Discovery and development of cocktail-type catalysis

doi:10.1016/S1872-2067(25)64824-8

Chinese Journal of Catalysis ›› 2025, Vol. 78: 7-24.DOI: 10.1016/S1872-2067(25)64824-8

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Discovery and development of cocktail-type catalysis

Anton L. Maximov^a^,^*(), Mikhail P. Egorov^b^,^*()

^aTopchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow 119991, Russia
^bZelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow 119991, Russia

Received:2025-05-18 Accepted:2025-07-28 Online:2025-11-18 Published:2025-10-14
Contact: *E-mail: max@ips.ac.ru (A. Maximov), mpe@ioc.ac.ru (M. Egorov).
About author:Anton Maximov (Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences) was born in 1970 in Moscow. He graduated from the Department of Chemistry of M. V. Lomonosov Moscow State University (MSU) in 1992, and received his Ph.D. degree in 1996 at MSU. He received his Doctor of Sciences degree in 2005 at the MSU. In 2013 he was awarded the Russian government prize in science and technology. In 2019, he was elected a corresponding member of the Russian Academy of Sciences, and in 2025, he became an Academician of the Russian Academy of Sciences in the field of chemistry He is the director of Topchiev Institute of Petrochemical Synthesis (from 2017). The co-author of >300 publications and 50 patents. His research interests focus on refining and petroleum chemistry, catalysis, C1-chemistry and biorefining.
Mikhail Egorov (Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences) was born in 1953 in Zvenigorod (Moscow region). He graduated from the Department of Chemistry of M. V. Lomonosov Moscow State University (MSU) in 1976, and received his Ph.D. degree in 1980 at MSU. In 1988-1989 he was a fellow of the Alexander von Humboldt Foundation. He received his Doctor of Sciences degree in 1992 at the Institute of Organic Chemistry of the USSR Academy of Sciences. In 1997, he was elected a corresponding member of the Russian Academy of Sciences, and in 2008, he became an Academician of the Russian Academy of Sciences in the field of organic chemistry. In 2001, he was awarded the Russian State Prize for outstanding achievements in science and technology. He was the director of Zelinsky Institute of Organic Chemistry (2003-2023). Currently, he is the Head of Division of Chemistry and Materials Sciences of Russian Academy of Sciences (from 2017). The co-author of >300 publications. His research interests focus on organic chemistry, physical organic chemistry and organometallic chemistry.

Abstract

Abstract:

Catalysis is a cornerstone of modern chemistry, enabling the development of sustainable processes and the production of essential chemicals. However, a fundamental challenge in catalysis lies in understanding the nature of the catalytic species and active centers, particularly the key mechanistic understanding of homogeneous and heterogeneous systems. This review describes the concept of “cocktail”-type catalysis, demonstrating that catalytic active species are not static but evolve through the interconversion of molecular complexes, clusters, and nanoparticles. By bridging homogeneous and heterogeneous catalysis, this paradigm challenges conventional mechanistic views and initiates discussions for a universal theory of catalysis. The findings highlight the importance of adaptive catalyst behavior, leading to more efficient, selective, and robust catalytic systems. The impact of the “cocktail”-type approach extends beyond fundamental research, offering practical applications in industrial catalysis, green chemistry, and synthetic methodologies. By embracing catalytic dynamics, new opportunities arise for designing next-generation catalysts that are both versatile and highly effective in diverse transformations.

Key words: Catalysis, Mechanisms, Homogeneous catalysis, Heterogeneous catalysis, Dynamics of catalytic centers, Catalyst activation, Catalyst degradation

Anton L. Maximov, Mikhail P. Egorov. Discovery and development of cocktail-type catalysis[J]. Chinese Journal of Catalysis, 2025, 78: 7-24.

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Figures/Tables 12

Fig. 1. Historical overview of progressing stages (“waves”) in the mechanistic understanding of the nature of transition-metal-catalyzed reactions (the ‘years’ axis reflects time periods with an influence on the mechanistic studies and on development of new applications in organic synthesis, rather than the year of the first discovery or mention). Reproduced with permission from Ref. [58]. Copyright 2017, Elsevier B.V.

Fig. 2. The structure of Pd2dba3 (a) and FE-SEM images of the formed palladium particles at low (b) and high (c) magnifications; the yellow arrow highlights a small particle. Adapted with permission from Ref. [62]. Copyright 2012, American Chemical Society.

Fig. 3. Analysis of the purity of Pd2dba3 with 1H NMR spectroscopy: NMR spectrum showing olefinic signals of major (blue) and minor (green) isomers of Pd2dba3 and signals of free dba (red), integral regions I1-I3 and mathematical equation for the analysis of purity. Adapted with permission from Ref. [62]. Copyright 2012, American Chemical Society.

Table 1 Variations in the purity of Pd2dba3 from different sources and the stability of Pd2dba in solution and in the solid-state (data from Ref. [62]).

Entry	Sample	Purity of Pd₂dba₃ (%)	Pd NPs content (%)
1	commercial source 1, as received	77	23
2	commercial source 2, as received	92	8
3	commercial source 3, as received	64	36
4	freshly synthesized	99	1
5	freshly synthesized, stored for 6 months in solid-state at r.t.	71	29
6	freshly synthesized, heated for 1 h at 50 °C in CDCl₃	77	23

Fig. 4. “Cocktail”-type catalysis with transformations of different types of catalyst active centers in a solution. Reproduced with permission from Ref. [60]. Copyright 2012, American Chemical Society.

Fig. 5. Formation of molecular metallic species, clusters, and nanoparticles from various types of precatalysts and their dynamic behavior in the “cocktail”-type catalytic system. L: ligand, X: heteroatom, S: solvent. Reproduced with permission from Ref. [59]. Copyright 2013, American Chemical Society.

Fig. 6. Overview of the analytical techniques used for the characterization of dynamic “cocktail”-type catalytic systems at different levels of matter organization. Adapted with permission from Ref. [61]. Copyright 2021, Elsevier B.V.

Fig. 7. Two types of pre-catalysts lead to similar “cocktail”-type catalysts: the sequence of steps in bottom-up catalyst evolution (homogeneous catalyst precursor) (A-C), and the sequence of steps in top-down catalyst evolution (heterogeneous catalyst precursor) (D-F). Reproduced with permission from Ref. [61]. Copyright 2021, Elsevier B.V.

Fig. 8. The dynamics of active sites in heterogeneous catalysis. Large balls represent nanoparticles or clusters, and small ones are single atoms. The orange and yellow arrows indicate reductive and oxidative processes, respectively. SMSI: strong metal-support Interaction; RMSI: reactive metal-support interaction. Reproduced with permission from Ref. [57]. Copyright 2020, Elsevier B.V.

Fig. 10. Two dynamic frameworks in catalysis-the cocktail of species and the cocktail of catalysts-operational pathways for synthetic transformations. The catalytic cycle leading to product formation is denoted by the circle with arrows: catalytic reactions with one type (1-3), two types (4-6) and three types (7) of active species. Reproduced with permission from Ref. [58]. Copyright 2017, Elsevier B.V.

Fig. 11. Unifying framework of “cocktail”-type catalysis depicting the complex dynamic nature of catalytically active species and connecting together dynamic phenomena in transition-metal-based systems. Reproduced with permission from Ref. [61]. Copyright 2021, Elsevier B.V

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Discovery and development of cocktail-type catalysis

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