Hydrogen Production with a Microbial Biocathode RozendalRené A. JeremiasseAdriaan W. V. M. HamelersHubertus J. N. BuismanCees 2008 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/m<sup>2</sup> at a potential of −0.7 V. This was 3.6 times higher than that of a control electrode (−0.3 A/m<sup>2</sup>). Furthermore, the microbial biocathode produced about 0.63 m<sup>3</sup> H<sub>2</sub>/m<sup>3</sup> cathode liquid volume/day at a cathodic hydrogen efficiency of 49% during hydrogen yield tests, whereas the control electrode produced 0.08 m<sup>3</sup> H<sub>2</sub>/m<sup>3</sup> 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/m<sup>2</sup> at a potential of −0.7 V). Scanning electron micrographs of both microbial biocathodes showed a well-developed biofilm on the electrode surface.