Mechanistic studies of zeolite catalysis via in situ solid-state nuclear magnetic resonance spectroscopy: progress and prospects
Chao Wang1, Min Hu1,2, Jun Xu1(), Feng Deng1()
. National Center for Magnetic Resonance in Wuhan, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan 430071, China . University of Chinese Academy of Sciences, Beijing 100049, China
Zeolites, with their exquisite microporous frameworks and tailorable acidities, serve as ubiquitous catalysts across a diverse spectrum of industrial applications, ranging from petroleum and coal processing to sustainable chemistry and environmental remediation. Optimizing their performance hinges on a thorough understanding of the structure-performance relationship. In situ solid-state nuclear magnetic resonance spectroscopy has emerged as a critical tool, providing unparalleled atomic-level insights into both structure and dynamic aspects of zeolite-catalyzed reactions. Herein, we review recent progress in the development and application of the in situ solid-state nuclear magnetic resonance technique to zeolite catalysis. We first review the in situ nuclear magnetic resonance techniques used in zeolite-catalyzed reaction, including batch-like and continuous-flow reaction modes. The conditions and limitations for these techniques are thoroughly summarized. Subsequently, we review the applications of in situ nuclear magnetic resonance techniques in zeolite-catalyzed reaction, focusing on some important catalytic reactions like methanol-to-hydrocarbons, ethanol dehydration, alkane activation, and beyond. Emphasis is placed on the strategies of specific in situ nuclear magnetic resonance methodologies to tackle critical challenges encountered in these fields, such as probing intermediates and unraveling reaction mechanisms. Additionally, we discuss the burgeoning opportunities and prospective challenges associated with in situ nuclear magnetic resonance studies of zeolite-catalyzed processes.
Just Accepted Date: 05 July 2024Issue Date: 28 November 2024
Cite this article:
Chao Wang,Min Hu,Jun Xu, et al. Mechanistic studies of zeolite catalysis via in situ solid-state nuclear magnetic resonance spectroscopy: progress and prospects[J]. Front. Chem. Sci. Eng.,
2025, 19(1): 1.
Pressure: < 70 barTemperature: < melting point of ampoule material
From ambient to high temperature
Suitable for reactants that are difficult to adsorb or undergo transformation;provides sufficient contact time for reactants with catalysts;capable of reheating after quenching the reaction; capable of quantifying transformation of observed species
Difficult to differentiate reactants, intermediates and products; not amenable to repeated/renewed usage; challenging to secure the tube assembly and facilitate NMR rotor rotation; difficult to maintain stable/unvarying pressure levels
Pressure: atmosphere pressureTemperature: low (i.e., liquid N2 temperature) temperature to 300 °C
From cryogenic to high temperature
Capable of reactant adsorption at low temperatures;the reaction can be rapidly quenched after a very short time; can be heated inside a MAS NMR probe; the rotor can be reloaded with the reactant
Challenging to differentiate the individual intermediate, reactant and product species; unable to withstand/tolerate elevated reaction pressures
HTHP (high-temperature and high-pressure) MAS NMR rotor [87?91]
Pressure: < 400 barTemperature: < 250 °C
< 250 °C
Can operate at high temperatures and pressures; able to maintain a constant pressure; can be used multiple times; can operate in liquid-solid, gas-liquid-solid, or other multi-phase systems
Specialized rotors are required
Continuous flow
CF MAS NMR [83,92]
Pressure: atmosphere pressureTemperature: < 400 °C
< 400 °C
Mimicking a real flow reaction in fixed-bed reactor; capable to combine with other operando spectroscopy or online chromatography/mass spectrometer
A lower MAS rate results in a reduced signal-to-noise ratio; sensitivity loss at high temperatures; hard to conduct at high pressure
Pulse-quench technique [93,94]
Pressure: atmosphere to high pressureTemperature: reaction temperature
Ambient temperature
Reaction can be quickly quenched; active species can be “frozen” on catalyst surface; facile to connect with online gas chromatography/mass spectrometer (GC/MS)
Analysis is performed on the used catalyst
Tab.1 Summary of in situ ssNMR techniques
Fig.1 Diagram of (a) HTHP MAS NMR rotors developed by Jaegers et al. Reprinted with permission from Ref. [88], copyright 2020, American Chemical Society. (b) The WHiMS rotors. Reprinted with permission from Ref. [90], copyright 2018, American Chemical Society.
Fig.2 Proposed reaction mechanism of MTH. (a) Direct reaction mechanism (Zeo represents zeolite); (b) HCP mechanism.
Fig.3 Combination of 13C-13C PDSD and 13C-1H HETCOR MAS NMR spectroscopy to identify the surface-acetate species and methyl acetate. (a) Zooms from 2D 13C-13C (blue) and 13C-1H (red) MAS ssNMR spectra, respectively, indicating surface acetate and methyl acetate resonances. (b) ssNMR signals of surface-bound formate in the 13C-1H spectra (light blue). (c) Zoom of aromatic signals from 2D 13C-13C (blue) and 13C-1H (light blue) MAS NMR spectra, respectively. The sample was prepared from 30 min 13C methanol reaction over H-SAPO-34 at 400 °C. Reprinted with permission from Ref. [152], copyright 2016, Wiley-VCH.
Fig.4 Identification of the formation of SMS-EFAL and its reactivity in MTH reaction. (a) 13C NMR spectra of trapped products obtained from reaction of 13C-methanol for 1 min, followed by co-feeding 13C-methanol and 13C-formaldehyde for another 1 min over dealuminated H-ZSM-5 at 250–350 °C. (b) 13C-{27Al} RESPDOR NMR spectra and 13C-27Al internuclear distance measurement, confirming the formation of SMS-EFAL. Theoretically optimized model of SMS-EFAL is also shown. (c) Reaction mechanism for the formation of the first C–C bond in MTH reaction. The theoretically calculated activation energy (Eact) and reaction energy (Ereact) values are given in kcal·mol–1. Reprinted with permission from Ref. [133], copyright 2018, Wiley-VCH.
Fig.5 Combination of solid-state 13C MAS NMR and solution 13C NMR to analyze the HCP from methanol conversion over H-ZSM-5. (a) The trapped products obtained from reaction of 13C methanol over H-ZSM-5 at 350 °C for 30 min. The 13C chemical shifts of both solid-state and liquid-state NMR are indicated for the observed carbocations (those from liquid-state NMR are in the parentheses). Asterisks denote spinning sidebands. For liquid-state NMR, the carbocations were regenerated and stabilized by adding concentrated sulfuric acid (98%) into the extract solution of the reacted H-ZSM-5 at room temperature. The confirmed cyclopentenyl cations are shown in the top. Reprinted with permission from Ref. [141], copyright 2015, Wiley-VCH. (b) The reaction mechanism for the formation of ethene and propene in methanol conversion over H-ZSM-5. Reprinted with permission from Ref. [140], copyright 2015, Wiley-VCH, and Ref. [141], copyright 2015, Elsevier.
Fig.6 (a) 2D 13C-13C refocused INADEQUATE spectrum of 13C enriched MTO activated H-ZSM-5. Signals corresponding to carbenium ions (black) and to other neutral carbon species (blue) are highlighted to distinguish them. The assignments of the different carbenium species are given in different colors. Asterisks (*) denote spinning sidebands. (b) Molecular structures of the carbenium ions are identified, color-coded according to their assignments. (c) Extracted horizontal traces of carbenium ion I with arrows in dashed lines indicating their positions in the 2D map. The corresponding double quantum frequency δDQ of each slice is also given in the figure. The chemical shifts of different 13C sites are given in parenthesis. Unlabelled peaks are from other carbenium ions or aromatic species. Reprinted with permission from Ref. [163], copyright 2017, the Royal Society of Chemistry.
Fig.7 Proposed reaction mechanism for the conversion of ethanol to hydrocarbons over ZSM-5 (EtOH: ethanol, DEE: diethyl ether, C2H4: ethene, C3H6: propene, C4H8: butene, C5+: olefinic hydrocarbons containing more than five carbon atoms, aromatics: hydrocarbons containing one or more aromatic rings, C2H4*: ethene surface species, C4H8*: butene surface species, C*ali: aliphatic surface species, C*aro: aromatic surface species. Route I (violet): dimerization of ethene to butene, Route II (green): formation of propene and butene via aliphatic surface intermediates, Route III (blue): formation of propene via aromatic surface intermediates). Reprinted with permission from Ref. [167], copyright 2016, Wiley-VCH.
Fig.8 Investigation of ethanol transformation over zeolites: (a) in situ flow 13C MAS NMR spectra of 13CH313CH2OH conversion over H-ZSM-5 with time on stream and at elevating temperatures; (b) proposed ethanol dehydration routes. Reprinted with permission from Ref. [169], copyright 2019, Springer Nature.
Fig.9 13C MAS NMR investigation of ethanol transformation over ZSM-5: (a) 2D 13C-13C PDSDNMR spectra of adsorbed species over ZSM-5 after 13C ethanol reaction; (b) proposed mechanism for the homologation-reaction of ethanol in ETH process. Reprinted with permission from Ref. [170], copyright 2019, Wiley-VCH.
Fig.10 (a) Advanced 2D 13C-13C INADEQUATE NMR experiment probing trapped carbocations of 13CH313CH2OH conversion. The assignments of the different carbenium ions are highlighted in different colors. (b) Ethene and propene formation via triple-cycle routes with the participation of different intermediate species in ETH over H-ZSM-5. Calculated free energy barriers at 250 °C are given in kcal·mol–1. (R the alkyl groups). Reprinted with permission from Ref. [172], copyright 2022, Elsevier.
Fig.11 Identification of surface species over Mo/H-ZSM-5 in methane transformation by ssNMR. (a) J-coupling based 2D MAS ssNMR 13C-1H correlations experiment to confirm the mobile molecules. (b) Dipolar-coupling based 2D MAS ssNMR 13C-1H correlations experiment to confirm the rigid molecules. The spectra were obtained after (13C-) MDA reaction over Mo/ZSM-5 at 725 °C for 50 min (in blue) and 2 h (in red). (c) Reaction mechanism for the formation of C–C bond from methane. Reprinted with permission from Ref. [226], copyright 2020, Wiley-VCH.
Fig.12 1H{95Mo} S-RESPDOR NMR spectra of (a) fresh Mo/ZSM-5, (b) Mo/ZSM-5 reacted for 30 min and (c) for 120 min of MDA reaction at 973 K. Normalized ΔS of (d) Br?nsted acid, (e) olefins, and (f) aromatics vs. MDA reaction time (ΔS = S0 – S). Reprinted with permission from Ref. [74], copyright 2021, Wiley-VCH.
Fig.13 13C CP/MAS NMR spectra of n-butane-1-13C adsorbed on Zn2+/H-BEA zeolite. The spectrum before sample heating at elevated temperatures is shown in (a). The sample was heated (b) at 453 K for 100 min, (c) at 523 K for 60 min, (d) at 573 K for 60 min, and (e) at 623 K for 60 min (All spectra were recorded at room temperature (about 298 K). The spectrum region from –30 to 50 ppm is highlighted in the frame for better observation of the detected signals. Asterisks denote spinning side bands). Reprinted with permission from Ref. [237], copyright 2020, Elsevier.
Fig.14 In situ solid state 13C NMR to investigate the propane aromatization over Ga/ZSM-5: (a) 13C CP/MAS NMR of the adsorbed hydrocarbon species on 1% Ga-ZSM-5 during propane aromatization reaction at 350 °C for 0–320 s; (b) propane conversion with reaction time over H-ZSM-5 and Ga/ZSM-5; (c) proposed propane direct and cyclopentenyl cations mediated aromatization routes. Reprinted with permission from Ref. [238], copyright 2021, Wiley-VCH.
Fig.15 HTHP MAS NMR to investigate the cyclohexanol dehydration over beta zeolite. (a) Concentration-time profiles of reactants and products in the alkylation of phenol by cyclohexanol and cyclohexene. The concentration was determined by 13C MAS NMR spectra. (b) Stacked plot of in situ13C MAS NMR spectra of 1-13C-phenol alkylation with 1-13C-cyclohexanol at 127 °C. Reprinted with permission from Ref. [98], copyright 2017, American Chemical Society. (c) Reaction pathways proposed on the basis of in situ13C NMR measurements of cyclohexanol dehydration. Reprinted with permission from Ref. [99], copyright 2018, Springer Nature.
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