Page 303 - Biofuels Refining and Performance
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282   Chapter Nine


                                           Electric current
           Pump              Pump        Anode     Cathode

                                              e −  e −
                                                              Microbial cell
                                                       −      Primary substrate
                                                      e
                                          e −           O 2   Fuel product
                                                              Oxidized fuel
                                                       H O
                                                        2
                      Bioreactor                  Membrane
           Figure 9.12 Bioreactor and biofuel cell combination.


             The advantage of this scheme is that it allows the electrochemical part
           to operate under conditions that are not compatible with the biological
           part of the device. The two parts can even be separated in time, oper-
           ating completely independently. The most widely used fuel in this
           scheme is hydrogen gas, allowing well-developed and highly efficient
              /O fuel cells to be conjugated with a bioreactor.
           H 2  2
             In recent years, ethanol has been developed as an alternative to the
           traditional methanol-powered biofuel cell due to the widespread avail-
           ability of ethanol for consumer use, its nontoxicity, and increased selec-
           tivity by alcohol. Ethanol fuel cells with immobilized enzymes have
           provided higher power densities than the latest state-of-the-art methanol
           biofuel cells. Open-circuit potentials ranging from 0.61 to 0.82 V and
                                             2
           power densities of 1.00–2.04 mW/cm have been produced.
           Mediatorless microbial fuel cells. Most biofuel cells need a mediator mol-
           ecule to speed up the electron transfer from the enzyme to the electrode.
           Recently, mediatorless microbial fuel cells have been developed. These use
           metal-reducing bacteria, such as members of the families Geobacteraceae
           or Shewanellaceae, which exhibit special cytochromes bound to their
           membranes. These are capable of transferring electrons to the elec-
           trodes directly. Rhodoferax ferrireducens, an iron-reducing microor-
           ganism, has the ability to directly transfer electrons to the surface of
           electrodes and does not require the addition of toxic electron-shuttling
           mediator compounds employed in other microbial fuel cells. Also, this
           metal-reducing bacterium is able to oxidize glucose at 80% electron effi-
           ciency (other organisms, such as Clostridium strains, oxidize glucose at
           only 0.04% efficiency). In other fuel cells that use immobilized enzymes,
           glucose is oxidized to gluconic acid and generates only two electrons,
           whereas in microbial fuel cells (MFCs) using R. ferrireducens, glucose
           is completely oxidized to CO releasing 24 electrons. These MFCs have
                                     2
           a remarkable long-term stability, providing a steady electron flow over
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