TY - JOUR

T1 - The Elusive Structure of Magadiite, Solved by 3D Electron Diffraction and Model Building

AU - Krysiak, Yaşar

AU - Maslyk, Marcel

AU - Silva, Bruna Nádia

AU - Plana-Ruiz, Sergi

AU - Moura, Hipassia M.

AU - Munsignatti, Erica O.

AU - Vaiss, Viviane S.

AU - Kolb, Ute

AU - Tremel, Wolfgang

AU - Palatinus, Lukáš

AU - Leitão, Alexandre Amaral

AU - Marler, Bernd

AU - Pastore, Heloise O.

N1 - Funding Information: Y.K. is very grateful to the Stipendienstiftung Rheinland-Pfalz and Forschung und Technologietransfer Universität Mainz for financial support. B.N.N.S., V.S.V., H.M.M., A.A.L., and H.O.P. thank to the National Council for Research and Technology (CNPq productivity grant for AAL and HOP and research grant process 309729/2017-3 for fellowships). This research was supported by the Czech Science Foundation (project number 19-08032S), by the Foundation for Research in the State of Minas Gerais (FAPEMIG, CEX APQ 02191/2017), and by the Foundation for Research in the State of São Paulo (FAPESP 14/06942-0), Brazil. The National Center for High Performance Data Processing (CENAPAD-SP, Brazil) is acknowledged for the computation facilities.

PY - 2021/5/11

Y1 - 2021/5/11

N2 - In addition to a great swelling ability, layered silicates also allow the functionalization of their interlayer region to form various robust green materials that are used as CO2 adsorbents, drug carriers, or catalysts. Here, the unique magadiite structure, which has resisted elucidation despite many attempts and applications the material offers, is finally described. A material-specific strategy allowed the use of 3D electron diffraction which led to the success of deciphering the atomic structure. In order to enable an ab initio structure solution of the electron beam sensitive material, a sodium-free dehydrated form of magadiite was synthetically isolated, and, from that, it was subsequently possible to derive a structure model for the sodium form of magadiite, later successfully refined against powder X-ray diffraction data. Furthermore, a geometry optimization and simulations of spectroscopic data with DFT methods confirm the obtained crystal structure of sodium magadiite. These results finally prompted a detailed description of the layers and of the chemically active interlayer region and provide a huge impact toward the design of new and more efficient materials based on functionalized magadiite and related structures.

AB - In addition to a great swelling ability, layered silicates also allow the functionalization of their interlayer region to form various robust green materials that are used as CO2 adsorbents, drug carriers, or catalysts. Here, the unique magadiite structure, which has resisted elucidation despite many attempts and applications the material offers, is finally described. A material-specific strategy allowed the use of 3D electron diffraction which led to the success of deciphering the atomic structure. In order to enable an ab initio structure solution of the electron beam sensitive material, a sodium-free dehydrated form of magadiite was synthetically isolated, and, from that, it was subsequently possible to derive a structure model for the sodium form of magadiite, later successfully refined against powder X-ray diffraction data. Furthermore, a geometry optimization and simulations of spectroscopic data with DFT methods confirm the obtained crystal structure of sodium magadiite. These results finally prompted a detailed description of the layers and of the chemically active interlayer region and provide a huge impact toward the design of new and more efficient materials based on functionalized magadiite and related structures.

UR - http://www.scopus.com/inward/record.url?scp=85106414700&partnerID=8YFLogxK

U2 - 10.1021/acs.chemmater.1c00107

DO - 10.1021/acs.chemmater.1c00107

M3 - Article

AN - SCOPUS:85106414700

VL - 33

SP - 3207

EP - 3219

JO - Chemistry of materials

JF - Chemistry of materials

SN - 0897-4756

IS - 9

ER -