The use of electrochemically active bacteria to break down organic matter, combined with the addition of a small voltage (> 0.2 V in practice) in specially designed microbial electrolysis cells (MECs), can result in a high yield of hydrogen gas. While microbial electrolysis was invented only a few years ago, rapid developments have led to hydrogen yields approaching 100%, energy yields based on electrical energy input many times greater than that possible by water electrolysis, and increased gas production rates. MECs used to make hydrogen gas are similar in design to microbial fuel cells (MFCs) that produce electricity, but there are important differences in architecture and analytical methods used to evaluate performance. We review here the materials, architectures, performance, and energy efficiencies of these MEC systems that show promise as a method for renewable and sustainable energy production, and wastewater treatment.

This paper, for the first time, describes the development of a microbial biocathode for hydrogen production that is based on a naturally selected mixed culture of electrochemically active micro-organisms. This is achieved through a three-phase biocathode startup procedure that effectively turned an acetate- and hydrogen-oxidizing bioanode into a hydrogen-producing biocathode by reversing the polarity of the electrode. The microbial biocathode that was obtained in this way had a current density of about -1.2 A/Nm2 at a potential of -0.7 V. This was 3.6 times higher than that of a control electrode (-0.3 A/m2). Furthermore, the microbial biocathode produced about 0.63 m3 H2/m3 cathode liquid volume/day at a cathodic hydrogen efficiency of 49% during hydrogen yield tests, whereas the control electrode produced 0.08 m3 H2/m3 cathode liquid volume/day at a cathodic hydrogen efficiency of 25%. The effluent of the biocathode chamber could be used to inoculate another electrochemical cell that subsequently also developed an identical hydrogen-producing biocathode (-1.1 A/m2 at a potential of -0.7 V). Scanning electron micrographs of both microbial biocathodes showed a well-developed biofilm on the electrode surface.

The oxygen evolution reaction (OER) and chlorine evolution reaction (CER) are electrochemical processes with high relevance to water splitting for (solar) energy conversion and industrial production of commodity chemicals, respectively. Carrying out the two reactions separately is challenging, since the catalytic intermediates are linked by scaling relations. Optimizing the efficiency of OER over CER in acidic media has proven especially difficult. In this regard, we have investigated the OER versus CER selectivity of manganese oxide (MnOx), a known OER catalyst. Thin films (∼5–20 nm) of MnOx were electrodeposited on glassy carbon-supported hydrous iridium oxide (IrOx/GC) in aqueous chloride solutions of pH ∼0.9. Using rotating ring–disk electrode voltammetry and online electrochemical mass spectrometry, it was found that deposition of MnOx onto IrOx decreases the CER selectivity of the system in the presence of 30 mM Cl– from 86% to less than 7%, making it a highly OER-selective catalyst. Detailed studies of the CER mechanism and ex-situ structure studies using SEM, TEM, and XPS suggest that the MnOx film is in fact not a catalytically active phase, but functions as a permeable overlayer that disfavors the transport of chloride ions.