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Unraveling the microscopic origins of the catalytic activity of aqueous interfaces

English title Unraveling the microscopic origins of the catalytic activity of aqueous interfaces
Applicant Khaliullin Rustam
Number 136413
Funding scheme Fellowships for advanced researchers
Research institution Institut für Chemie Universität Zürich
Institution of higher education Institution abroad - IACH
Main discipline Physical Chemistry
Start/End 01.05.2012 - 31.08.2015
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All Disciplines (3)

Discipline
Physical Chemistry
Organic Chemistry
Condensed Matter Physics

Keywords (6)

catalysis; aqueous interfaces; organic synthesis; molecular dynamics; electronic structure; molecular systems

Lay Summary (English)

Lead
Lay summary
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In nature aqueous surfaces and interfaces are ubiquitous and are involved in a wide variety of biological processes. It is therefore remarkable that, up until recently, organic synthesis in laboratory has mainly neglected water. This situation has been rapidly changing ever since Sharpless and co-workers demonstrated that many classes of organic transformations exhibit increased reaction rates, enhanced selectivity and improved yields when performed in heterogeneous water emulsions.

A thorough understanding of the role that aqueous interfaces play in the catalytic phenomenon described by Sharpless and others is crucial for designing effective laboratory and industrial-scale synthetic processes. However, obtaining detailed information about molecular-scale transformations at these interfaces interfaces represents a formidable challenge. Experimental investigation of complex dynamics of chemical species at liquid-liquid interfaces today is expensive, technically difficult, and often produces results without a clear interpretation. At the same time, computer simulations are either insufficiently accurate or so computationally demanding that studying interfacial processes is unfeasible. For these reasons, our knowledge of the mechanism of reactions in water emulsions is fragmentary and the origin of the catalytic effect at aqueous interfaces remains unclear.

The main aim of this research project is studying the microscopic origins of the enhanced reactivity phenomenon observed in heterogeneous water emulsions. To achieve this goal, the principal investigator will develop and apply efficient and accurate methods for molecular dynamics simulations specifically tailored to take advantage of aspects of the electronic structure that are characteristic of molecular systems.

The proposed research will provide well-founded input for a rational design of synthetic processes that can more effectively utilize the catalytic properties of aqueous interfaces. Furthermore, the developed computational algorithms will make completely new phenomena accessible in computer simulations. They can be immediately applied to study physico-chemical processes in molecular systems such as environmentally important chemical transformations at water surfaces in the atmosphere, the transport of ions and molecules across interfaces in phase-transfer catalysis and phase transitions in ionic liquids and liquid crystals. The theoretical advances in this work will also provide a mathematical foundation for the development of more sophisticated methods for computer simulations of solvation, association-dissociation, self-assembly and many other condensed phase phenomena in complex molecular systems of chemical, biochemical and nanotechnological interest.

Direct link to Lay Summary Last update: 21.02.2013

Responsible applicant and co-applicants

Employees

Publications

Publication
Covalency of hydrogen bonds in liquid water can be probed by proton nuclear magnetic resonance experiments
Elgabarty Hossam, Khaliullin Rustam, Kuhne Thomas (2015), Covalency of hydrogen bonds in liquid water can be probed by proton nuclear magnetic resonance experiments, in Nature Communications, 6, 8318.
Nature of the Asymmetry in the Hydrogen-Bond Networks of Hexagonal Ice and Liquid Water
Kuehne Thomas D., Khaliullin Rustam Z. (2014), Nature of the Asymmetry in the Hydrogen-Bond Networks of Hexagonal Ice and Liquid Water, in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 136(9), 3395-3399.
On the role of interfacial hydrogen bonds in "on-water" catalysis
Karhan Kristof, Khaliullin Rustam, Kuehne Thomas (2014), On the role of interfacial hydrogen bonds in "on-water" catalysis, in Journal of Chemical Physics, 141(22), 22D528.
Efficient Linear-Scaling Density Functional Theory for Molecular Systems
Khaliullin Rustam Z., VandeVondele Joost, Hutter Juerg (2013), Efficient Linear-Scaling Density Functional Theory for Molecular Systems, in JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 9(10), 4421-4427.
Electronic signature of the instantaneous asymmetry in the first coordination shell of liquid water
Kuehne Thomas D., Khaliullin Rustam Z. (2013), Electronic signature of the instantaneous asymmetry in the first coordination shell of liquid water, in NATURE COMMUNICATIONS, 4, 1450.
Microscopic properties of liquid water from combined ab initio molecular dynamics and energy decomposition studies
Khaliullin Rustam Z., Kuehne Thomas D. (2013), Microscopic properties of liquid water from combined ab initio molecular dynamics and energy decomposition studies, in PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 15(38), 15746-15766.
Tetrahedral, when in fluid state
Doemer Manuel, Spura Thomas, Khaliullin Rustam Z., Kuehne Thomas D. (2013), Tetrahedral, when in fluid state, in NACHRICHTEN AUS DER CHEMIE, 61(12), 1203-1206.
Vibrational Signature of Water Molecules in Asymmetric Hydrogen Bonding Environments
Zhang Chao, Khaliullin Rustam Z., Bovi Daniele, Guidoni Leonardo, Kuehne Thomas D. (2013), Vibrational Signature of Water Molecules in Asymmetric Hydrogen Bonding Environments, in JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 4(19), 3245-3250.

Collaboration

Group / person Country
Types of collaboration
Prof. Joost VandeVondele, Swiss Federal Institute of Technology Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication
Prof. Jürg Hutter, University of Zürich Switzerland (Europe)
- in-depth/constructive exchanges on approaches, methods or results
- Publication

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
250th ACS National Meeting, Boston, United States Talk given at a conference Donor-acceptor interactions in the hydrogen-bond networks of hexagonal ice and liquid water 16.08.2015 Boston, United States of America Khaliullin Rustam;
250th ACS National Meeting, Boston, United States Talk given at a conference Linear scaling density functional theory based on local seamlessly interconnected orbital domains 16.08.2015 Boston, United States of America Khaliullin Rustam;
American Conference on Theoretical Chemistry 2014 Poster The nature of the asymmetry in the hydrogen-bond networks of hexagonal ice and liquid water 21.07.2014 Telluride, CO, United States of America Khaliullin Rustam;
American Conference on Theoretical Chemistry 2014 Poster Efficient linear-scaling density functional theory for molecular systems 21.07.2014 Telluride, CO, United States of America Khaliullin Rustam;
245th ACS National Meeting & Exposition Talk given at a conference Asymmetry in the first coordination shell of liquid water 07.04.2013 New Orleans, USA, United States of America Khaliullin Rustam;
Machine learning in atomistic simulations Talk given at a conference Neural-network energy decomposition analysis of the instantaneous asymmetry in the first coordination shell in liquid water 10.09.2012 Lugano, Switzerland, Switzerland Khaliullin Rustam;


Self-organised

Title Date Place
Seminar in THEOS group, EPFL Lausanne, Switzerland 10.12.2014 Lausanne, Switzerland
Skoltech Energy Cluster Seminar: Nanoscale simulations for clean renewable energy applications 03.04.2014 Skolkovo Institute of Science and Technology, Russia

Communication with the public

Communication Title Media Place Year
Media relations: print media, online media Neue Messmethode für die Anziehungskraft von Wasserstoffbrückenbindungen Paderborn University press release International 2015
New media (web, blogs, podcasts, news feeds etc.) Resolution of controversy about structure of liquid water University of Mainz: public relations International 2013
Media relations: print media, online media Water structure controversy laid to rest? Chemistry World International 2013

Abstract

In nature aqueous surfaces and interfaces are ubiquitous and are involved in a wide variety of biological synthetic pathways. It is therefore remarkable that, up until recently, in vitro organic synthesis has mainly neglected water. This situation has been rapidly changing ever since Sharpless and co-workers demonstrated that many classes of organic transformations exhibit increased reaction rates, enhanced selectivity and improved yields when performed in heterogeneous water emulsions.A thorough understanding of the role that aqueous interfaces play in the catalytic phenomenon described by Sharpless et al. is crucial for designing effective laboratory and industrial-scale synthetic processes. However, obtaining detailed information about molecular-scale transformations at these interfaces interfaces represents a formidable challenge. Experimental investigation of complex dynamics of chemical species at liquid-liquid interfaces today is expensive, technically difficult, and often produces results without a clear interpretation. At the same time, computer simulations are either insufficiently accurate or so computationally demanding that studying interfacial processes on appropriate time and length scales is unfeasible. For these reasons, our knowledge of the mechanism of reactions in water emulsions is fragmentary and the origin of the catalytic effect at aqueous interfaces remains unclear.I propose a collaboration with Professor Kuhne at the University of Mainz in Germany with the goal of studying the microscopic origins of the enhanced reactivity phenomenon observed in heterogeneous water emulsions. To this end, I will develop and apply efficient and accurate methods for first-principle molecular dynamics simulations specifically tailored to take advantage of aspects of the electronic structure that are characteristic of molecular systems.The proposed research will provide well-founded input for a rational design of synthetic processes that can more effectively utilize the catalytic properties of aqueous interfaces. Furthermore, the developed computational algorithms will make completely new phenomena accessible in computer simulations. They can be immediately applied to study physico-chemical processes in molecular systems such as environmentally important chemical transformations at water surfaces in the atmosphere, the transport of ions and molecules across interfaces in phase-transfer catalysis and phase transitions in ionic liquids and liquid crystals. The theoretical advances in this work will also provide a mathematical foundation for the development of more sophisticated methods for computer simulations of solvation, association-dissociation, self-assembly and many other condensed phase phenomena in complex molecular systems of chemical, biochemical and nanotechnological interest.
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