Catalysis in Chemistry and Biology

The following sections are included:

• Contents
• The International Solvay Institutes
• Solvay Scientific Committee for Chemistry
• Acknowledgements
• Participants
• Auditors
• Opening Address by Professor M. Henneaux
• Preface by Professor K. Wüthrich

Although soluble catalysts have been used in organic chemistry for many years, until the 1960s they involved simple acids, bases, or metal salts. In most cases, the metals were ignored in any mechanistic considerations. For example, copper salts can catalyze the cyclopropanation of olefins using diazo compounds; however, the role of copper was not considered in early mechanisms. Simple soluble nickel and cobalt precursor complexes were used in some industrial processes but were not extensively studied. Heterogeneous catalysis especially for hydrogenation has a much longer history of use in organic synthesis…

The following sections are included:

• Present view of homogeneous catalysis
• My recent research contributions to the field of homogeneous catalysis
• Outlook to future developments of research on homogeneous catalysis
• Acknowledgments
• References

The following sections are included:

• Present view of homogenous catalysis
• My recent research contributions to field of homogeneous catalysis
• Outlook to future developments of research on homogeneous catalysis
• Acknowledgments
• References

The following sections are included:

• Present state of research on homogeneous catalysis
• My recent research contributions to homogeneous catalysis
• Outlook to future developments of research on homogeneous catalysis
• Acknowledgments
• References

Chirality is the basis for the origin of asymmetry in our body and culture [1]. Enzymes are the catalysts providing the asymmetry in our body and have also been applied as catalysts in academia and industry for over a century [2]…

My group has been involved in enantioselective homogeneous catalysis since the early days when the noteworthy milestones for the field included oxidative and reductive transformations, which were highlighted by the Nobel Prize in Chemistry to Sharpless (epoxidation and dihydroxylation) along with Noyori and Knowles (hydrogenation). In the intervening period, the discipline of homogeneous catalysis has made significant strides. Although, there are large swaths of reaction space that await exploration and discovery, in connection with the Solvay conference we focus on new directions for the discipline that involve its evolution beyond the objectives that have been traditionally pursued (Fig. 1). For the purposes of this discussion, these include: stereodivergent strategies, designing/managing multiple catalytic processes, use of reactive building blocks, and the interface with biocatalysis. The last of these items can be considered a subset of the second…

The following sections are included:

• My view of the present state of research on catalytic synthesis
• My recent research contributions to sustainable catalytic synthesis
• Outlook to future developments of research on homogeneous catalysis
• Acknowledgments
• References

The following sections are included:

• Current state of catalyst design
• My recent research contributions to developing efficient homogeneous catalysts
• Outlook to future developments of research on homogeneous catalyst design
• Acknowledgments
• References

The following sections are included:

• Present view of homogeneous catalysis
• My recent research contribution to the field of homogeneous catalysis
• Outlook to future developments of research on homogeneous catalysis
• Acknowledgments
• References

The following sections are included:

• My view of the present state of research on organocatalysis
• My recent research contributions to organocatalysis
• Acknowledgments
• References

The Session 1 on “Homogeneous Catalysis”, chaired by Prof. Robert Grubbs, was devoted to reports on basic research on catalysis in homogenous solutions and applications thereof.

The organisation of the first Solvay Conference in 1911 was suggested by Walther Nernst who also played a decisive role in the development of one of the most important industrial processes based on heterogeneous catalysis: the synthesis of ammonia from the elements. In 1905 he had established his heat theorem, later known as the Third Law of Thermodynamics, which allows evaluating the equilibrium constant of a chemical reaction, and a controversy with Fritz Haber prompted the latter to work again on the catalysis of ammonia synthesis. This eventually lead to the Haber– Bosch process which started to be implemented in 1913. The successful catalyst (a doubly promoted iron catalyst) had been found by A. Mittasch after checking several thousand samples. This strategy, nowadays denoted as high throughput screening, is still widely in use for optimizing existing and finding novel catalysts…

The following sections are included:

• View of the present state of research on molecular catalysis
• Recent research contributions to molecular catalysis
• Outlook for future developments of research on molecular catalysis
• Acknowledgments
• References

The following sections are included:

• Some challenges to research in the field of heterogeneous catalysis
• Research contributions to a theory of heterogeneous catalysis
• Outlook to future developments of the theory of heterogeneous catalysis
• Acknowledgments
• References

The following sections are included:

• My view of the present state of research on heterogeneous catalysis
• My recent research contributions to heterogeneous catalysis
• Outlook to future developments of research on heterogeneous catalysis
• References

The following sections are included:

• My view of the present state of computational research on heterogeneous catalysis
• My recent research contributions to heterogeneous catalysis
• Outlook to future developments of research on heterogeneous catalysis
• Acknowledgements
• References

The following sections are included:

• My view of the present state of research on Au catalysis
• My recent research contributions to Au catalysis
• Outlook for further developments in Au catalysis
• References

The following sections are included:

• My view of the present state of research on catalysis
• My recent research contributions to heterogeneous catalysis
• Outlook to future developments of research on heterogeneous catalysis
• Acknowledgments
• References

The following sections are included:

• My view of the present state of research on the above fields
• My recent research contributions to the above fields
• Outlook to future developments of research in the above fields
• Acknowledgments
• References

The Session 2 on “Heterogeneous Catalysis and Characterization of Catalyst Surfaces”, chaired by Prof. Gerhard Ertl, included extensive reference to industrial applications of catalysis on solid supports, and discussions on the experimental techniques used in this field presented special highlights.

The following sections are included:

• Reaction pathways enabled by crystalline, microporous materials
• Examples of recent contributions from M. E. Davis and collaborators
• Examples of potential future developments with crystalline, microporous materials
• References

The following sections are included:

• My view of the present state of research on zeolite catalysis
• My recent research contributions to the prediction of catalyst performance, the example of the alkylation of isobutane and propylene [17]
• Outlook to future developments of research on the prediction of catalyst performance
• Acknowledgments
• References

The following sections are included:

• Present state of research on confinement effects and transition state selectivity in catalysis by microporous solids
• Recent research contributions to catalysis by microporous materials
• Perspectives, advances and opportunities in catalysis by microporous solids
• Acknowledgments
• References

The following sections are included:

• My view of the present state of research on control of heteroatom site distribution in zeolites
• My recent research contributions to control of heteroatom site distribution in zeolites
• Outlook for future developments of research on control of heteroatom site distribution in zeolites
• References

The following sections are included:

• Zeolites in catalysis
• Trends in the synthesis of zeolite catalysts
• Conclusions and perspectives
• References

The following sections are included:

• My view of the present state of research on molecular sieve zeotypes
• My recent research contributions to molecular sieve zeotypes
• Outlook to future developments of research on molecular sieve zeotypes
• Acknowledgements
• References

The following sections are included:

• Potential for breakthroughs in MOF catalysis
• Acknowledgments
• References

The Session 3 on “Catalysis by Microporous Materials”, chaired by Prof. Mark E. Davis, was devoted to a detailed characterization of this particular class of solid support catalysts, with special emphasis on model analysis of the processes catalyzed by these materials.

The following sections are included:

• View of the present state of catalysis under extreme conditions
• Contributions in this session to catalysis under extreme conditions
• Outlook to future developments of research on catalysis under extreme conditions
• Acknowledgments
• References

The following sections are included:

• My view of the present state of research on characterization in catalysis
• My recent research contributions to electron microscopy in catalysis
• Outlook for future developments of electron microscopy research in catalysis
• References

The following sections are included:

• My view of the present state of research on catalyst characterization
• My recent research contributions to catalyst characterization
• Outlook to future Developments of research on catalyst characterization
• Acknowledgments
• References

The technology converting CO molecules into liquid fuels via hydrogenation is known as Fischer–Tropsch synthesis (FTS). It was first developed by two German scientists, Fischer and Tropsch, in the 1920s and has now become the core technology for Gas-to-Liquid (GTL) and Coal-to-Liquid (CTL) in industry. Chemicals produced via FTS have also gone beyond liquid fuels, including other high-value hydrocarbons, such as light olefins, wax and oxygenates. Despite significant advances in both fundamental understandings and commercial applications, there are two major drawbacks in FTS technology: (1) a wide distribution of hydrocarbons with different chain lengths, i.e. a poor product selectivity; (2) the large consumption of H₂, which requires the energy intensive Water-Gas-Shift (WGS) process to generate more H₂ to replenish the coal-derived syngas. Recently, we developed a technology, completely different from conventional FTS, based on a nanocomposite catalyst composed of metal oxide and zeolite (OX-ZEO). Such a composite enables the direct conversion of coal-based syngas (with H₂/CO ratio at ∼0.5–0.8) to light olefins, which thus does not need the additional WGS process. The selectivity of light hydrocarbons containing two to four C atoms (C₂–C₄) is over 94% and that of light olefins (${\text{C}}_2^{=}-{\text{C}}_4^{=}$) reaches 80%. The CO activation and C–C coupling are separated onto two different types of active sites with complementary properties. Particularly, the selective chain growth via C-C coupling is controlled within the confined environment of zeolite pores. This OX-ZEO differs from conventional FTS in the design concept, catalyst and reaction mechanisms.

The following sections are included:

• My view of the present state of research on electrocatalysis
• My recent research contributions to electrocatalysis
• Outlook to future developments of research on electrocatalysis
• References

The following sections are included:

• My view of the present state of research on catalysis in extreme conditions
• My recent research contributions to catalysis in extreme conditions
• Outlook to future developments of research on catalysis in extreme conditions
• Acknowledgments
• References

The following sections are included:

• My view of the present state of research on single-site catalysis
• My recent research contributions to single-site catalysis
• Outlook to future developments of research on single-site catalysis
• Acknowledgments
• References

Session 4 on “Catalysis under Extreme Conditions: Studies at High Pressure and High Temperatures – Relations with Processes in Nature”, chaired by Prof. Henk N. W. Lekkerkerker, broadened the scope of the two preceding sessions with the presentation of exciting illustrations.

The following sections are included:

• Overview of catalysis by protein enzymes
• Open questions and challenges
• References

Chemists and biologists have long dreamed of creating catalysts whose rates and selectivities match those of natural enzymes. Given the complexity of even the simplest enzymatic systems, along with our incomplete understanding of their mechanisms, such an aim has seemed virtually unrealizable. Nevertheless, recent advances in the field of protein design that build on powerful computational and evolutionary methods give cause for optimism.

The following sections are included:

• Status of the physical basis for enzymatic catalysis
• Recent Work from Our Lab on Enzymatic Catalysis
• Outlook to future developments of research on enzymatic catalysis
• Acknowledgments
• References

The following sections are included:

• My view of the present state of research on enzymatic catalysis
• My recent research contributions to enzymatic catalysis
• Future research direction: THz-calorimetry
• Acknowledgments
• References

There is now a substantial body of single molecule experiments on biomolecular motors, supplementing the extensive structural and ensemble data on these systems. Our current focus is on the motor, F₁-ATPase, a component of the enzyme ATP Synthase that uses proton gradients to synthesize ATP. Our interest is in seeing what information single molecule studies may provide on the relation between structural changes and the rates of various processes involved in the ATP binding, release, hydrolysis and synthesis. Our approach is to utilize a class of kinetic-thermodynamic relations used for chemical reactions and originally coming from the field of electron and other transfer reactions. To adapt those relations to biomolecular motors we incorporated into the kinetic-thermodynamic free energy expressions an elastic interaction between the rotor and stator subunits of the motor, and coupled the rotor to the chemical and physical processes. The theory is aimed at adding insights to the different of rates in terms of protein structure. On the more technical side another aim is to relate one type of single molecule experiment to another and to ensemble experiments. Theory-based predictions are made and compared with experiment. Some of our recent PNAS studies are summarized, together with more recent results.

The following sections are included:

• My view of the present state of research on enzymatic reaction mechanisms
• My recent research contributions to enzymatic reaction mechanisms
• Outlook to future developments of research on enzymatic reaction mechanisms
• Acknowledgments
• References

The following sections are included:

• Biological catalysis: understanding the role of protein motions in enzymatic catalysis
• My recent research contributions to enzymatic catalysis
• Outlook for resolution of the role of protein dynamics in catalysis
• Acknowledgments
• References

The following sections are included:

• My view of the present state of research on catalysis by protein enzymes
• My recent research contributions to catalysis by protein enzymes
• Outlook to future developments of research on catalysis by protein enzymes
• Acknowledgments
• References

The Sessions 5 and 6 on “Catalysis by Protein Enzymes”, chaired by Prof. JoAnne Stubbe, and “Catalysis by Ribozymes in Molecular Machines”, chaired by Prof. David Lilley, presented an exciting contrast to the initial four Sessions.

The following sections are included:

• RNA catalysis
• The catalytic mechanisms of nucleolytic ribozymes
• Outlook to future developments of research on RNA catalysis
• Acknowledgments
• References

The following sections are included:

• My view of the present state of research on catalysis by ribozymes in molecular machines
• My recent research contributions to catalysis by ribozymes in molecular machines
• Outlook to future developments of research on catalysis by ribozymes in molecular machines
• Acknowledgments
• References

The following sections are included:

• My view of the present state of research on catalysis by ribozymes
• My recent research contributions to catalysis by ribozymes
• Outlook to future developments of research on catalysis by ribozymes
• Acknowledgments
• References

After the fast-paced discoveries of natural ribozymes and their mechanisms in the 1980s, the publication of new classes of RNA enzymes had slowed to a rate of about one per decade. In following text I discuss the reasons for the scarcity of novel class validations, and note some technical advances that have greatly accelerated ribozyme discovery and analysis very recently. These advances create the right conditions for researchers to maintain an accelerated rate of novel ribozyme discovery in the coming years. Such a renaissance in ribozyme exploration creates tantalizing opportunities to discover more natural ribozymes that promote chemical transformations beyond phosphate ester chemistry.

The following sections are included:

• My view of the present state of research on catalysis on the ribosome
• My recent research contributions to catalysis on the ribosome
• Acknowledgments
• References

The following sections are included:

• Chemical, historical, and evolutionary perspectives on research of RNA catalysis
• Progress in RNA catalysis research and contemporary questions
• Outlook to future developments of research on RNA catalysis
• References

The Sessions 5 and 6 on “Catalysis by Protein Enzymes”, chaired by Prof. JoAnne Stubbe, and “Catalysis by Ribozymes in Molecular Machines”, chaired by Prof. David Lilley, presented an exciting contrast to the initial four Sessions.

The following section is included:

• Index