This proposal is in response to the Energy Materials and Processes Science Theme proposal call requesting resources to support three research programs at PNNL: the DOE Basic Energy Sciences "Center for Molecular Electrocatalysis" and "Modulating Catalysts with an Enzyme-like Outer Coordination Sphere"; and the Open Call LDRD "Biomimetic Conversion of Methane to Methanol". The focus of these related research programs is the development of bio-inspired molecular electrocatalysts for energy storage, energy production, and/or carbon fixation reactions, such as: H+ reduction/H2 oxidation; N2 reduction/NH3 oxidation; CO2 reduction, CH4 oxidation. The development of electrocatalysts that can efficiently interconvert electrical energy and chemical fuels is a critical component in the implementation of environmentally friendly, alternative energy sources, such as solar or wind, to support the nation's energy needs. The goal of these projects is to develop a comprehensive understanding of how changes in catalyst structure and environment control reactivity and longevity. The EMSL facilities provide the instrumental and computational resources needed to study the details of catalysts' structure, intermediary species, mechanism, and lifetimes. These critical studies will enable the discovery of reactivity trends with different catalyst structures and conditions that will guide the design of future, more efficient catalyst architectures.