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Spatially Resolved NMR Spectroscopy for Operando Studies of Heterogeneous Hydrogenation with Parahydrogen

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Abstract

Magnetic resonance imaging (MRI) is a unique tool for operando studies owing to its non-invasive manner of signal detection. MRI can provide information about structure of the reactor, distribution of the reagents and products in the reactor, and heat and mass transport processes. However, the heterogeneous solid phase of a catalyst in a reactor largely distorts the static magnetic field of an MRI instrument, which leads to a major loss in spectroscopic resolution and measurement sensitivity. On top of that, many chemical reactions involve gases, so that the reduced spin density compared to liquids is yet another complication in such studies. To overcome these challenges, a proper choice of model catalytic reactors for NMR-based experiments is required. In this study, the configuration of model catalytic reactors was varied to explore its effect on the spatially resolved 1H NMR spectra acquired during heterogeneous hydrogenation of propene to propane with parahydrogen over several supported metal catalysts. The results demonstrate that a judicial choice of a reactor geometry in combination with signal enhancement provided by parahydrogen makes such studies feasible and informative.

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References

  1. R. Hou, Catalytic and process study of the selective hydrogenation of acetylene and 1,3-butadiene (Springer, Singapore Singapore, 2017)

    Book  Google Scholar 

  2. A.N.R. Bos, K.R. Westerterp, Mechanism and kinetics of the selective hydrogenation of ethyne and ethene. Chem. Eng. Process. Process Intensif. 32, 1–7 (1993)

    Article  Google Scholar 

  3. L. Liu, A. Corma, Metal catalysts for heterogeneous catalysis: from single atoms to nanoclusters and nanoparticles. Chem. Rev. 118, 4981–5079 (2018)

    Article  Google Scholar 

  4. G. Eigenberger, W. Ruppel, in Ullmann’s Encycl. Ind. Chem. (Wiley, Weinheim, 2012)

    Google Scholar 

  5. J. Ulpts, L. Kiewidt, W. Dreher, J. Thöming, 3D characterization of gas phase reactors with regularly and irregularly structured monolithic catalysts by NMR imaging and modeling. Catal. Today 310, 176–186 (2018)

    Article  Google Scholar 

  6. J. Ulpts, W. Dreher, L. Kiewidt, M. Schubert, J. Thöming, In situ analysis of gas phase reaction processes within monolithic catalyst supports by applying NMR imaging methods. Catal. Today 273, 91–98 (2016)

    Article  Google Scholar 

  7. J. Ulpts, W. Dreher, M. Klink, J. Thöming, NMR imaging of gas phase hydrogenation in a packed bed flow reactor. Appl. Catal. A Gen. 502, 340–349 (2015)

    Article  Google Scholar 

  8. E.S. Kononenko, A.I. Svyatova, I.V. Skovpin, L.M. Kovtunova, E.Y. Gerasimov, I.V. Koptyug, Getting the most out of parahydrogen-induced signal enhancement for mri of reacting heterogeneous systems. J. Phys. Chem. C 126, 14914–14921 (2022)

    Article  Google Scholar 

  9. E. Díaz, S. Ordóñez, Characterisation of catalysts and adsorbents by inverse gas chromatography, calorimetry and thermal methods in catalysis (Springer, Berlin, 2013), pp.521–542

    Google Scholar 

  10. L. Vaugon, A. Finiels, T. Cacciaguerra, V. Hulea, A. Galarneau, C. Aquino, J.-P. Dath, D. Minoux, C. Gerardin, F. Fajula, Impact of pore architecture on the hydroconversion of long chain alkanes over micro and mesoporous catalysts. Pet. Chem. 60, 479–489 (2020)

    Article  Google Scholar 

  11. F. Meemken, P. Müller, K. Hungerbühler, A. Baiker, Simultaneous probing of bulk liquid phase and catalytic gas-liquid-solid interface under working conditions using attenuated total reflection infrared spectroscopy. Rev. Sci. Instrum. 85, 084101 (2014)

    Article  ADS  Google Scholar 

  12. D. Ferri, A. Baiker, Advances in infrared spectroscopy of catalytic solid-liquid interfaces: the case of selective alcohol oxidation. Top. Catal. 52, 1323–1333 (2009)

    Article  Google Scholar 

  13. C.M. Kalamaras, G.G. Olympiou, A.M. Efstathiou, The water-gas shift reaction on Pt/γ-Al2O3 catalyst: Operando SSITKA-DRIFTS-mass spectroscopy studies. Catal. Today 138, 228–234 (2008)

    Article  Google Scholar 

  14. N.Y. Topsoe, J.A. Dumesic, H. Topsoe, Vanadia-Titania catalysts for selective catalytic reduction of nitric-oxide by ammonia. J. Catal. 151, 241–252 (1995)

    Article  Google Scholar 

  15. R. Horn, N.J. Degenstein, K.A. Williams, L.D. Schmidt, Spatial and temporal profiles in millisecond partial oxidation processes. Catal. Letters 110, 169–178 (2006)

    Article  Google Scholar 

  16. Y. Dong, M. Geske, O. Korup, N. Ellenfeld, F. Rosowski, C. Dobner, R. Horn, What happens in a catalytic fixed-bed reactor for n-butane oxidation to maleic anhydride? Insights from spatial profile measurements and particle resolved CFD simulations. Chem. Eng. J. 350, 799–811 (2018)

    Article  Google Scholar 

  17. V.V. Zhivonitko, A.I. Svyatova, K.V. Kovtunov, I.V. Koptyug, Recent MRI studies on heterogeneous catalysis. Annu. Rep. NMR Spectrosc. 95, 83–145 (2018)

    Article  Google Scholar 

  18. A. Svyatova, E.S. Kononenko, K.V. Kovtunov, D. Lebedev, E.Y. Gerasimov, A.V. Bukhtiyarov, I.P. Prosvirin, V.I. Bukhtiyarov, C.R. Müller, A. Fedorov, I.V. Koptyug, Spatially resolved NMR spectroscopy of heterogeneous gas phase hydrogenation of 1,3-butadiene with para hydrogen. Catal. Sci. Technol. 10, 99–104 (2020)

    Article  Google Scholar 

  19. I.V. Koptyug, A.V. Kulikov, A.A. Lysova, V.A. Kirillov, V.N. Parmon, R.Z. Sagdeev, NMR imaging of the distribution of the liquid phase in a catalyst pellet during α-methylstyrene evaporation accompanied by its vapor-phase hydrogenation. J. Am. Chem. Soc. 124, 9684–9685 (2002)

    Article  Google Scholar 

  20. A.A. Lysova, I.V. Koptyug, Magnetic resonance imaging methods for in situ studies in heterogeneous catalysis. Chem. Soc. Rev. 39, 4585 (2010)

    Article  Google Scholar 

  21. L.F. Gladden, F.J.R. Abegão, C.P. Dunckley, D.J. Holland, M.H. Sankey, A.J. Sederman, MRI: Operando measurements of temperature, hydrodynamics and local reaction rate in a heterogeneous catalytic reactor. Catal. Today 155, 157–163 (2010)

    Article  Google Scholar 

  22. S.B. Duckett, N.J. Wood, Parahydrogen-based NMR methods as a mechanistic probe in inorganic chemistry. Coord. Chem. Rev. 252, 2278–2291 (2008)

    Article  Google Scholar 

  23. C.R. Bowers, Sensitivity enhancement utilizing parahydrogen, in Encycl. Magn. Reson. (John Wiley & Sons, Ltd, Chichester, 2007), pp.750–769

    Google Scholar 

  24. K.V. Kovtunov, E.V. Pokochueva, O.G. Salnikov, S.F. Cousin, D. Kurzbach, B. Vuichoud, S. Jannin, E.Y. Chekmenev, B.M. Goodson, D.A. Barskiy, I.V. Koptyug, Hyperpolarized NMR spectroscopy: d-DNP, PHIP, and SABRE techniques. Chem. An Asian J. 13, 1857–1871 (2018)

    Article  Google Scholar 

  25. E.V. Pokochueva, D.B. Burueva, O.G. Salnikov, I.V. Koptyug, Heterogeneous catalysis and parahydrogen-induced polarization. ChemPhysChem 22, 1421–1440 (2021)

    Article  Google Scholar 

  26. R. Eisenberg, T.C. Eisenschmid, M.S. Chinn, R.U. Kirss, Homogeneous transition metal catalyzed reactions (American Chemical Society, 1992), pp.47–74

    Book  Google Scholar 

  27. V.V. Zhivonitko, V.-V. Telkki, I.V. Koptyug, Characterization of microfluidic gas reactors using remote-detection MRI and parahydrogen-induced polarization. Angew. Chemie Int. Ed. 51, 8054–8058 (2012)

    Article  Google Scholar 

  28. K.V. Kovtunov, D.A. Barskiy, A.M. Coffey, M.L. Truong, O.G. Salnikov, A.K. Khudorozhkov, E.A. Inozemtseva, I.P. Prosvirin, V.I. Bukhtiyarov, K.W. Waddell, E.Y. Chekmenev, I.V. Koptyug, High-resolution 3D proton MRI of hyperpolarized gas enabled by parahydrogen and Rh/TiO 2 heterogeneous catalyst. Chem. A Eur. J. 20, 11636–11639 (2014)

    Article  Google Scholar 

  29. K.V. Kovtunov, A.S. Romanov, O.G. Salnikov, D.A. Barskiy, E.Y. Chekmenev, I.V. Koptyug, Gas phase UTE MRI of propane and propene. Tomography 2, 49–55 (2016)

    Article  Google Scholar 

  30. K.V. Kovtunov, D. Lebedev, A. Svyatova, E.V. Pokochueva, I.P. Prosvirin, E.Y. Gerasimov, V.I. Bukhtiyarov, C.R. Müller, A. Fedorov, I.V. Koptyug, Robust in situ magnetic resonance imaging of heterogeneous catalytic hydrogenation with and without hyperpolarization. ChemCatChem 11, 969–973 (2019)

    Article  Google Scholar 

  31. C.R. Bowers, D.P. Weitekamp, Parahydrogen and synthesis allow dramatically enhanced nuclear alignment. J. Am. Chem. Soc. 109, 5541–5542 (1987)

    Article  Google Scholar 

  32. B.A. Jung, M. Weigel, Spin echo magnetic resonance imaging. J. Magn. Reson. Imaging 37, 805–817 (2013)

    Article  Google Scholar 

  33. E.W. Zhao, H. Zheng, R. Zhou, H.E. Hagelin-Weaver, C.R. Bowers, Shaped ceria nanocrystals catalyze efficient and selective para-hydrogen-enhanced polarization. Angew. Chemie Int. Ed. 54, 14270–14275 (2015)

    Article  Google Scholar 

  34. R. Zhou, W. Cheng, L.M. Neal, E.W. Zhao, K. Ludden, H.E. Hagelin-Weaver, C.R. Bowers, Parahydrogen enhanced NMR reveals correlations in selective hydrogenation of triple bonds over supported Pt catalyst. Phys. Chem. Chem. Phys. 17, 26121–26129 (2015)

    Article  Google Scholar 

  35. O.G. Salnikov, D.B. Burueva, E.Y. Gerasimov, A.V. Bukhtiyarov, A.K. Khudorozhkov, I.P. Prosvirin, L.M. Kovtunova, D.A. Barskiy, V.I. Bukhtiyarov, K.V. Kovtunov, I.V. Koptyug, The effect of oxidative and reductive treatments of titania-supported metal catalysts on the pairwise hydrogen addition to unsaturated hydrocarbons. Catal. Today 283, 82–88 (2017)

    Article  Google Scholar 

  36. K.V. Kovtunov, D.A. Barskiy, O.G. Salnikov, A.K. Khudorozhkov, V.I. Bukhtiyarov, I.P. Prosvirin, I.V. Koptyug, Parahydrogen-induced polarization (PHIP) in heterogeneous hydrogenation over bulk metals and metal oxides. Chem. Commun. 50, 875–878 (2014)

    Article  Google Scholar 

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Acknowledgements

The ITC team thanks RSF (grant # 22-43-04426) for support of NMR experiments. L.M.K. thanks the Ministry of Science and Higher Education of the Russian Federation within the governmental order for Boreskov Institute of Catalysis (project AAAA-A21-121011390011-4) for the support of catalyst preparation and characterization.

Funding

The ITC team used funding of RSF (grant # 22-43-04426). L.M. Kovtunova used funding of the Ministry of Science and Higher Education of the Russian Federation within the governmental order for Boreskov Institute of Catalysis (project AAAA-A21-121011390011-4).

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Authors and Affiliations

  1. International Tomography Center, SB RAS, 3A Institutskaya St., Novosibirsk, 630090, Russia

    Ivan V. Skovpin, Alexandra I. Trepakova, Larisa M. Kovtunova & Igor V. Koptyug

  2. Novosibirsk State University, 2 Pirogova St., Novosibirsk, 630090, Russia

    Alexandra I. Trepakova

  3. Boreskov Institute of Catalysis SB RAS, 5 Lavrenteva Pr, Novosibirsk, 630090, Russia

    Ivan V. Skovpin, Larisa M. Kovtunova & Igor V. Koptyug

Authors
  1. Ivan V. Skovpin
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  2. Alexandra I. Trepakova
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  3. Larisa M. Kovtunova
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  4. Igor V. Koptyug
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Contributions

I.V.K. supervised the work; L.M.K. contributed in catalyst preparation and characterization; I.V.S. and A.I.T. conducted the hydrogenation experiments; A.I.T. processed data and prepared the figures; I.V.S. wrote the original draft; I.V.K. reviewed and edited the manuscript. The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

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Correspondence to Ivan V. Skovpin.

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The study was conducted without the use of any human and/or animal studies.

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This paper is a part of the special issue of Applied Magnetic Resonance “Bernhard Blümich: on the Occasion of His 70th Birthday”.

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Skovpin, I.V., Trepakova, A.I., Kovtunova, L.M. et al. Spatially Resolved NMR Spectroscopy for Operando Studies of Heterogeneous Hydrogenation with Parahydrogen. Appl Magn Reson 54, 1271–1282 (2023). https://doi.org/10.1007/s00723-023-01587-y

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