NMR-Festkörper-Hochauflösung für Strukturuntersuchungen Festkörper-NMR-Untersuchungen der Struktur und Dynamik in anorganischen Materialien Dieter Freude Abteilung Grenzflächenphysik, Universität Leipzig, www.grenzflaechenphysik.de Vortrag am 10. Februar 2004 an der Universität Karlsruhe, Forschergruppe 338, Professor Hans Buggisch Elementarschritte der heterogenen Katalyse In situ-MAS NMR-Spektroskopie NMR-Festkörper-Hochauflösung für Strukturuntersuchungen Faujasite

Current Contents® 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000 NMR IR Raman MS EPR DK 1994 1995 1996 1997 1998 1999 2001 The Current Contents© (Physical, Chemical and Earth Sciences) referred in the last years to more than 200 000 publications, among them 35 000 spectroscopic studies, about 9 000 NMR studies, among them to 2 000 studies of solids. From all NMR studies refer ca. 35% to 1H, ca. 25% to 13C, ca. 8% to 31P, ca. 8% to 15N, ca. 4% to 29Si and ca. 2% to 19F as I = ½ nuclei. Ca. 3% refer to 27Al and ca. 1% to 11B, 1% to 7Li, 1% to 23Na, 1% to 51V (half-integer spin nuclei I >½). Ca. 4% refer to 2H, ca. 0.5% to 14N and 0,5% to 6Li (integer spin nuclei with I = 1).

Vergleich im Jahre 2000 zwischen Physical, Chemical & Earth Sciences und Life Sciences 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000 NMR IR Raman MS EPR X-ray spectroscopy DK X-ray structure Phys Life

Harry Pfeifer's NMR-Experiment 1951 in Leipzig H. Pfeifer: Über den Pendelrückkoppelempfänger und die Beobachtungen von magnetischen Kernresonanzen, Diplomarbeit, Universität Leipzig, 1952

Laser supported high-temperature MAS NMR Laser-Einsatz: Laser supported high-temperature MAS NMR

Stop-and-go A laser beam makes it possible to switch from room temperature, at which chemical reactions in zeolites are commonly too slow to be measured, to temperatures up to 800 K, at which the reaction takes place within a few seconds. Irreversible reactions: The stop-and-go technique utilizes the heating rate of the laser-supported probe to expose the sample to short periods at high temperatures and splits the measuring time in consecutive stop and go periods. During the go periods the time development of irreversible reactions can be monitored at high temperatures by equidistant 1H MAS NMR signals. The reaction state after each go period is recorded by a 13C MAS NMR spectrum at room temperature during the stop period. Reversible reactions: FID accumulation and phase cycling can be realized by multiple repetition of the heating-cooling cycle. The recording of one complete heating and cooling cycle by means of several FIDs equidistant in time is denoted herein as one FID set.

Hochfeld-Festkörper-NMR: Festkörper-NMR-Spektroskopie im hohen Magnetfeld, einschließlich DOR und MQMAS für Quadrupolkerne wie 17O 3QMAS pulse program DOR rotor  The Bruker Avance 750 spectrometer in Leipzig, painting by Dr. Taro Ito

Was ist Ziel neuer Festkörper-NMR-Techniken zur Untersuchung von Quadrupolkernen? Verbesserung der Auflösung zur genaueren Bestimmung der chemischen Verschiebung von Signalen Verbesserung der Auflösung zur genaueren Bestimmung von Quadrupolparametern Verbesserung der Nachweisempfindlichkeit Theoretische Linienform des Zentralübergangs mit Anisotropiefaktor h = 0,2 und geringer Gaußverbreiterung für das ohne Probenrotation aufgenommene statische Spektrum, das MAS-Spektrum und das MQMAS NMR-Spektrum. DOR-Spektrum sieht wie MQMAS aus, hat aber meist viele Seitenbänder.

Einquanten- und Multiquantenübergänge Der Aluminiumkern hat den Spin I = 5/2. Entsprechend ergeben sich sechs Energieniveaus im starken äußeren Magnetfeld.

Satelliten, Zentralübergang, Verbreit. 2. Ordnung

MAS, Verbr. 2. Ordnung, symmetrische Übergänge

MQMAS and DOR MQMAS pulse sequences: Selection of the desired coherence transfer path by the phase cycling. double rotation: 2 = 54,74° 1 = 30,56° Iy/Ix tuned to J Z Na-LSX 3QMAS Na,K-LSX 17O MAS 17O DOR 11,7 T 17,6 T

Double rotation wide-bore probe νouter  1.8 kHz, νinner  7.6 kHz, narrow-bore probe νouter  1.5 kHz, νinner  7.5 kHz,

NMR-Diffusometrie (Kärger): PFG NMR-Messtechnik

Festkörper-Technik für Diffusometrie: SFG NMR-Messtechnik für Temperaturen bis 700 K Result: The magnetic field gradient in the fringe field of the BRUKER wide-bore 17.6 T magnet amounts 40.56 T m-1 for a proton resonance frequency of 303 MHz.

1H MAS NMR of porous materials

1H MAS NMR spectra with and without dipolar dephasing by 27Al high power irradiation and difference spectra. Non- framework aluminium (EF), OH group of the framework (F). Spectra shows SiOH groups at framework defects, at the surface, SiOHAl-bridging hydroxyl groups, Al – OH group. modul30 II/D calc. temp. 900 °C dehydrated modul30 I/D calc. temp. 550 °C dehydrated 2.2 ppm 2.9 ppm 2.9 ppm 1.7 ppm 2.2 ppm 1.7 ppm without dephasing with dephasing 4.2 ppm 2.9 ppm 2.9 ppm difference spectrum 10 8 6 4 2 2 4 10 8 6 4 2 2 4  / ppm  / ppm

29Si MAS NMR

29Si MAS NMR-Spektrum von Silicalit 1, das aus einem SiO2-Gerüst mit 24 unterschiedlichen Si-Positionen pro Einheitszelle besteht (Fyfe 1987)

27Al MAS NMR

Hydrothermally treated zeolites ZSM-5 four-fold coordinated five-fold coordinated six-fold coordinated nL = 195 MHz nRot = 15 kHz nL = 195 MHz nRot = 30 kHz nL = 130 MHz nRot = 10 kHz AlPO4-14, 27Al 3Q MAS spectrum

17 O NMR, hydrothermal enrichment H217O H217O (25 - 43% enriched), vapor pressure of 2.4 kPa in a nitrogen stream zeolite embedded in quartz glass particles temperature between 150 °C and 250 °C duration of some hours, water is recycled N 2 zeolite reactor heater N 2 ice condenser

Question: Exists a correlation between 17O chemical shift and T-O-T bond angle  ? In 29Si NMR a relation exists between the isotropical value of the chemical shift and the mean value of the Si-O-T angles a (T=Si, Al), cf. Radeglia and Engelhardt [1]:   d (29Si) = -223.9r - 7.2 + 5m . r = cosa /(cosa - 1) is the s-character of the oxygen hybrid orbitals, and m the coordination number of Si atoms to Al atoms, commonly Q4(m Al). 17O DAS NMR studies of the SiO2 polymorph coesite by Grandinetti et. al. [2] yielded the correlations: 17O DOR NMR for the oxygen sites of hydrated Na-A ( ) and Na,K-LSX ( ).  (17O) /ppm = 214 + 136  (17O) /ppm = 0.65a /° + 134 correlation coefficients: 0.924 and 0.91 Grandinetti et. al. [2] and Bull et. al. [3], [4] claimed that a monotone correlation between Si-O-Si bond angle and 17O chemical shift d does not exist. [1] Chem. Phys. Lett. 114 (1985) 28 [2] J. Phys. Chem. 99 (1995) 12341 [3] J. Am. Chem. Soc. 120 (1998) 3510 [4] J. Am. Chem. Soc. 122 (2000) 4948

Mobility in the Brønsted Center Proton mobility of bridging hydroxyl groups in zeolites H-Y and H-ZSM-5 was monitored in the temperature range from 160 to 790 K. The full width at half maximum of the 1H MAS NMR spectrum narrows by a factor of 24 for zeolite H-ZSM-5 and a factor of 55 for zeolite 85 H-Y. For the latter an activation energy of 78 kJ mol has been determined. The values of the activation energy for the proton mobility around an aluminum atom are useful for the evaluation of quantum chemical models. zeolite 85 H-Y Ea = 78 kJ/mol zeolite H-ZSM-5 Ea = 18 kJ/mol

Proton transfer between Brønsted sites and benzene molecules in zeolites H-Y In situ 1H MAS NMR spectro-scopy of the proton transfer between bridging hydroxyl groups and benzene molecu-les yields temperature depen-dent exchange rates over more than five orders of magnitude. H-D exchange and NOESY MAS NMR experiments were performed by both conventional and laser heating up to 600 K.

Exchange rate as a dynamic measure of Brønsted acidity Arrhenius plot of the H-D and H-H exchange rates for benzene molecules in the zeolites 85 H-Y and 92 H-Y. The values which are marked by blue or red were measured by laser heating or conventional heating, respectively. The variation of the Si/Al ratio in the zeolite H-Y causes a change of the deprotonation energy and can explain the differences of the exchange rate of one order of magnitude in the temperature region of 350600 K. However, our experimental results are not sufficient to exclude that a variation of the pre-exponential factor caused by steric effects like the existence of non-framework aluminium species is the origin of the different rates of the proton transfer.

Herzlichen Dank für die Beiträge von Horst Ernst Thomas Loeser Johanna Kanellopoulos Jörg Kärger Bernd Knorr Dieter Michel Lutz Moschkowitz Ulf Pingel Dagmar Prager Daniel Prochnow Deutsche Forschungsgemeinschaft Max-Buchner-Stiftung