Spatially resolved NMR spectroscopy of heterogeneous gas phase hydrogenation of 1,3-butadiene with <i>para</i>hydrogen

Svyatova, Alexandra; Kononenko, Elizaveta S.; Kovtunov, Kirill V.; Lebedev, Dmitry; Gerasimov, Evgeny Yu.; Bukhtiyarov, Andrey V.; Prosvirin, Igor P.; Bukhtiyarov, Valerii I.; Müller, Christoph R.; Fedorov, Alexey; Koptyug, Igor V.

doi:10.1039/c9cy02100k

Cited by 16 publications

(19 citation statements)

References 51 publications

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“…In the reactor, the group was able to monitor, on a scale of several millimeters, the distribution of products and educts online during catalysis, thus obtaining information about reaction zones and flow profiles inside the reactor. [ 137,138 ] Into the reactant gas flow, they added hyperpolarized xenon, using the well‐known temperature dependence of the chemical shift of 129 Xe to calibrate the temperature inside an in situ reaction chamber. [ 139 ] HP xenon gas thus proved to be a more accurate temperature probe than an external thermocouple.…”

Section: Recent Applicationsmentioning

confidence: 99%

¹²⁹Xe NMR on Porous Materials: Basic Principles and Recent Applications

Wisser

Hartmann

2020

Adv Materials Inter

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A large number of functional and catalytic materials exhibit porosity, often on different length scales and with a hierarchical structure. The assessment of pore sizes, pore geometry, and pore interconnectivity is complex and usually not feasible by classical spectroscopic and diffraction techniques. One of the most powerful methods to probe these parameters is nuclear magnetic resonance (NMR) spectroscopy of xenon, which is introduced into the pore system. Adsorbed to the pore walls, it acts as probe nucleus. In this tutorial review, an introduction into the basic principles of 129Xe NMR spectroscopy and the models developed to determine pore sizes in different materials are given. The possibilities and limitations of this method for obtaining insights into hierarchical structures of functional materials are highlighted and a review of recent works is presented.

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Section: Recent Applicationsmentioning

confidence: 99%

¹²⁹Xe NMR on Porous Materials: Basic Principles and Recent Applications

Wisser

Hartmann

2020

Adv Materials Inter

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“…For that reason, in 2019 a new type of model MRI-compatible glass reactors with a thin catalytic layer was developed and used in operando studies of heterogeneous hydrogenation with parahydrogen. [112,113] Besides causing only a minor perturbation of the magnetic field homogeneity, the reactors also provide efficient heat and mass transfer. First experiments were performed on reactors comprising Rh nanoparticles supported on a titania layer deposited on a glass tube.…”

Section: Mri Of Catalytic Reactorsmentioning

confidence: 99%

“…Later the approach was largely extended to different active metals (Pt, Pd, Rh, Ir) and support layers (CeO 2 , SiO 2 , Al 2 O 3 , TiO 2 ) in the hydrogenation of 1,3-butadiene which leads to the formation of several different products. [113] NMR spectra were acquired along the Z-axis of the reactor to obtain selective spatial distributions of different products (Figure 10b).…”

Section: Mri Of Catalytic Reactorsmentioning

confidence: 99%

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Heterogeneous Catalysis and Parahydrogen‐Induced Polarization

et al. 2021

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Parahydrogen‐induced polarization with heterogeneous catalysts (HET‐PHIP) has been a subject of extensive research in the last decade since its first observation in 2007. While NMR signal enhancements obtained with such catalysts are currently below those achieved with transition metal complexes in homogeneous hydrogenations in solution, this relatively new field demonstrates major prospects for a broad range of advanced fundamental and practical applications, from providing catalyst‐free hyperpolarized fluids for biomedical magnetic resonance imaging (MRI) to exploring mechanisms of industrially important heterogeneous catalytic processes. This review covers the evolution of the heterogeneous catalysts used for PHIP observation, from metal complexes immobilized on solid supports to bulk metals and single‐atom catalysts and discusses the general visions for maximizing the obtained NMR signal enhancements using HET‐PHIP. Various practical applications of HET‐PHIP, both for catalytic studies and for potential production of hyperpolarized contrast agents for MRI, are described.

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“…The control of a reactant transport in microporous heterogeneous catalysts is a focal point of a permanent scientific and practical interest because it directly affects the catalyst performance: reaction rates and product selectivity. [1] The porous matrix can regulate the reacting species mobility in a number of ways. In general, the geometry of catalyst pores affects the diffusion of reagents to the active sites.…”

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confidence: 99%

Molecular Mobility of Tert‐butyl Alcohol Confined in a Breathing MIL‐53 (Al) Metal‐Organic Framework

et al. 2020

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We present a detailed solid‐state NMR characterization of the molecular dynamics of tert‐butyl alcohol (TBA) confined inside breathing metal‐organic framework (MOF) MIL‐53(Al). 27Al MAS NMR has demonstrated that TBA adsorption induces the iX phase of MIL‐53 material with partially shrunk channels. 2H solid‐state NMR has shown that the adsorbed alcohol exhibits anisotropic rotations of the methyl groups around two C3 axes and librations of the molecule as a whole about the axis passing through the TBA C−O bond. These librations are realized by two distinct ways: fast molecule orientation change during the translational jump diffusion along the channel with characteristic time τD of about 10−9 s at 300 K; slow local librations at a single coordination site, representing framework hydroxyl groups, with τl≈10−6 s at 300 K. Self‐diffusion coefficient of the alcohol in the MOF has been estimated: D=3.4×10−10 m2 s−1 at 300 K. It has been inferred that both the framework flexibility and the interaction with framework hydroxyl groups define the dynamics of TBA confined in the channels of MIL‐53 (Al).

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Spatially resolved NMR spectroscopy of heterogeneous gas phase hydrogenation of 1,3-butadiene with parahydrogen

Abstract: Glass tube reactors with Pd, Pt, Rh or Ir nanoparticles dispersed on a thin layer of TiO2, CeO2, SiO2 or Al2O3 provided mechanistic insight into the hydrogenation of 1,3-butadiene using parahydrogen.

Cited by 16 publications

References 51 publications

¹²⁹Xe NMR on Porous Materials: Basic Principles and Recent Applications

¹²⁹Xe NMR on Porous Materials: Basic Principles and Recent Applications

Heterogeneous Catalysis and Parahydrogen‐Induced Polarization

Molecular Mobility of Tert‐butyl Alcohol Confined in a Breathing MIL‐53 (Al) Metal‐Organic Framework

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Spatially resolved NMR spectroscopy of heterogeneous gas phase hydrogenation of 1,3-butadiene with parahydrogen

Abstract: Glass tube reactors with Pd, Pt, Rh or Ir nanoparticles dispersed on a thin layer of TiO2, CeO2, SiO2 or Al2O3 provided mechanistic insight into the hydrogenation of 1,3-butadiene using parahydrogen.

Cited by 16 publications

References 51 publications

129Xe NMR on Porous Materials: Basic Principles and Recent Applications

129Xe NMR on Porous Materials: Basic Principles and Recent Applications

Heterogeneous Catalysis and Parahydrogen‐Induced Polarization

Molecular Mobility of Tert‐butyl Alcohol Confined in a Breathing MIL‐53 (Al) Metal‐Organic Framework

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Product

Resources

About

¹²⁹Xe NMR on Porous Materials: Basic Principles and Recent Applications

¹²⁹Xe NMR on Porous Materials: Basic Principles and Recent Applications