UNIverse - Public Research Portal
Project cover

Heteroatom Defects at the Electrified Interface: Inner-Sphere Interactions, Electrostatics, Site Distribution, and Role in Electrocatalysis

Research Project
 | 
01.01.2023
 - 31.12.2027

Electrocatalysis 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.

Funding

Heteroatom Defects at the Electrified Interface: Inner-Sphere Interactions, Electrostatics, Site Distribution, and Role in Electrocatalysis

SNF Starting Grants (GrantsTool), 01.2024-12.2028 (60)
PI : Delley, Murielle.

Members (1)

Profile Photo

Murielle Delley

Principal Investigator