Active Sites in H-Mordenite Catalysts Probed by NMR and FTIR

Mordenites are widely used in catalysis and environmental protection. The catalytic properties of mordenite are largely determined by the composition of its crystal framework, i.e., the SiO2/Al2O3 molar ratio (MR), and the cationic form. In H-mordenites, the most important characteristic becomes the structure and distribution of acid sites, which depends on the number and distribution of Al tetrahedra in the framework. In the present work, the local structure of these centers in H-mordenite catalysts with a nominal MR varied from 9.9 to 19.8 was studied in detail using a combination of magic angle spinning nuclear magnetic resonance (MAS NMR) and Fourier transform infrared spectroscopy (FTIR). 27Al MAS NMR indicates the presence of extra-framework Al in most of the studied samples that results in a higher real MR of the zeolitic framework compared to the nominal value. Concentrations of Lewis and Brønsted acid sites, as well as of silanol groups were estimated by elemental analysis, NMR, and FTIR spectroscopy. The values of site concentrations obtained from band intensities of adsorbed CO and those of OH groups are compared with the amount of framework and extra-framework aluminum. The advantages and restrictions of different methods of active site characterization are discussed.

[1]  M. Shelyapina,et al.  Ion Exchange in Natural Clinoptilolite: Aspects Related to Its Structure and Applications , 2022, Minerals.

[2]  F. Tian,et al.  Zeolites as Carriers of Nano-Fertilizers: From Structures and Principles to Prospects and Challenges , 2022, Applied Nano.

[3]  M. Shelyapina,et al.  LOCAL STRUCTURE OF PROTONATED MORDENITES WITH SiO2/Al2O3 ≈ 15 PROBED BY MULTINUCLEAR NMR , 2022, Journal of Structural Chemistry.

[4]  D. N. Shchepkin,et al.  Determination of the Extinction Coefficient of Carbon Monoxide Adsorbed on Titanium Dioxide , 2022, Optics and Spectroscopy.

[5]  OUP accepted manuscript , 2022, National Science Review.

[6]  M. Shelyapina,et al.  Aluminum distribution in mordenite-zeolite framework: A new outlook based on density functional theory calculations , 2021, Journal of Solid State Chemistry.

[7]  Ning Wang,et al.  Advances in Catalytic Applications of Zeolite‐Supported Metal Catalysts , 2021, Advanced materials.

[8]  I. Zvereva,et al.  1H NMR Study of the HCa2Nb3O10 Photocatalyst with Different Hydration Levels , 2021, Molecules.

[9]  Tessema Derbe,et al.  A Short Review on Synthesis, Characterization, and Applications of Zeolites , 2021, Advances in Materials Science and Engineering.

[10]  S. Azhari,et al.  Modified Zeolite as Purification Material in Wastewater Treatment: A Review , 2021 .

[11]  V. Petranovskii,et al.  Recent Advances in Catalysis Based on Transition Metals Supported on Zeolites , 2021, Frontiers in Chemistry.

[12]  M. Shelyapina,et al.  The effect of chemical composition on the properties of LTA zeolite: A theoretical study , 2021 .

[13]  I. Zvereva,et al.  A comparative analysis of natural zeolites from various Cuban and Mexican deposits: structure, composition, thermal properties and hierarchical porosity , 2021, Journal of Thermal Analysis and Calorimetry.

[14]  Z. Gan,et al.  Distribution of Aluminum Species in Zeolite Catalysts: 27Al NMR of Framework, Partially-Coordinated Framework, and Non-Framework Moieties. , 2021, Journal of the American Chemical Society.

[15]  C. Popov,et al.  Recent Progress in Synthesis and Application of Nanosized and Hierarchical Mordenite—A Short Review , 2021, Catalysts.

[16]  W. Schwieger,et al.  Preparation and Potential Catalytic Applications of Hierarchically Structured Zeolites with Macropores , 2021, Advanced Materials Interfaces.

[17]  I. Zvereva,et al.  NMR Study of Intercalates and Grafted Organic Derivatives of H2La2Ti3O10 , 2020, Molecules.

[18]  E. Khramov,et al.  Properties of Iron-Modified-by-Silver Supported on Mordenite as Catalysts for NOx Reduction , 2020, Catalysts.

[19]  M. Shelyapina,et al.  Local Structures of Two-Dimensional Zeolites—Mordenite and ZSM-5—Probed by Multinuclear NMR , 2020, Molecules.

[20]  M. Shelyapina,et al.  Mechanism of formation of framework Fe3+ in bimetallic Ag-Fe mordenites - Effective catalytic centers for deNOx reaction , 2020, Microporous and Mesoporous Materials.

[21]  H. Nouali,et al.  Influence of the Compensating Cation Nature on the Water Adsorption Properties of Zeolites , 2020, Molecules.

[22]  Chao Li,et al.  High ethylene selectivity in methanol-to-olefin (MTO) reaction over MOR nanosheets. , 2020, Angewandte Chemie.

[23]  V. Valtchev,et al.  New synthesis routes and catalytic applications of ferrierite crystals. Part 2: The effect of OSDA type on zeolite properties and catalysis , 2020, Microporous and Mesoporous Materials.

[24]  J. Hancsók,et al.  Isomerization of n-C5/C6 Bioparaffins to Gasoline Components with High Octane Number , 2019, Energies.

[25]  I. Zvereva,et al.  Comprehensive Analysis of the Copper Exchange Implemented in Ammonia and Protonated Forms of Mordenite Using Microwave and Conventional Methods , 2019, Molecules.

[26]  M. Shelyapina,et al.  Recognition of depth composition profiles of copper-exchanged mordenites applying analytical methods with different depth vision , 2019, Materials Chemistry and Physics.

[27]  J. Hrenović,et al.  Removal of emerging pathogenic bacteria using metal-exchanged natural zeolite bead filter. , 2019, Water science and technology : a journal of the International Association on Water Pollution Research.

[28]  W. Schmidt,et al.  Studying Proton Mobility in Zeolites by Varying Temperature Infrared Spectroscopy , 2019, Molecules.

[29]  I. Zvereva,et al.  Proton mobility in Ruddlesden–Popper phase H2La2Ti3O10 studied by 1H NMR , 2019, Ceramics International.

[30]  H. Bateni,et al.  Development of Heterogeneous Catalysts for Dehydration of Methanol to Dimethyl Ether: A Review , 2018, Catalysis in Industry.

[31]  A. Gabrienko,et al.  Direct Measurement of Zeolite Brønsted Acidity by FTIR Spectroscopy: Solid-State 1H MAS NMR Approach for Reliable Determination of the Integrated Molar Absorption Coefficients , 2018, The Journal of Physical Chemistry C.

[32]  I. Zvereva,et al.  Mobility of water molecules in sodium- and copper-exchanged mordenites: Thermal analysis and 1 H NMR study , 2018, Microporous and Mesoporous Materials.

[33]  I. Zvereva,et al.  Microwave assisted versus convention Cu2+ exchange in mordenite , 2018 .

[34]  Shengping Wang,et al.  Modifying the acidity of H-MOR and its catalytic carbonylation of dimethyl ether , 2016 .

[35]  C. Ferrara,et al.  Solid-state NMR characterization of the structure and thermal stability of hybrid organic-inorganic compounds based on a HLaNb2O7 Dion-Jacobson layered perovskite. , 2016, Physical chemistry chemical physics : PCCP.

[36]  I. Zvereva,et al.  Effect of preparation method on the valence state and encirclement of copper exchange ions in mordenites , 2016 .

[37]  M. Shelyapina,et al.  A comparative analysis of the protonated and copper exchanged mordenites with SiO2/Al2O3 molar ratio equal to 10 , 2016 .

[38]  Michel Waroquier,et al.  Advances in theory and their application within the field of zeolite chemistry. , 2015, Chemical Society reviews.

[39]  Daniela Pietrogiacomi,et al.  The simultaneous selective catalytic reduction of N2O and NOX with CH4 on Co- and Ni-exchanged mordenite , 2015 .

[40]  M. Fardis,et al.  Water Coordination, Proton Mobility, and Lewis Acidity in HY Nanozeolites: A High-Temperature 1H and 27Al NMR Study , 2015 .

[41]  A. Pestryakov,et al.  Hydrophilicity of Mordenites with Different SiO2/Al2O3 Molar Ratio , 2015 .

[42]  B. Weckhuysen,et al.  Zeolites and Zeotypes for Oil and Gas Conversion , 2015 .

[43]  A. Elzatahry,et al.  The isopropylation of naphthalene with propene over H-mordenite: The catalysis at the internal and external acid sites , 2014 .

[44]  J. Čejka,et al.  Zeolites with Continuously Tuneable Porosity , 2014, Angewandte Chemie.

[45]  J. Casci,et al.  Insights into Brønsted acid sites in the zeolite mordenite , 2014 .

[46]  V. Valtchev,et al.  Tailored crystalline microporous materials by post-synthesis modification. , 2013, Chemical Society reviews.

[47]  A. Tsyganenko.  Variable Temperature IR Spectroscopy in the Studies of Oxide Catalysts , 2011, Topics in Catalysis.

[48]  V. Hronský.  Measurement of Sample Temperatures and Temperature Gradients in Magic-Angle Spinning Nmr , 2013 .

[49]  Joel B. Miller,et al.  Electrical and ionic conductivity effects on magic-angle spinning nuclear magnetic resonance parameters of CuI. , 2010, The Journal of chemical physics.

[50]  Zhicheng Liu,et al.  An Overview of Recent Development in Composite Catalysts from Porous Materials for Various Reactions and Processes , 2010, International journal of molecular sciences.

[51]  C. Grey,et al.  Low Temperature 1H MAS NMR Spectroscopy Studies of Proton Motion in Zeolite HZSM-5 , 2009 .

[52]  K. Harris,et al.  In situ solid-state (1)H NMR studies of hydration of the solid acid catalyst ZSM-5 in its ammonium form. , 2009, Solid state nuclear magnetic resonance.

[53]  A. Tsyganenko,et al.  Integrated absorption coefficient of adsorbed CO , 2008 .

[54]  K. Lazar,et al.  Structure, acidity and redox properties of MCM-22 ferrisilicate , 2008 .

[55]  WerrBn LonwnNsrBrN,et al.  THE DISTRIBUTION OF ALUMINUM IN THE TETRAHEDRA OF SILICATES AND ALUMINATES , 2007 .

[56]  A. Tsyganenko,et al.  FTIR study of CO adsorption on basic zeolites , 2006 .

[57]  M. Shelyapina,et al.  Electronic structure and electric-field-gradients distribution in Y3Al5O12: An ab initio study , 2006 .

[58]  Frédéric Thibault-Starzyk,et al.  Infrared Evidence of a Third Brønsted Site in Mordenites , 2004 .

[59]  G. Vayssilov,et al.  Characterization of Oxide Surfaces and Zeolites by Carbon Monoxide as an IR Probe Molecule , 2003 .

[60]  R. Marzke,et al.  Characterization of H and Cu mordenites with varying SiO2/Al2O3 ratios, by optical spectroscopy, MAS NMR of 29Si, 27Al and 1H, temperature programmed desorption and catalytic activity for nitrogen oxide reduction , 2002 .

[61]  C. Henriques,et al.  NO+ ions as IR probes for the location of OH groups and Na+ ions in main channels and side pockets of mordenite , 2001 .

[62]  N. Essayem,et al.  Characterization of protonic sites in H3PW12O40 and Cs1.9H1.1PW12O40: a solid-state 1H,2H,31P MAS-NMR and inelastic neutron scattering study on samples prepared under standard reaction conditions , 2000 .

[63]  Y. Sugi.  Shape-selective alkylation of biphenyl catalyzed by H-Mordenites , 2000 .

[64]  M. Vicanek.  Electron transport processes in reflection electron energy loss spectroscopy (REELS) and X-ray photoelectron spectroscopy (XPS) , 1999 .

[65]  J. Weitkamp,et al.  Catalysis and Zeolites , 1999 .

[66]  J. Fraissard,et al.  Study of high-silica H-ZSM-5 acidity by 1H NMR techniques using water as base , 1998 .

[67]  G. Magnacca,et al.  A case study: surface chemistry and surface structure of catalytic aluminas, as studied by vibrational spectroscopy of adsorbed species , 1996 .

[68]  H. Gies,et al.  One- and Two-Dimensional High-Resolution Solid-State NMR Studies of Zeolite Lattice Structures , 1991 .

[69]  J. Klinowski,et al.  Two-dimensional J-scaled 29Si NMR COSY of highly siliceous mordenite , 1991 .

[70]  G. Wilkes,et al.  Solid-state 29Si NMR of TEOS-based multifunctional sol-gel materials , 1989 .

[71]  D. Barthomeuf.  Zeolite acidity dependence on structure and chemical environment: correlations with catalysis , 1987 .

[72]  G. Lawes,et al.  Scanning Electron Microscopy and X-Ray Microanalysis , 1987 .