Empowering gas-phase operando NMR and MRI of packed-bed reactors through rational catalyst design

Empowering gas-phase operando NMR and MRI of packed-bed reactors through rational catalyst design Научная публикация

Журнал

Chemical Engineering Journal
ISSN: 1385-8947

Вых. Данные

Год: 2026, Том: 535, Номер статьи : 175379, Страниц : 10 DOI: 10.1016/j.cej.2026.175379

Авторы

Kononenko Elizaveta S. ^1,2 , Skovpin Ivan V. ¹ , Burueva Dudari B. ¹ , Rogozhnikov Vladimir N. ³ , Gerasimov Evgeny Yu. ³ , Kovtunova Larisa M. ^3,1 , Koptyug Igor V. ¹

Организации

1	International Tomography Center SB RAS, 3A Institutskaya St., 630090, Novosibirsk, Russia
2	Novosibirsk State University, 2 Pirogova St., 630090, Novosibirsk, Russia
3	Boreskov Institute of Catalysis SB RAS, 5 Acad. Lavrentiev Pr., Novosibirsk, 630090, Russia

Understanding the spatial organization and dynamics of physicochemical processes in operating catalytic reactors is essential for optimizing their performance. Unfortunately, the power of NMR-based techniques is impaired in such studies due to severe broadening and distortions of NMR signals caused by the heterogeneity of granular catalyst. To surmount this critical obstacle, we utilized for the first time hollow spheres used as catalyst supports. Granular beds of the catalyst comprising Rh nanoparticles supported on hollow alumina spheres provided an excellent magnetic field homogeneity within the NMR detection volume. This enabled acquisition of 1H NMR spectra of reacting gases with linewidths up to 0.1 ppm under flow conditions. Consequently, operando magnetic resonance spectroscopy (MRS) of heterogeneous propene hydrogenation allowed quantitative monitoring of substrate-to-product conversion profiles along the catalyst bed with 1.25 mm spatial resolution for short time. The reaction zone was further visualized by infrared thermography, correlating the localization of heat release with chemical conversion in this exothermic reaction. Chemical shift-selective 3D magnetic resonance imaging (MRI) enabled separate spatial visualization of the reactant and product distributions within the heterogeneous catalytic system. MRS experiments using parahydrogen for signal enhancement conclusively confirmed high magnetic field homogeneity by resolving the antiphase shape of the NMR signals of hyperpolarized propane and enabling spatially resolved detection of hyperpolarization buildup and decay within the granular catalyst layer. Overall, the results demonstrate that the combination of hollow catalyst supports with advanced NMR techniques enables non-invasive operando analysis of gas-phase catalytic processes with high spatial and spectral resolution, and offers new opportunities for studying reaction mechanisms and hyperpolarization dynamics in heterogeneous systems.

Kononenko E.S. , Skovpin I.V. , Burueva D.B. , Rogozhnikov V.N. , Gerasimov E.Y. , Kovtunova L.M. , Koptyug I.V.
Empowering gas-phase operando NMR and MRI of packed-bed reactors through rational catalyst design
Chemical Engineering Journal. 2026. V.535. 175379 :1-10. DOI: 10.1016/j.cej.2026.175379 OpenAlex

Принята к публикации:	18 мар. 2025 г.
Поступила в редакцию:	24 нояб. 2025 г.
Опубликована online:	19 мар. 2026 г.
Опубликована в печати:	23 мар. 2026 г.

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