Prof. Dr. Murielle Delley Department of Chemistry Profiles & Affiliations OverviewResearch Publications Projects & Collaborations Projects & Collaborations OverviewResearch Publications Projects & Collaborations Profiles & Affiliations Projects & Collaborations 3 foundShow per page10 10 20 50 Heteroatom Defects at the Electrified Interface: Inner-Sphere Interactions, Electrostatics, Site Distribution, and Role in Electrocatalysis Research Project | 1 Project MembersElectrocatalysis of electro-organic reactions by transition metal sulfides and oxides provide exciting opportunities for sustainable production of chemicals using renewable electricity and earth-abundant catalysts. Heteroatom defects in sulfides and oxides (i.e. vacancies and substitutions at non-metal sites) have been highlighted as key to improved electrocatalytic performances. However, defect engineering has so far relied on empirical approaches due to a limited control over defects and an insufficient understanding of the principles underlying defect effects at the electrified interface of sulfides and oxides. While heteroatom defects are known to modulate charge-transfer properties in electrocatalytic materials, the role of inner-sphere processes and the presence of a distribution of different defect sites has largely been neglected. Furthermore, while heteroatom-defect effects have been studied e.g. for water splitting processes, they are substantially less explored for electro-organic synthesis. Herein, I propose to tackle these challenges to open new research avenues in the development of improved electrocatalysts using defect-engineered abundant materials. The goal of this research program is to elucidate the fundamentals that gate heteroatom-defect effects on electrocatalytic syntheses at the electrified interface of abundant solid catalysts, in particular cobalt sulfide (CoSx) and cobalt oxide (CoOx). My laboratory will generate a systematic series of heteroatom-defective materials, and assess the properties of the materials and the defect site distribution by advanced spectroscopy and electroanalytic methods. An important aim of this program is to assess the role of inner-sphere processes at defective surfaces in electrocatalysis, which are likely essential for high activity and selectivity. We will perform operando spectro-electrochemistry to probe the reactivity at the surface of CoSx and CoOx. The fundamental insights gained herein will then be used as a powerful basis to pioneer the elucidation of the role of heteroatom defects in critical electro-organic reactions that use sustainable chemical feedstocks to produce added-value chemicals. By using methods that transcend traditional disciplines this research program will achieve a critical understanding of the fundamental principles gating heteroatom-defect effects on electrocatalysis. These insights are relevant to a range of interfacial systems beyond electrocatalytic technologies. The proposed research will open fascinating opportunities for defect engineering of abundant materials in the electrocatalysis of key organic reactions that are urgently needed for the development of sustainable chemical processes using renewable energy. Branco Weiss Fellowship for Murielle Delley: Electric-Field Assisted Catalysis by Abundant Inorganic Materials Through Interfacial Fundamentals Research Project | 3 Project MembersFor a sustainable future we need energy- and resource-efficient catalytic processes that can be controlled externally and use catalysts made of earth-abundant elements. Binary inorganic materials, such as transition metal phosphides and chalcogenides, have shown great promise to replace noble metal catalysts in some areas, but catalysis has not been broadly explored. The goal is to develop customizable catalysis by abundant inorganic materials for complex chemistry and added-value chemical products through a fundamental understanding of their interfacial chemistry. Electric fields could provide an external control on catalysis that is complementary to the more common temperature and pressure controls used in chemical industry. Electrostatic effects, such as electric fields are thought to be a major contributor to enzymatic catalysis, but have not been broadly explored in chemical synthesis. Herein, we will probe electric fields as external controls on catalysis of reductive and oxidative transformations by abundant materials using electrochemical methods and in-situ surface-enhanced infrared absorption spectroscopy. These studies will be supported by elucidation of the structure, thermochemistry, and elementary reactivity of the operative surfaces and the fine-tuning of their catalytic properties by chemical tailoring. Together, these strategies could open up great opportunities for the technological application of binary materials in sustainable chemical processes and for chemical synthesis. Novel Catalysis by Transition Metal Phosphides and Chalcogenides Using Molecular Perspectives on their Interfacial Chemistry Research Project | 3 Project MembersThe global demand for functionalized chemical products requires active and selective catalysts. Many current technologies are based on rare and expensive noble metal catalysts. Transition metal phosphides and the biomimetic transition metal chalcogenides are promising earth-abundant replacements for noble metal catalysts in many processes. These binary materials (M n X m ) show promise for catalytic water splitting and hydrotreating, but have barely been explored in catalysis for fine-chemical synthesis. The stability, conductivity, and promising catalytic properties of M n X m suggest that there is a plethora of catalysis and electrocatalysis yet to be discovered. Due to their binary composition, M n X m surfaces will likely exhibit complementary selectivity compared to conventional metal catalysts. The goal of the proposed research program is to develop M n X m materials as catalysts for complex chemistry and added-value chemical products. The aim is to broadly survey catalysis of reductive and oxidative transformations with M n X m . The catalytic properties of M n X m will be tuned by chemical surface modifications. The rational development of M n X m as catalysts will rest on fundamental studies of structure, thermochemistry, and interfacial reactivity of the operative surfaces on a molecular-level. This will be achieved by spectroscopic surface characterization, especially in-situ surface-enhanced infrared absorption spectroscopy, stoichiometric equilibration reactions with selected reagents, and parallel study of anchored molecular analogues. The combination of catalytic survey and catalyst tuning with the underlying fundamentals will be a powerful approach to reveal novel catalysis by transition metal phosphides and chalcogenides with properties and selectivity that are currently unattainable for metal catalysts. This research could open up great opportunities for the technological application of inexpensive, earth-abundant binary materials for chemical synthesis. 1 1 OverviewResearch Publications Projects & Collaborations
Projects & Collaborations 3 foundShow per page10 10 20 50 Heteroatom Defects at the Electrified Interface: Inner-Sphere Interactions, Electrostatics, Site Distribution, and Role in Electrocatalysis Research Project | 1 Project MembersElectrocatalysis of electro-organic reactions by transition metal sulfides and oxides provide exciting opportunities for sustainable production of chemicals using renewable electricity and earth-abundant catalysts. Heteroatom defects in sulfides and oxides (i.e. vacancies and substitutions at non-metal sites) have been highlighted as key to improved electrocatalytic performances. However, defect engineering has so far relied on empirical approaches due to a limited control over defects and an insufficient understanding of the principles underlying defect effects at the electrified interface of sulfides and oxides. While heteroatom defects are known to modulate charge-transfer properties in electrocatalytic materials, the role of inner-sphere processes and the presence of a distribution of different defect sites has largely been neglected. Furthermore, while heteroatom-defect effects have been studied e.g. for water splitting processes, they are substantially less explored for electro-organic synthesis. Herein, I propose to tackle these challenges to open new research avenues in the development of improved electrocatalysts using defect-engineered abundant materials. The goal of this research program is to elucidate the fundamentals that gate heteroatom-defect effects on electrocatalytic syntheses at the electrified interface of abundant solid catalysts, in particular cobalt sulfide (CoSx) and cobalt oxide (CoOx). My laboratory will generate a systematic series of heteroatom-defective materials, and assess the properties of the materials and the defect site distribution by advanced spectroscopy and electroanalytic methods. An important aim of this program is to assess the role of inner-sphere processes at defective surfaces in electrocatalysis, which are likely essential for high activity and selectivity. We will perform operando spectro-electrochemistry to probe the reactivity at the surface of CoSx and CoOx. The fundamental insights gained herein will then be used as a powerful basis to pioneer the elucidation of the role of heteroatom defects in critical electro-organic reactions that use sustainable chemical feedstocks to produce added-value chemicals. By using methods that transcend traditional disciplines this research program will achieve a critical understanding of the fundamental principles gating heteroatom-defect effects on electrocatalysis. These insights are relevant to a range of interfacial systems beyond electrocatalytic technologies. The proposed research will open fascinating opportunities for defect engineering of abundant materials in the electrocatalysis of key organic reactions that are urgently needed for the development of sustainable chemical processes using renewable energy. Branco Weiss Fellowship for Murielle Delley: Electric-Field Assisted Catalysis by Abundant Inorganic Materials Through Interfacial Fundamentals Research Project | 3 Project MembersFor a sustainable future we need energy- and resource-efficient catalytic processes that can be controlled externally and use catalysts made of earth-abundant elements. Binary inorganic materials, such as transition metal phosphides and chalcogenides, have shown great promise to replace noble metal catalysts in some areas, but catalysis has not been broadly explored. The goal is to develop customizable catalysis by abundant inorganic materials for complex chemistry and added-value chemical products through a fundamental understanding of their interfacial chemistry. Electric fields could provide an external control on catalysis that is complementary to the more common temperature and pressure controls used in chemical industry. Electrostatic effects, such as electric fields are thought to be a major contributor to enzymatic catalysis, but have not been broadly explored in chemical synthesis. Herein, we will probe electric fields as external controls on catalysis of reductive and oxidative transformations by abundant materials using electrochemical methods and in-situ surface-enhanced infrared absorption spectroscopy. These studies will be supported by elucidation of the structure, thermochemistry, and elementary reactivity of the operative surfaces and the fine-tuning of their catalytic properties by chemical tailoring. Together, these strategies could open up great opportunities for the technological application of binary materials in sustainable chemical processes and for chemical synthesis. Novel Catalysis by Transition Metal Phosphides and Chalcogenides Using Molecular Perspectives on their Interfacial Chemistry Research Project | 3 Project MembersThe global demand for functionalized chemical products requires active and selective catalysts. Many current technologies are based on rare and expensive noble metal catalysts. Transition metal phosphides and the biomimetic transition metal chalcogenides are promising earth-abundant replacements for noble metal catalysts in many processes. These binary materials (M n X m ) show promise for catalytic water splitting and hydrotreating, but have barely been explored in catalysis for fine-chemical synthesis. The stability, conductivity, and promising catalytic properties of M n X m suggest that there is a plethora of catalysis and electrocatalysis yet to be discovered. Due to their binary composition, M n X m surfaces will likely exhibit complementary selectivity compared to conventional metal catalysts. The goal of the proposed research program is to develop M n X m materials as catalysts for complex chemistry and added-value chemical products. The aim is to broadly survey catalysis of reductive and oxidative transformations with M n X m . The catalytic properties of M n X m will be tuned by chemical surface modifications. The rational development of M n X m as catalysts will rest on fundamental studies of structure, thermochemistry, and interfacial reactivity of the operative surfaces on a molecular-level. This will be achieved by spectroscopic surface characterization, especially in-situ surface-enhanced infrared absorption spectroscopy, stoichiometric equilibration reactions with selected reagents, and parallel study of anchored molecular analogues. The combination of catalytic survey and catalyst tuning with the underlying fundamentals will be a powerful approach to reveal novel catalysis by transition metal phosphides and chalcogenides with properties and selectivity that are currently unattainable for metal catalysts. This research could open up great opportunities for the technological application of inexpensive, earth-abundant binary materials for chemical synthesis. 1 1
Heteroatom Defects at the Electrified Interface: Inner-Sphere Interactions, Electrostatics, Site Distribution, and Role in Electrocatalysis Research Project | 1 Project MembersElectrocatalysis of electro-organic reactions by transition metal sulfides and oxides provide exciting opportunities for sustainable production of chemicals using renewable electricity and earth-abundant catalysts. Heteroatom defects in sulfides and oxides (i.e. vacancies and substitutions at non-metal sites) have been highlighted as key to improved electrocatalytic performances. However, defect engineering has so far relied on empirical approaches due to a limited control over defects and an insufficient understanding of the principles underlying defect effects at the electrified interface of sulfides and oxides. While heteroatom defects are known to modulate charge-transfer properties in electrocatalytic materials, the role of inner-sphere processes and the presence of a distribution of different defect sites has largely been neglected. Furthermore, while heteroatom-defect effects have been studied e.g. for water splitting processes, they are substantially less explored for electro-organic synthesis. Herein, I propose to tackle these challenges to open new research avenues in the development of improved electrocatalysts using defect-engineered abundant materials. The goal of this research program is to elucidate the fundamentals that gate heteroatom-defect effects on electrocatalytic syntheses at the electrified interface of abundant solid catalysts, in particular cobalt sulfide (CoSx) and cobalt oxide (CoOx). My laboratory will generate a systematic series of heteroatom-defective materials, and assess the properties of the materials and the defect site distribution by advanced spectroscopy and electroanalytic methods. An important aim of this program is to assess the role of inner-sphere processes at defective surfaces in electrocatalysis, which are likely essential for high activity and selectivity. We will perform operando spectro-electrochemistry to probe the reactivity at the surface of CoSx and CoOx. The fundamental insights gained herein will then be used as a powerful basis to pioneer the elucidation of the role of heteroatom defects in critical electro-organic reactions that use sustainable chemical feedstocks to produce added-value chemicals. By using methods that transcend traditional disciplines this research program will achieve a critical understanding of the fundamental principles gating heteroatom-defect effects on electrocatalysis. These insights are relevant to a range of interfacial systems beyond electrocatalytic technologies. The proposed research will open fascinating opportunities for defect engineering of abundant materials in the electrocatalysis of key organic reactions that are urgently needed for the development of sustainable chemical processes using renewable energy.
Branco Weiss Fellowship for Murielle Delley: Electric-Field Assisted Catalysis by Abundant Inorganic Materials Through Interfacial Fundamentals Research Project | 3 Project MembersFor a sustainable future we need energy- and resource-efficient catalytic processes that can be controlled externally and use catalysts made of earth-abundant elements. Binary inorganic materials, such as transition metal phosphides and chalcogenides, have shown great promise to replace noble metal catalysts in some areas, but catalysis has not been broadly explored. The goal is to develop customizable catalysis by abundant inorganic materials for complex chemistry and added-value chemical products through a fundamental understanding of their interfacial chemistry. Electric fields could provide an external control on catalysis that is complementary to the more common temperature and pressure controls used in chemical industry. Electrostatic effects, such as electric fields are thought to be a major contributor to enzymatic catalysis, but have not been broadly explored in chemical synthesis. Herein, we will probe electric fields as external controls on catalysis of reductive and oxidative transformations by abundant materials using electrochemical methods and in-situ surface-enhanced infrared absorption spectroscopy. These studies will be supported by elucidation of the structure, thermochemistry, and elementary reactivity of the operative surfaces and the fine-tuning of their catalytic properties by chemical tailoring. Together, these strategies could open up great opportunities for the technological application of binary materials in sustainable chemical processes and for chemical synthesis.
Novel Catalysis by Transition Metal Phosphides and Chalcogenides Using Molecular Perspectives on their Interfacial Chemistry Research Project | 3 Project MembersThe global demand for functionalized chemical products requires active and selective catalysts. Many current technologies are based on rare and expensive noble metal catalysts. Transition metal phosphides and the biomimetic transition metal chalcogenides are promising earth-abundant replacements for noble metal catalysts in many processes. These binary materials (M n X m ) show promise for catalytic water splitting and hydrotreating, but have barely been explored in catalysis for fine-chemical synthesis. The stability, conductivity, and promising catalytic properties of M n X m suggest that there is a plethora of catalysis and electrocatalysis yet to be discovered. Due to their binary composition, M n X m surfaces will likely exhibit complementary selectivity compared to conventional metal catalysts. The goal of the proposed research program is to develop M n X m materials as catalysts for complex chemistry and added-value chemical products. The aim is to broadly survey catalysis of reductive and oxidative transformations with M n X m . The catalytic properties of M n X m will be tuned by chemical surface modifications. The rational development of M n X m as catalysts will rest on fundamental studies of structure, thermochemistry, and interfacial reactivity of the operative surfaces on a molecular-level. This will be achieved by spectroscopic surface characterization, especially in-situ surface-enhanced infrared absorption spectroscopy, stoichiometric equilibration reactions with selected reagents, and parallel study of anchored molecular analogues. The combination of catalytic survey and catalyst tuning with the underlying fundamentals will be a powerful approach to reveal novel catalysis by transition metal phosphides and chalcogenides with properties and selectivity that are currently unattainable for metal catalysts. This research could open up great opportunities for the technological application of inexpensive, earth-abundant binary materials for chemical synthesis.
