J., Ania, C., Azevedo, D., Vilarrasa-Garcia, E., Santos, B. F., Bu, X. H., Chang, Z., Bunzen, H., Champness, N. R., ... Fairen-Jimenez, D. (2022). How reproducible are surface areas calculated from the BET equation? Advanced Materials, 34(27), Article 2201502. https://doi.org/10.1002/adma.202201502

@article{dbbd1bbeb4364eeaa570c536db6f22d1,

title = "How reproducible are surface areas calculated from the BET equation?",

abstract = "Porosity and surface area analysis play a prominent role in modern materials science. At the heart of this sits the Brunauer–Emmett–Teller (BET) theory, which has been a remarkably successful contribution to the field of materials science. The BET method was developed in the 1930s for open surfaces but is now the most widely used metric for the estimation of surface areas of micro- and mesoporous materials. Despite its widespread use, the calculation of BET surface areas causes a spread in reported areas, resulting in reproducibility problems in both academia and industry. To prove this, for this analysis, 18 already-measured raw adsorption isotherms were provided to sixty-one labs, who were asked to calculate the corresponding BET areas. This round-robin exercise resulted in a wide range of values. Here, the reproducibility of BET area determination from identical isotherms is demonstrated to be a largely ignored issue, raising critical concerns over the reliability of reported BET areas. To solve this major issue, a new computational approach to accurately and systematically determine the BET area of nanoporous materials is developed. The software, called “BET surface identification” (BETSI), expands on the well-known Rouquerol criteria and makes an unambiguous BET area assignment possible.",

keywords = "adsorption, BET theory, porosimetry, porous materials, surface area",

author = "Osterrieth, {Johannes W.M.} and James Rampersad and David Madden and Nakul Rampal and Luka Skoric and Bethany Connolly and Allendorf, {Mark D.} and Vitalie Stavila and Snider, {Jonathan L.} and Rob Ameloot and Jo{\~a}o Marreiros and Conchi Ania and Diana Azevedo and Enrique Vilarrasa-Garcia and Santos, {Bianca F.} and Bu, {Xian He} and Ze Chang and Hana Bunzen and Champness, {Neil R.} and Griffin, {Sarah L.} and Banglin Chen and Lin, {Rui Biao} and Benoit Coasne and Seth Cohen and Moreton, {Jessica C.} and Col{\'o}n, {Yamil J.} and Linjiang Chen and Rob Clowes and Coudert, {Fran{\c c}ois Xavier} and Yong Cui and Bang Hou and D'Alessandro, {Deanna M.} and Doheny, {Patrick W.} and Mircea Dinc{\u a} and Chenyue Sun and Christian Doonan and Huxley, {Michael Thomas} and Evans, {Jack D.} and Paolo Falcaro and Raffaele Ricco and Omar Farha and Idrees, {Karam B.} and Timur Islamoglu and Pingyun Feng and Huajun Yang and Forgan, {Ross S.} and Dominic Bara and Shuhei Furukawa and Eli Sanchez and Jorge Gascon and Selvedin Telalovi{\'c} and Ghosh, {Sujit K.} and Soumya Mukherjee and Hill, {Matthew R.} and Sadiq, {Muhammed Munir} and Patricia Horcajada and Pablo Salcedo-Abraira and Katsumi Kaneko and Radovan Kukobat and Jeff Kenvin and Seda Keskin and Susumu Kitagawa and Otake, {Ken ichi} and Lively, {Ryan P.} and DeWitt, {Stephen J.A.} and Phillip Llewellyn and Lotsch, {Bettina V.} and Emmerling, {Sebastian T.} and P{\"u}tz, {Alexander M.} and Carlos Mart{\'i}-Gastaldo and Padial, {Natalia M.} and Javier Garc{\'i}a-Mart{\'i}nez and Noemi Linares and Daniel Maspoch and {Su{\'a}rez del Pino}, {Jose A.} and Peyman Moghadam and Rama Oktavian and Morris, {Russel E.} and Wheatley, {Paul S.} and Jorge Navarro and Camille Petit and David Danaci and Rosseinsky, {Matthew J.} and Katsoulidis, {Alexandros P.} and Martin Schr{\"o}der and Xue Han and Sihai Yang and Christian Serre and Georges Mouchaham and Sholl, {David S.} and Raghuram Thyagarajan and Daniel Siderius and Snurr, {Randall Q.} and Goncalves, {Rebecca B.} and Shane Telfer and Lee, {Seok J.} and Ting, {Valeska P.} and Rowlandson, {Jemma L.} and Takashi Uemura and Tomoya Iiyuka and {van der Veen}, {Monique A.} and Davide Rega and {Van Speybroeck}, Veronique and Rogge, {Sven M.J.} and Aran Lamaire and Walton, {Krista S.} and Bingel, {Lukas W.} and Stefan Wuttke and Jacopo Andreo and Omar Yaghi and Bing Zhang and Yavuz, {Cafer T.} and Nguyen, {Thien S.} and Felix Zamora and Carmen Montoro and Hongcai Zhou and Angelo Kirchon and David Fairen-Jimenez",

note = "Funding Information: This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (NanoMOFdeli), ERC‐2016‐COG 726380, Innovate UK (104384) and EPSRC IAA (IAA/RG85685). N.R. acknowledges the support of the Cambridge International Scholarship and the Trinity‐Henry Barlow Scholarship (Honorary). O.K.F. and R.Q.S. acknowledge funding from the U.S. Department of Energy (DE‐FG02‐08ER15967). R.S.F. and D.B. acknowledge funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (SCoTMOF), ERC‐2015‐StG 677289. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy's National Nuclear Security Administration under contract DE‐NA‐0003525. The authors gratefully acknowledge funding from the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office, through the Hydrogen Storage Materials Advanced Research Consortium (HyMARC). This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government. J.D.E. acknowledges the support of the Alexander von Humboldt Foundation and the Center for Information Services and High Performance Computing (ZIH) at TU Dresden. S.K.G. and S.M. acknowledge SERB (Project No. CRG/2019/000906), India for financial support. K.K. and R.K. acknowledge Active Co. Research Grant for funding. S.K. acknowledges funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (COSMOS), ERC‐2017‐StG 756489. N.L. and J.G.M acknowledge funding from the European Commission through the H2020‐MSCA‐RISE‐2019 program (ZEOBIOCHEM – 872102) and the Spanish MICINN and AEI/FEDER (RTI2018‐099504‐B‐C21). N.L. thanks the University of Alicante for funding (UATALENTO17‐05). ICN2 is supported by the Severo Ochoa program from the Spanish MINECO (Grant No. SEV‐2017‐0706) S.M.J.R. and A.L. wish to thank the Fund for Scientific Research Flanders (FWO), under grant nos. 12T3519N and 11D2220N. L.S. was supported by the EPSRC Cambridge NanoDTC EP/L015978/1. C.T.Y. and T.S.N. acknowledges funds from the National Research Foundation of Korea, NRF‐2017M3A7B4042140 and NRF‐2017M3A7B4042235. P.F. and H. Y. acknowledge US Department of Energy, Office of Basic Energy Sciences, Materials Sciences and Engineering Division under Award No. DE‐SC0010596 (P.F.). R.O. would like to acknowledge funding support during his Ph.D. study from Indonesian Endowment Fund for Education‐LPDP with the contract No. 202002220216006. Daniel Siderius: Official contribution of the National Institute of Standards and Technology (NIST), not subject to copyright in the United States of America. Daniel Siderius: Certain commercially available items may be identified in this paper. This identification does not imply recommendation by NIST, nor does it imply that it is the best available for the purposes described. B.V.L, S.T.E and A.M.P acknowledge funding from the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Program (Grant agreement no. 639233, COFLeaf). Publisher Copyright: {\textcopyright} 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.",

year = "2022",

month = jul,

day = "7",

doi = "10.1002/adma.202201502",

language = "English",

volume = "34",

journal = "Advanced Materials",

issn = "0935-9648",

publisher = "Wiley-VCH Verlag",

number = "27",

}

Osterrieth, JWM, Rampersad, J, Madden, D, Rampal, N, Skoric, L, Connolly, B, Allendorf, MD, Stavila, V, Snider, JL, Ameloot, R, Marreiros, J, Ania, C, Azevedo, D, Vilarrasa-Garcia, E, Santos, BF, Bu, XH, Chang, Z, Bunzen, H, Champness, NR , Griffin, SL, Chen, B, Lin, RB, Coasne, B, Cohen, S, Moreton, JC, Colón, YJ, Chen, L, Clowes, R, Coudert, FX, Cui, Y, Hou, B, D'Alessandro, DM, Doheny, PW, Dincă, M, Sun, C, Doonan, C, Huxley, MT, Evans, JD, Falcaro, P, Ricco, R, Farha, O, Idrees, KB, Islamoglu, T, Feng, P, Yang, H, Forgan, RS, Bara, D, Furukawa, S, Sanchez, E, Gascon, J, Telalović, S, Ghosh, SK, Mukherjee, S, Hill, MR, Sadiq, MM, Horcajada, P, Salcedo-Abraira, P, Kaneko, K, Kukobat, R, Kenvin, J, Keskin, S, Kitagawa, S, Otake, KI, Lively, RP, DeWitt, SJA, Llewellyn, P, Lotsch, BV, Emmerling, ST, Pütz, AM, Martí-Gastaldo, C, Padial, NM, García-Martínez, J, Linares, N, Maspoch, D, Suárez del Pino, JA, Moghadam, P, Oktavian, R, Morris, RE, Wheatley, PS, Navarro, J, Petit, C, Danaci, D, Rosseinsky, MJ, Katsoulidis, AP, Schröder, M, Han, X, Yang, S, Serre, C, Mouchaham, G, Sholl, DS, Thyagarajan, R, Siderius, D, Snurr, RQ, Goncalves, RB, Telfer, S, Lee, SJ, Ting, VP, Rowlandson, JL, Uemura, T, Iiyuka, T, van der Veen, MA, Rega, D, Van Speybroeck, V, Rogge, SMJ, Lamaire, A, Walton, KS, Bingel, LW, Wuttke, S, Andreo, J, Yaghi, O, Zhang, B, Yavuz, CT, Nguyen, TS, Zamora, F, Montoro, C, Zhou, H, Kirchon, A & Fairen-Jimenez, D 2022, 'How reproducible are surface areas calculated from the BET equation?', Advanced Materials, vol. 34, no. 27, 2201502. https://doi.org/10.1002/adma.202201502