We introduce a simple solution-based strategy to decouple morphological and functional effects of annealing nanostructured, porous electrodes by encapsulation with a SiO(2) confinement scaffold before high temperature treatment. We demonstrate the effectiveness of this approach using porous hematite (α-Fe(2)O(3)) photoanodes applied for the storage of solar energy via water splitting and show that the feature size and electrode functionality due to dopant activation can be independently controlled. This allows a significant increase in water oxidation photocurrent from 1.57 mA cm(-2) (in the control case) to 2.34 mA cm(-2) under standard illumination conditions in 1 M NaOH electrolyte-the highest reported for a solution-processed hematite photoanode. This increase is attributed to the improved quantum efficiency, especially with longer wavelength photons, due to a smaller particle size, which is afforded by our encapsulation strategy.