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Summary: The development of electrosynthetic technologies for H2O2 production is appealing from a sustainability perspective. The use of carbonate species as mediators in water oxidation to peroxide has emerged as a viable route to do so but still many questions remain about the mechanism that must be addressed. To this end, this work combines electrochemical and spectroscopic methods to investigate reaction pathways and factors influencing the efficiency of this reaction. Our results indicate that CO32− is the key species that undergoes electrochemical oxidation, prior to reacting with water away from the catalyst. Through spectroelectrochemical experiments, we noted that CO32− depletion is a factor that limits the selectivity of the process. In turn, we showed how the application of pulsed electrolysis can augment this, with an initial set of optimized parameters increasing the selectivity from 20% to 27%. In all, this work helps pave the way for future development of practical H2O2 electrosynthetic systems.

Summary: With an increasing global emphasis on renewable energy, electrosynthetic technologies stand to play a substantial role in generating the fuels and chemicals that power today’s society. While directions such as water electrolysis and CO2 directions have been heavily researched in the last decade, the scope of electrosynthesis can be greatly expanded to cover the full range of chemical targets that serve as building blocks for materials, pharmaceuticals, fertilizers, and more. To this end, the main challenges lie in the discovery of novel reaction routes and innovative catalytic systems that circumvent conventional limitations of electrocatalysis. Against this backdrop, this perspective will focus on the use of emerging methodologies to pioneer new electrosynthetic reaction systems. In this work, strategies of environmental control, phase change materials, reactant-selective membranes, and mediated approaches are discussed, before touching on the innovative spectroscopic approaches used to probe these systems and wrapping up with a forward-thinking outlook.

Summary: Biohybrid photo/electrosynthetic systems synergize microbial metabolic pathways and inorganic materials to generate the fuels and chemicals to power our society. They aim to combine the strengths of product selectivity from biological cells and efficient charge generation and light absorption of inorganic materials. However crucial mechanistic questions still remain. In this review we address significant knowledge gaps that must be closed and recent efforts to do so to push biohybrid systems closer to applicability. In particular, we focus on noteworthy advances that have recently been made in applying state-of-the-art analytical spectroscopic, electrochemical, and microelectronic techniques to help pinpoint key complexities of the microbe-materials interface. We discuss the basic function of these techniques, how they have been translated over to study biohybrid systems, and which key insights and implications have been extracted. Finally, we delve into the key advances necessary for the design of next generation biohybrid energy conversion systems.