Tuning Interfacial Chemistry to Direct the Electrosynthesis of Metal Oxide Semiconductors

ConspectusMetal oxide semiconductors have many features that make them attractive for both fundamental and applied studies. For example, these compounds contain elements (e.g., Fe, Cu, Ti, etc.) that are derived from minerals rendering them earth-abundant and, most often, are also not toxic. Therefore, they have been examined for possible applicability in a very diverse range of technological applications including photovoltaic solar cells, charge storage devices, displays, smart windows, touch screens, etc. The fact that metal oxide semiconductors have both n- and p-type conductivity makes them amenable for use as hetero- or homojunctions in microelectronic devices and as photoelectrodes in solar water-splitting devices. This Account presents a review of collaborative research on the electrosynthesis of metal oxides from our respective groups against the backdrop of key developments on this topic. The many variants that interfacial chemical modification schemes offer are shown herein to lead to the targeted synthesis of a wide array of not only simple binary metal oxides but also more complex chemistries involving multinary compound semiconductors and alloys.This Account presents our perspective on how parallel developments in the understanding of and ability to manipulate electrode-electrolyte interfaces have correspondingly enabled the innovation of a broad array of electrosynthetic strategies. These coupled with the advent of versatile tools to probe interfacial processes (undoubtedly, a child of the nanotechnology "revolution") afford an operando examination of how effective the strategies are to secure the targeted metal oxide product as well as the mechanistic nuances. Flow electrosynthesis, for example, removes many of the complications accruing from the accumulation of interfering side products─veritably, this is an Achilles heel of the electrosynthesis approach. Coupling flow electrosynthesis with downstream analysis tools based on spectroscopic or electroanalytical probes opens up the possibility of immediate process feedback and optimization. The combination of electrosynthesis, stripping voltammetry, and electrochemical quartz crystal nanogravimetry (EQCN), either in a static or in a dynamic (flow) platform, is shown below to offer intriguing possibilities for metal oxide electrosynthesis. While many of the examples below are based on our current and recent research and in other laboratories, unlocking even more potential will hinge on future refinements and innovations that surely are around the corner.