Although the vast majority of energy consumed worldwide is derived from fossil fuels, the growing interest in making cleaner alternative energies more economically viable has motivated recent research efforts aimed to improve photovoltaic, wind, and biomass power generation. Clean power generation also requires clean burning fuels, such as H2 and O2, so that energy can still be provided on demand at all times, despite the intermittent nature inherent to solar or wind power. My research has focused on the rational approach to synthesizing earth-abundant nanomaterials with applications in the generation of clean alternative fuels and understanding the structure-property relationships which directly influence their performance. Herein, we describe the development of low-cost, earth-abundant layered metal chalcogenides as high-performance electrocatalysts for hydrogen evolution, and hematite photoanodes for photoelectrochemical oxygen evolution. This work has revealed a particularly interesting concept where catalytic performance can be enhanced by controlling the phase behavior of the material and taking advantage of previously unexploited properties to overcome the challenges traditionally limiting the performance of these layered materials for hydrogen evolution catalysis.