XPS study of the stability variations of [M(COD)Cl]2 (M = Ir, Rh) complexes anchored on modified silica in reactions of spin-selective hydrogenation of unsaturated hydrocarbons by parahydrogen

Cover Page

Cite item

Full Text

Open Access Open Access
Restricted Access Access granted
Restricted Access Subscription Access

Abstract

Changes in the composition of anchored [M(COD)Cl]2–NH2–C3H6–SiO2 and [M(COD)Cl]2–P(Ph)2–C2H4–SiO2 (where M = Ir, Rh) catalysts in reactions of gas-phase selective hydrogenation of propene, propyne and 1,3-butadiene with parahydrogen (p-H2) were studied using XPS. The atomic ratio M/Cl has been proposed as an indicator of the stability of the structure of the anchored complex, both at the stage of sample preparation and in the reaction. Based on a comparison of XPS data and the results of catalytic testing using parahydrogen-induced polarization, it is shown that the stability of the anchored {[M(COD)Cl]2–Linker–SiO2} complex during hydrogen activation is a key factor in the catalytic behavior of systems. Such stability is influenced not only by the chosen metal and linker, but also by the nature of the hydrogenated substrate.

Full Text

Restricted Access

About the authors

A. V. Nartova

Boreskov Institute of Catalysis SB RAS

Author for correspondence.
Email: nartova@catalysis.ru
Russian Federation, ave. Acad. Lavrentieva, 5, Novosibirsk, 630090

R. I. Kvon

Boreskov Institute of Catalysis SB RAS

Email: nartova@catalysis.ru
Russian Federation, ave. Acad. Lavrentieva, 5, Novosibirsk, 630090

L. M. Kovtunova

Boreskov Institute of Catalysis SB RAS

Email: nartova@catalysis.ru
Russian Federation, ave. Acad. Lavrentieva, 5, Novosibirsk, 630090

A. M. Dmitrachkov

Boreskov Institute of Catalysis SB RAS

Email: nartova@catalysis.ru
Russian Federation, ave. Acad. Lavrentieva, 5, Novosibirsk, 630090

I. V. Skovpin

Boreskov Institute of Catalysis SB RAS; International Tomography Center SB RAS

Email: nartova@catalysis.ru
Russian Federation, ave. Acad. Lavrentieva, 5, Novosibirsk, 630090; st. Institutskaya, 3A, Novosibirsk, 630090

V. I. Bukhtiyarov

Boreskov Institute of Catalysis SB RAS

Email: nartova@catalysis.ru
Russian Federation, ave. Acad. Lavrentieva, 5, Novosibirsk, 630090

References

  1. Fernando N.K., Cairns A.B., Murray C.A., Thompson A.L., Dickerson J.L, Garman E.F., Ahmed N., Ratclif L.E., Regoutz A. // J. Phys. Chem. A. 2021. V. 125. P. 7473. https://doi.org/10.1021/acs.jpca.1c05759
  2. Квон Р.И., Нартова А.В., Ковтунова Л.М., Бухтияров В.И. // ЖСХ. 2023. Т. 64. № 2. C. 106142. https://doi.org/10.26902/jsc_id106142
  3. Skovpin I.V., Kovtunova L.M., Nartova A.V., Kvon R.I., Bukhtiyarov V.I., Koptyug I.V. // Catal. Sci. Technol. 2022. V. 12. № 10. P. 3247. https://doi.org/10.1039/d1cy02258j
  4. Nartova A.V., Kvon R.I., Kovtunov, L.M., Skovpin I.V., Koptyug I.V., Bukhtiyarov V.I. // Int. J. Mol. Sci. 2023. V. 24. № 21. P. 15643. https://doi.org/10.3390/ijms242115643
  5. Bowers C.R., Weitekamp D.P. // J. Am. Chem. Soc. 1987. V. 109. P. 5541. https://doi.org/10.1021/ja00252a049
  6. Сковпин И.В., Свиязов С.В., Буруева Д.Б., Ковтунова Л.М., Нартова А.В., Квон Р.И., Бухтияров В.И., Коптюг И.В. // Докл. РАН. Химия, Науки о материалах. 2023. Т. 512. С. 120. https://doi.org/10.31857/S2686953522600933
  7. Immobilized Catalysts. Ed. Kirschning A. Berlin, Heidelberg, Springer Berlin Heidelberg, 2004. V. 242. 336 p.
  8. Can L., Yan L. Eds. Bridging Heterogeneous and Homogeneous Catalysis. Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany, 2014.
  9. Рассолов А.В., Иванов Г.А., Брагина Г.О., Баева Г.Н., Смирнова Н.С., Казаков А.В., Усачев Н.Я., Стахеев А.Ю. // Кинетика и катализ. 2021. T. 62. № 5. C. 591. https://doi.org/10.31857/S0453881121050075
  10. Рассолов А.В., Брагина Г.О., Баева Г.Н., Машковский И.С., Смирнова Н.С., Герасимов Е.Ю., Бухтияров А.В., Зубавичус Я.В, Стахеев А.Ю. // Кинетика и катализ. 2022. T. 63. № 6. C. 798. https://doi.org/10.31857/S045388112005010X
  11. Помогайло А.Д., Калинина К.С., Голубева Н.Д., Джардималиева Г.И., Помогайло С.И., Кнерельман С.И., Протасова С.Г., Ионов А.М. // Кинетика и катализ. 2015. Т. 56. C. 704. https://doi.org/10.7868/S0453881115050159
  12. Motokura K., Ding S., Usui K., Kong Y. // ACS Catal. 2021. V. 11. P. 11985. https://doi.org/10.1021/acscatal.1c03426
  13. Esfandiari M., Havaei G., Zahiri S., Mohammadnezhad G. // Coord. Chem. Rev. 2022. V. 472. P. 214778. https://doi.org/10.1016/j.ccr.2022.214778
  14. Quignard F., Choplin A. Comprehensive Coordination Chemistry II, eBook, Elsevier. 2003. P. 445.
  15. Zhang J.F., Zhong R., Zhou Q., Hong X., Huang S., Cui H.Z., Hou X.F. // ChemCatChem. 2017.V. 9. P. 2496.
  16. Balcar H., Čejka J., Sedlaček J., Svoboda J., Zednik J., Bastl Z., Bosaček V., Vohlidal J. // J. Mol. Catal. A: Chem. 2003. V. 203. P. 287.
  17. Reinhard S., Šoba P., Rominger F., Blume J. // Adv. Synth. Catal. 2003. V. 345. P. 589.
  18. Arshad M., Ghiac M. // Appl. Catal. A: Gen. 2011. V. 399. P. 75.
  19. Gutmann T., Ratajczyk T., Xu Y., Breitzke H., Grunberg A., Dillenberger S., Bommerich U., Trantzschel T., Bernarding J., Buntkowsky G. // Solid State NMR. 2010. V. 38. № 4. P. 90. https://doi.org/10.1016/j.ssnmr.2011.03.001
  20. Duckett S.B., Mewis R.E. // Acc. Chem. Res. 2012. V. 45. P. 1247. https://doi.org/10.1021/ar2003094
  21. Eills J., Budker D., Cavagnero S., Chekmenev E.Y., Elliot S.J., Jannin S., Lesage A., Matysik J., Meersmann T., Prisner T., Reimer J.A., Yang H., Koptyug I.V. // Chem. Rev. 2023. V. 123. P. 1417. https://doi.org/10.1021/acs.chemrev.2c00534
  22. Freakley S.J., Ruiz-Esquius J., Morgan D.J. // Surface and Interface Analysis, 2017. V. 49. № 8. P. 794. https://doi.org/10.1002/sia.6225
  23. Смирнов М.Ю., Ковтунова Л.М., Калинкин А.В., Сковпин И.В., Коптюг И.В., Бухтияров В.И. // Кинетика и катализ. 2023. T. 64. № 6. C. 1.
  24. Giordano G., Crabtree R.H., Heintz R.M., Forster D., Morris D.E. / Inorganic syntheses. Ed. Shriver D.F. Wiley, 1979. V. XIX. P. 218.
  25. Moulder J.F., Stckle W.F., Sobol P.E., Bomben K.D. // Handbook of X-Ray Photoelectron Spectroscopy, Eden Prairie. MN: Perkin-Elmer, 1992, 261 p.
  26. Tougaard QUASES-IMFP-TPP2M Ver 2.2 Calculation of inelastic electron mean free path. http://www.quases.com/products/quases-imfp-tpp2m/

Supplementary files

Supplementary Files
Action
1. JATS XML
Download
2. Fig. 1. Data on the enhancement of the NMR signal (a) and conversion (b) in the reaction of hydrogenation of 1,3-butadiene with parahydrogen in the presence of the studied catalysts.

Download (863KB)
Indexing metadata
3. Fig. 2. Change in the atomic ratio Cl/Ir during long-term recording of XPS spectra of crystals of the [Ir(COD)Cl]2 complex under UHV conditions.

Download (246KB)
Indexing metadata
4. Fig. 3. P2s + Cl2p region of the XPS spectrum for the Rh–P sample depending on the reaction conditions and after reduction in the cell.

Download (293KB)
Indexing metadata