Palladium nanoparticles for catalysis

Palladium nanoparticles for catalysis


Why palladium?
Palladium is one of the most versatile elements from the platinum group metals. Palladium nanoparticles are extensively used as catalysts in a number of industrially relevant reactions. In particular, palladium is recognized as the preferred catalyst for selective hydrogenation of hydrocarbons (e.g. hydrogenation of alkynes in the alkyne/alkene mixtures), selective oxidation of alcohols and methane combustion.

Pd-P4VP.jpg
Where is the room for research?
In reaction conditions, palladium nanoparticles may undergo phase transitions to palladium hydrides, carbides or oxides. Formation of these phases can dramatically change the catalytic activity and selectivity of the catalysts. Despite numerous theoretical and experimental investigation the structure-reactivity relationships and the mechanistic understanding of the catalytic reaction on the surface of palladium nanoparticles is still debated. Therefore, investigation of these phase transitions and their effect on the catalytic properties is the problem of both practical importance and fundamental scientific interest.
What problems do we solve?
We investigate the evolution of atomic and electronic structure of palladium-based catalysts by in situ, operando and time-resolved X-ray absorption spectroscopy and X-ray diffraction. Term "operando" means that we perform our measurements under industrially relevant conditions, when our material is working as catalysts for a model reaction (e.g. hydrogenation of acetylene or oxidation of alcohols). We have proposed an approach that allows to discriminate hydride, carbide and oxide phases, as well as their distribution in the volume of the nanoparticles, by simultaneous application of XRPD, EXAFS and XANES. In addition, new and original approaches for XANES analysis in combination with theoretical simulations have been developed.

This project is succesfull thanks to these guys


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Who worked in close collaboration with


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Some publications


This list contains 36 publications with total Impact-Factor of 175.218

1. O. A. Usoltsev, A. A. Skorynina, B. O. Protsenko, V. Martin-Diaconescu, R. Pellegrini, A. V. Soldatov, J. van Bokhoven, A. L. Bugaeva "Evolution of surface and bulk structure of supported palladium nanoparticles by in situ X-ray absorption and infrared spectroscopies: Effect of temperature, CO and CH4 gas" Applied Surface Science 2023 614 156171 (Impact-factor: 7.392 ) DOI: 10.1016/j.apsusc.2022.156171

2. Andrei A. Tereshchenko, Vera V. Butova, Alexander A. Guda, Olga A. Burachevskaya, Aram L. Bugaev, Aleksei N. Bulgakov, Alina A. Skorynina, Yury V. Rusalev, Ilya V. Pankov, Vadim A. Volochaev, Majd Al-Omoush, Ilya V. Ozhogin, Gennadii S. Borodkin, and Alexander V. Soldatov "Rational Functionalization of UiO-66 with Pd Nanoparticles: Synthesis and In Situ Fourier-Transform Infrared Monitoring " Inorganic Chemistry 2022 61 (9) 3875-3885 (Impact-factor: 4.93 ) DOI: 10.1021/acs.inorgchem.1c03340

3. Andrei Tereshchenko, Danil Pashkov, Alexander Guda, Sergey Guda, Yury Rusalev, Alexander Soldatov "Adsorption Sites on Pd Nanoparticles Unraveled by Machine-Learning Potential with Adaptive Sampling" Molecules 2022 27 (2) 357 (Impact-factor: 4.412 ) DOI: 10.3390/molecules27020357  

4. A. L. Bugaev, O. A. Usoltsev, A. A. Guda, K. A. Lomachenko, M. Brunelli, E. Groppo, R. Pellegrini, A. V. Soldatov, J. A. van Bokhoven "Hydrogenation of ethylene over palladium: Evolution of the catalyst structure by operando synchrotron-based techniques" Faraday Discussions 2021 229 197-207 (Impact-factor: 4.008 ) DOI: 10.1039/C9FD00139E  

5. A. Yu. Pnevskaya, E. G. Kozyr, B. J. F. Al-Jaf, O. A. Usoltsev "First Principal Simulation of Palladium Nanocatalysts Surfaces" Journal of Surface Investigation: X-ray, Synchrotron and Neutron Techniques 2021 15 1270–1277 (Impact-factor: 0.594 ) DOI: 10.1134/S102745102106015X

6. A. Ramirez, P. Ticali, D. Salusso, T. Cordero-Lanzac, S. Ould-Chikh, C. Ahoba-Sam, A. L. Bugaev, E. Borfecchia, S. Morandi, M. Signorile, S. Bordiga, J. Gascon, and U. Olsbye "Multifunctional Catalyst Combination for the Direct Conversion of CO2 to Propane" JACS Au 2021 1 (9) 1719-1732 DOI: 10.1021/jacsau.1c00302  

7. J. Vercammen, M. Bocus, S. Neale, Aram Bugaev, S, Van Minnebruggen, J. Hajek, P. Tomkins, Alexander Soldatov, A. Krajnc, G. Mali, V. Van Speybroeck, D. E. De Vos "Shape-Selective C-H Activation of Aromatics to Biarylic Compounds Using Molecular Palladium in Zeolites" Nature Catalysis 2020 3 1002–1009 (Impact-factor: 41.813 ) DOI: 10.1038/s41929-020-00533-6  

8. N. Van Velthoven, M. Henrion, J. Dallenes, A. Krajnc, A.L. Bugaev, P. Liu, S. Bals, A.V. Soldatov, G. Mali, D.E. De Vos "S,O-Functionalized Metal-Organic Frameworks as Heterogeneous Single-Site Catalysts for the Oxidative Alkenylation of Arenes via C-H activation" ACS Catalysis 2020 10 (9) 5077-5085 (Impact-factor: 13.084 ) DOI: 10.1021/acscatal.0c00801

9. N. Van Velthoven, Y. Wang, H. Van Hees, M. Henrion, A.L. Bugaev, G. Gracy, K. Amro, A.V. Soldatov, J.G. Alauzun, P. H. Mutin, and D.E. De Vos "Heterogeneous Single-Site Catalysts for C-H Activation Reactions: Pd(II)-loaded S,O-Functionalized Metal Oxide-Bisphosphonates" ACS Applied Materials & Interfaces 2020 12 (42) 47457–47466 (Impact-factor: 9.229 ) DOI: 10.1021/acsami.0c12325

10. A. Bugaev, M. Zabilskiy, A. Skorynina, O. Usoltsev, A. Soldatov, J. van Bokhoven "In situ formation of surface and bulk oxides in small palladium nanoparticles" Chemical Communications 2020 56 13097-13100 (Journal Cover) (Impact-factor: 6.222 ) DOI: 10.1039/D0CC05050D  

11. C. Ahoba-Sam, E. Borfecchia, A. Lazzarini, A. Bugaev, A. A. Isah, M. Taoufik, S. Bordiga, U. Olsbye "On the conversion of CO2 to value added products over composite PdZn and H-ZSM-5 catalysts: excess Zn over Pd, a compromise or a penalty?" Catalysis Science & Technology 2020 10 (13) 4373-4385 (Impact-factor: 6.119 ) DOI: 10.1039/d0cy00440e

12. Andrei Tereshchenko, Alexander A. Guda, Vladimir Polyakov, Yury V. Rusalev, Vera Butova and Alexander V Soldatov "Pd nanoparticles growth monitored by DRIFT spectroscopy of adsorbed CO" Analyst 2020 145 7534-7540 (Impact-factor: 3.978 ) DOI: 10.1039/D0AN01303J

13. O.A. Usoltsev, A.L. Bugaev, A.A. Guda, S.A. Guda, A.V. Soldatov "Absorption of hydrocarbons on palladium catalysts: From simple models towards machine learning analysis of X-ray absorption spectroscopy data" Topics in Catalysis 2020 63 58–65 (Impact-factor: 2.910 ) DOI: 10.1007/s11244-020-01221-2

14. A.A. Skorynina, A.A. Tereshchenko, O.A. Usoltsev, A.L. Bugaev, K.A. Lomachenko, A.A. Guda, E. Groppo, R. Pellegrini, C. Lamberti, A.V. Soldatov "Time-dependent carbide phase formation in palladium nanoparticles" Radiation Physics and Chemistry 2020 175 108079 (Impact-factor: 2.858 ) DOI: 10.1016/j.radphyschem.2018.11.033  

15. E.G. Kamyshova, A.A. Skorynina, A. L. Bugaev, C. Lamberti, A.V. Soldatov "Formation and growth of Pd nanoparticles in UiO-67 MOF by in situ EXAFS" Radiation Physics and Chemistry 2020 175 108144 (Impact-factor: 2.858 ) DOI: 10.1016/j.radphyschem.2019.02.003  

16. Kirichkov M.V., Bugaev A.L., Skorynina A.A., Butova V.V., Budnyk A.P., Guda A.A., Trigub A.L., Soldatov A.V. "In situ time-resolved decomposition of β-hydride phase in palladium nanoparticles coated with metal-organic framework" Metals 2020 10 (6) 810 (Impact-factor: 2.259 ) DOI: 10.3390/met10060810

17. A. L. Bugaev, A. A. Guda, I. A. Pankin, E. Groppo, R. Pellegrini, A. Longo, A. V. Soldatov, C. Lamberti "The role of palladium carbides in the catalytic hydrogenation of ethylene over supported palladium nanoparticles" Catalysis Today 2019 336 40-44 (Impact-factor: 4.888 ) DOI: 10.1016/j.cattod.2019.02.068  

18. Guda, A. A.; Guda, S. A.; Lomachenko, K. A.; Soldatov, M. A.; Pankin, I. A.; Soldatov, A. V.; Braglia, L.; Bugaev, A. L.; Martini, A.; Signorile, M.; Groppo, E.; Piovano, A.; Borfecchia, E.; Lamberti, C. "Quantitative structural determination of active sites from in situ and operando XANES spectra: From standard ab initio simulations to chemometric and machine learning approaches" Catalysis Today 2019 336 3-21 (Impact-factor: 4.888 ) DOI: 10.1016/j.cattod.2018.10.071

19. A. Tereshchenko, V. Polyakov, A. Guda, T. Lastovina, Yu. Pimonova, A. Bulgakov, A. Tarasov, L. Kustov, V. Butova, A. Trigub and A. Soldatov "Ultra-Small Pd Nanoparticles on Ceria as an Advanced Catalyst for CO Oxidation" Catalysts 2019 9 (4) 385 (Impact-factor: 3.465 ) DOI: 10.3390/catal9040385  

20. A.L. Bugaev, A.A. Guda, K.A. Lomachenko, A.V. Soldatov "Kinetics of the Atomic Structure of Palladium Nanoparticles during the Desorption of Hydrogen According to X-Ray Diffraction" JETP Letters 2019 109 (9) 594–599 (Impact-factor: 1.412 ) DOI: 10.1134/S002136401909008X  

21. A.L. Bugaev, A.A. Skorynina, E.G. Kamyshova, K.A. Lomachenko, A.A. Guda, A.V. Soldatov, C. Lamberti "In situ X-ray absorption spectroscopy data during formation of active Pt- and Pd-sites in functionalized UiO-67 metal-organic frameworks" Data in Brief 2019 25 104280 DOI: 10.1016/j.dib.2019.104280

22. A. L. Bugaev, A. A. Guda, I. A. Pankin, E. Groppo, R. Pellegrini, A. Longo, A. V. Soldatov, C. Lamberti "Operando X-ray absorption spectra and mass spectrometry data during hydrogenation of ethylene over palladium nanoparticles" Data in Brief 2019 24 103954 DOI: 10.1016/j.dib.2019.103954  

23. E. Groppo, A. Lazzarini, M. Carosso, A.L. Bugaev, M. Manzoli, R. Pellegrini, C. Lamberti, D. Banerjee, A. Longo "Dynamic behavior of Pd/P4VP catalyst during the aerobic oxidation of 2-propanol: a simultaneous SAXS/XAS/MS operando study" ACS Catalysis 2018 8 6870–6881 (Impact-factor: 12.221 ) DOI: 10.1021/acscatal.8b01421  

24. A.L. Bugaev, O.A. Usoltsev, A.A. Guda, K.A. Lomachenko, I.A. Pankin, Yu.V. Rusalev, H. Emerich, E. Groppo, R. Pellegrini, A.V. Soldatov, J.A. van Bokhoven, C. Lamberti "Palladium Carbide and Hydride Formation in the Bulk and at the Surface of Palladium Nanoparticles" The Journal of Physical Chemistry C 2018 122 (22) 12029–12037 (Impact-factor: 4.536 ) DOI: 10.1021/acs.jpcc.7b11473  

25. R. Arrigo, K. Badmus, F. Baletto, M. Boeije, M. Bowker, K. Brinkert, A. Bugaev, V. Bukhtiyarov, et al. "The challenges of characterising nanoparticulate catalysts: general discussion" Faraday Discussions 2018 208 339-394 (Impact-factor: 3.427 ) DOI: 10.1039/C8FD90014K  

26. R. Arrigo, K. Badmus, F. Baletto, M. Boeije, K. Brinkert, A. Bugaev, V. Bukhtiyarov, et al. "Theory as a driving force to understand reactions on nanoparticles: general discussion" Faraday Discussions 2018 208 147-185 (Impact-factor: 3.427 ) DOI: 10.1039/C8FD90013B  

27. A.L. Bugaev, O.A. Usoltsev, A. Lazzarini, K.A. Lomachenko, A.A. Guda, R. Pellegrini, M. Carosso, J. Vitillo, E. Groppo, J. van Bokhoven, A.V. Soldatov and C. Lamberti "Time-resolved operando studies of carbon supported Pd nanoparticles under hydrogenation reactions by X-ray diffraction and absorption" Faraday Discussions 2018 208 187-205 (Impact-factor: 3.427 ) DOI: 10.1039/C7FD00211D  

28. A.L. Bugaev, A.A. Guda, K.A. Lomachenko, E.G. Kamyshova, M.A Soldatov, G. Kaur, S. Øien-Ødegaard, L. Braglia, A. Lazzarini, M. Manzoli, S. Bordiga, U. Olsbye, K. Petter Lillerud, A.V Soldatov and C. Lamberti "Operando study of palladium nanoparticles inside UiO-67 MOF for catalytic hydrogenation of hydrocarbons" Faraday Discussions 2018 208 287-306 (Impact-factor: 3.427 ) DOI: 10.1039/C7FD00224F  

29. A. Bugaev , V. Polyakov, A. Tereshchenko, A. Isaeva, A. Skorynina, E. Kamyshova, A. Budnyk, T. Lastovina, A. Soldatov "Chemical Synthesis and Characterization of Pd/SiO2: The Effect of Chemical Reagent" Metals 2018 8 (2) 135 (Impact-factor: 1.984 ) DOI: 10.3390/met8020135    

30. A.L. Bugaev, A.A. Guda, K.A. Lomachenko, V.V. Shapovalov, A. Lazzarini, J.G. Vitillo, L.A. Bugaev, E. Groppo, R. Pellegrini, A.V. Soldatov, J.A. van Bokhoven, C. Lamberti "Core-shell structure of palladium hydride nanoparticles revealed by combined X-ray absorption spectroscopy and X-ray diffraction" Journal of Physical Chemistry C 2017 121 (33) 18202–18213 (Journal Cover) (Impact-factor: 4.536 ) DOI: 10.1021/acs.jpcc.7b04152  

31. A.L. Bugaev, A.A. Guda, A. Lazzarini, K.A. Lomachenko, E. Groppo, R. Pellegrini, A. Piovano, H. Emerich, A.V. Soldatov, L.A. Bugaev, V.P. Dmitriev, J.A. van Bokhoven, C. Lamberti "In Situ Formation of Hydrides and Carbides in Palladium Catalyst: When XANES is better than EXAFS and XRD" Catalysis Today 2017 283 (1) 119–126 (Impact-factor: 4.312 ) DOI: 10.1016/j.cattod.2016.02.065  

32. A. L. Bugaev, A. A. Guda, K. A. Lomachenko, A. Lazzarini, V. V. Srabionyan, J. G. Vitillo, A. Piovano, E. Groppo, L. A. Bugaev, A. V. Soldatov, V. P. Dmitriev, R. Pellegrini, J. A. van Bokhoven and C. Lamberti "Hydride phase formation in carbon supported palladium hydride nanoparticles by in situ EXAFS and XRD" Journal of Physics: Conference Series 2016 712 (1) 012032 DOI: 10.1088/1742-6596/712/1/012032    

33. A.L. Bugaev, A.A. Guda, K.A. Lomachenko, L.A. Bugaev, A.V. Soldatov "Pd hydride and carbide studied by means of Pd K-edge X-ray absorption near-edge structure analysis" Bulletin of the Russian Academy of Sciences. Physics 2015 79 (9) 1180-1185 (Impact-factor: 0.313 ) DOI: 10.3103/s1062873815010098    

34. A.L. Bugaev, A.A. Guda, K.A. Lomachenko, V.V. Srabionyan, L.A. Bugaev, A.V. Soldatov, C. Lamberti, V.P. Dmitriev, J.A. van Bokhoven "Temperature- and Pressure-Dependent Hydrogen Concentration in Supported PdH x Nanoparticles by Pd K-Edge X-ray Absorption Spectroscopy" The Journal of Physical Chemistry C 2014 118 (19) 10416-10423 (Impact-factor: 4.772 ) DOI: 10.1021/jp500734p    

35. V.V. Srabionyan, A.L. Bugaev, V.V. Pryadchenko, L.A. Avakyan, J.A. van Bokhoven, L.A. Bugaev "EXAFS study of size dependence of atomic structure in palladium nanoparticles" Journal of Physics and Chemistry of Solids 2014 75 (4) 470-476 (Impact-factor: 1.517 ) DOI: 10.1016/j.jpcs.2013.12.012    

36. A.L. Bugaev, V.V. Srabionyan, A.V. Soldatov, L.A. Bugaev, J.A. van Bokhoven "The role of hydrogen in formation of Pd XANES in Pd-nanoparticles" Journal of Physics: Conference Series 2013 430 (1) 012028 DOI: 10.1088/1742-6596/430/1/012028