For 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.

The 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.