MICROBIAL FUEL CELL
By : Bruce Logan
I'd like to give you a sort of a a one slide
introduction to the bigger picture and that is as
environmental engineer I mostly started out like
many environmental engineers worrying about
water and a water infrastructure and
providing both potable water and
providing sanitation and as you think
about the global water infrastructure
you start to realize how much energy
this all takes not just in the US but to
provide water and sanitation to the
world takes an enormous amount of energy
and if that's all provided based on
fossil fuels then what we're really
doing through this water infrastructures
is contributing to climate change we
don't want to do that because climate
change will of course continue to
disrupt water cycles which will probably
lead to greater energy consumption and
so forth it's my experience that people
don't have a more personal appreciation
for how much energy or how much power we
consume in our lives and so it's it's
one thing to say well we're going to
build a nuclear power plant that's a
gigawatt of power production who can
imagine a gigawatt so let's put it on a
more personal level look at the 2,000
calories you eat every day and energy
per day is power so if you were to take
that energy per day and convert it to a
hundred watt light bulb how many hundred
watt light bulbs could you run off the
food that you eat every day anybody want
to guess
I hope somebody wants to guess you can
random number generator but what do you
think 110 100 a thousand a million half
okay
anybody else 30 good okay so everybody
at least is coming up with some number
in their mind I hope so mostly I've
never gotten half before most people
will say somewhere around a few light
bulbs - 10 20 maybe as much as a hundred
and and the answer is really one pretty
good so but you think about that you
think oh my gosh all this food I eat you
know I can never burn that off that must
be a huge amount of energy and yet
that's it one light bulb so think about
how to reassign this energy for the
water infrastructure on that basis and
and you know we're not perfect that's
how many calories we eat but if you look
at what goes down the drain shall we say
that's about 25 watts and if you convert
that to light bulbs that's actually
enough to run a compact fluorescent
which generates just about as much light
as that hundred watt bulb
so our our annual water infrastructure
in the US was about 30 gigawatts or
about five to six percent of all the
electricity that we produce in this
country goes into our water
infrastructure and maybe half of that
goes for wastewater treatment these are
very fuzzy numbers and they're
discussions about this but the really
important point is that at any
wastewater treatment plant
there's about four to ten times the
amount of energy in that water than we
use to treat that wastewater and so if
we could extract just a small fraction
of that energy in the wastewater we
could make wastewater self-sufficient
and in fact if you look at making
wastewater self-sufficient and maybe
even recapturing the energy in the
wastewater so we got seventeen gigawatts
in the wastewater we're no longer using
15 gigawatts to produce no longer
producing can
assuming fifteen gigawatts of
electricity so that's roughly 45
gigawatts in primary energy so you're
looking at if we can make this
sustainable and produce energy somewhere
between maybe 40 and 60 gigawatts of an
a gigawatt that's a that's a nuclear
power plant these are not small numbers
so we should be thinking about them and
if we could figure out how to harness
that energy then we have all this
cellulosic energy that we could harness
in a non combustion based process these
are water based processes right and we
can look start to look forward to other
sources of renewable energy to maybe
power our water infrastructure things
like salinity gradient energy there's
almost a terawatt of energy that's
released where fresh water flows into
salt water and then there's a lot of
waste heat energy any power plant that
produces a gigawatt of electricity also
produces 2 gigawatts of waste heat and
so thinking about how to recover some of
this energy and to use it maybe for our
water infrastructure but for other
reasons as well now I'm gonna focus most
of my time on this idea of waste water
I'll come back and just say a few words
at the end so how can we capture this
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energy well a microbial fuel cell is a
device where bacteria can grow on one
electrode they break down organic matter
they release those electrons from the
organic matter it's just like how we get
energy right we eat food we oxidize it
we remove electrons we send those
electrons through respiratory enzymes
and then when we're done with them we
release them to oxygen right so we need
to eat and we need to breathe so we have
to continue that flow of electrons so
these bacteria can do this we keep them
separate separate separated from the
oxygen and that creates when they
release those electrons a potential
between the two of electrodes of about a
half a volt they've when you have a
voltage times current you have power and
so that's how you generate power in the
system and it's a really simple system
in concept two electrodes on either side
of a container bolted together here and
you just put some
waste water in there and you generate
electricity so if you don't want
electricity maybe you want some other
biofuels what about this system to make
something else so let's say we have a
membrane here and the oxygen is being
bubbled into the cathode so we have the
same thing going on in the last slide
except it's not that cathode is exposed
to air it's exposed to oxygen in air and
water take that system and take away the
oxygen and now what happens
well absolutely nothing really because
the bacteria can't generate enough
voltage to drive any sort of reaction
over here so if we help them out if we
add in a little bit of power into this
system we boost the voltage that they
make then we can actually drive hydrogen
evolution here because we've got
electrons going this way protons going
that way that's what a hydrogen fuel
cell is right it's protons and electrons
and we can involve hydrogen at the
cathode and we can do it for about a
tenth of the energy that we need or a
tenth of the voltage that we need to
split water because we're not splitting
water on the anode where we're using a
thermodynamically favorable reaction
that only needs a small boost of about a
1/2 two-tenths of a volt to drive
hydrogen evolution at that cathode ok
maybe you don't like the hydrogen
economy and you want to make something
else take this system which is making
hydrogen and if you want just say split
water at the anode and use some
renewable energy source to provide that
power and then put some with antigen x'
on that cathode and those methanogens
will produce methane now you can do this
electro chemically you can evolve
methane electrochemically without any
bacteria but it takes precious metals
and you get a lot of other products
besides methane here you get one thing
you get methane and you can do it with a
source of co2 so turning co2 into
something useful so these are microbial
electrochemical technologies they have
microbes on the anode and maybe not the
cathode or they have them on the cathode
and maybe not the Anna
or maybe they have them on both the
anode and the cathode but there's got to
be microbes somewhere or it's not a
microbial technology there may be
electricity that's generated or we may
use a power source to boost that and to
drive the reactions that we want at that
cathode and there may be no membrane
there may be one membrane there may be
stacks of membranes between these
electrodes these are all different types
of technologies that can be used to
convert different types of organic
matter into electricity and almost
anything that's biodegradable can be
used to produce that current we can at
the cathode as I explained reduce oxygen
or reduce protons to hydrogen or we can
do value added production whereby those
electrons or hydrogen from the cathode
is used to make other products but I
really want to focus our talk here on
waste water as the main source of energy
or fuel for the microbial fuel cell and
I want to tell you about how to develop
these technologies so the focus points
are going to take one step back I want
to tell you a little bit about the
electro microbiology what's on the anode
and a little bit about the methanogens
that might grow on a cathode then I'd
like to discuss some of the materials
that go into making these systems and
then leave lead us into how we use those
materials and those microbes to scale up
these systems and make them useful then
right before I conclude I just want to
say a few minutes about salinity
gradient energy the aw SP talks actually
there's two of them that you get to do
and this is the one that you chose and
there's another one on salinity gradient
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energy so I'll just give you a little
insight into that so first the electro
microbiology this is what some would say
is a new sub discipline of microbiology
it's really just based on relatively
recent discoveries that microbes can
accept can donate electrons to
electrode or accept electrons from an
electrode and so I want to first talk
about these ones that can generate
electrical current
so eggs o of eggs o outside the body
electro jens generating electrical
current outside the body outside the
microbe what microbes are doing this so
what we did was we went out to our
favorite place to get microbes which is
a wastewater treatment plant we went to
two different wastewater treatment
plants and then we went to a natural
setting and a bog a wetland bog area we
put these different samples in microbial
fuel cells we generated power we
evaluated how well those samples worked
and then we looked with various
molecular biology techniques to see what
was in there so this is a cycle number
every cycle means that we filled up one
of those little cube like reactors that
I showed you at the beginning we
generated some voltage and some power
then the bacteria ate up all the food we
emptied it out we refilled it so this is
the first second third fifth filling
tenth 15 so we went through this 20
times and you can see the two wastewater
treatment plants and each cycle produced
more and more voltage and really
paralleled each other exactly it was
amazing two different treatment plants
almost exactly the same performance and
yet the bog shot up and then continued
on pretty well but you know by the end
of things they were all producing about
the same amount of voltage so we were
thinking okay these guys look really
good you know maybe not so much there so
what's in there what are these microbes
and that are in there that are doing
that so we used pyrosequencing
to look at the types of bacteria and you
can see these are the three samples and
these are triplicate reactors so all
three reactors three different samples
and almost in all cases you can see a
huge preponderance of these blue bars
which are Delta Proteobacteria so almost
all Delta proteobacteria and then down
at the genus and species level almost
all geo vector sulfur reduce ins so we
wondered about how
that difference arose at the beginning
and you can see at the beginning the two
wastewater treatment plants this is a
principal component analysis which shows
us how similar dissimilar these samples
are at the beginning the wastewater
samples were quite similar to each other
and much different than the BOK right
but by the end they all grouped together
independent of what their inoculum was
that is they were enriched and converged
to very similar communities at the end
of the tests so we said well in these
reactors it must be geo bacter but we
wondered if the way we did the
experiment influenced the outcome
because we set the same resistance on
all the reactors maybe that was not
right so we took these same cube
reactors we ran duplicates this time and
we set each of the anodes at different
potentials so a range of potentials from
minus 0.25 all the way up to 0.8 1 volts
and you can see that no matter what
potential we set we ended up with
Proteobacteria and when we analyzed
which Proteobacteria there were they
were almost all G of actor so the answer
is it's all G of actor sulfur reduce ins
except for one little minor point which
was that the student working on this
went in and got a nice little reactor
and it came up Oh it's most similar to
geo backed herself or reduce ins but the
problem was is that it had all these
properties that actually were quite
different from geo Vactor sulfur reduce
ins most importantly it it cannot use
fumarate as an electron acceptor and it
had some other characteristics which
allowed us to classify it as a
completely different species so even
though it's most similar to it leads us
to believe in our reactors it was not -
you backed her sulfur reduces but
another species that could tolerate the
high phosphate buffer concentrations we
use on the other characteristics of the
reactor so how do these geo bacter
bacteria do this electron transfer well
it turns out that they make these pill I
which are able to allow them to send
those electrons from inside the cell to
outside the cell what we call these
conductive pili nano wires and this is
kind of really cool because think about
how much effort people have been making
to make nano wires and these bacteria
may have been doing this for like a
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billion years we don't know so they can
respire by sending these electrons out
presumably to things like metal oxides
in nature but to our electrode in our
reactors you have those geo bacter which
produce these nano wires other types of
cells like xu and L will produce
conductive appendages as well you have
some bacteria which produce chemical
mediators which move back and forth
between the cells and the surface
Pseudomonas aeruginosa is a good example
of this you have others that need to
make direct contact they they have
nothing to send it out there but if
they're at that surface they can use
that and then you have other microbes
which live in these communities for
reasons we don't fully understand but
they live off the byproducts of some of
these other products what about okay so
that's the electrode Jen's what about
the electrode Trost right nature like
cycles if we have something that's going
to send something out there's usually
going to be something out there that's
going to consume that that product so
what about these electro tropes what
about things that accept these products
there are microbes that can catalyze
dissolved oxygen reduction so electrons
coming off the cathode to oxygen to
nitrate I want to talk about the ones
that can reduce co2 to make methane the
classic Mike the classic theory on on
how bacteria interact with methanogens
is the fermentated bacteria break down
something like glucose releasing acetate
and hydrogen some the fountains use the
acetate other methanogens use the
hydrogen now this is a pretty fast
process these electrons flow very
quickly through these fermentated of
organisms
and then when they the hydrogen is used
by the meth Anjan the methanogens a fast
but it actually processes that hydrogen
very very quickly and so what you have
in terms of classic microbiology theory
is that is called interspecies hydrogen
transfer and it's sort of based on the
slow diffusion in the liquid of hydrogen
between these two microorganisms well
that doesn't make sense
it's like connecting two highways with
the dirt road why would anybody do that
why not cut to the chase right go from
one enzyme to another enzyme and now
even bother making hydrogen so we would
call that electro methanogenesis in that
it's electrically making that methane
not be a hydrogen or acetate so what
what sort of evidence is there that this
could be occurring first are there are
there type microorganisms like we saw
for geo bacter out there that might do
this who are they what what are they
doing and and and if so how are they
doing it so imagine you have a cathode
you're just sending current to that and
you enrich it for methanogens and we did
that and we found that the culture was
predominantly Amitha no bacterium plus
tree and when we compared the amount of
hydrogen that could come off that
electrode without the meth antigen to
the amount of methane we could get we
found we got far more methane than could
be explained by just hydrogen evolution
off that electrode so we said well it
must be catalyzing the release of those
electrons how else could it grow that
how else could it make methane that fast
if it wasn't due to direct electron
transfer so we went and got a type
strain a storage strain and we did the
same test but it produced much much less
methane per unit time however it still
had much higher methane production rates
than could be explained by abiotic
hydrogen production well this was a pure
culture but this was not a pure culture
so we said okay let's go back and see
let's go back like we do but geo bacter
we'll go back to our favor
Bogg and we'll go to a wastewater
treatment plant this time we went to an
anaerobic digester let's inoculate a
bunch of reactors and see what grows
there so we inoculated these reactors
with the bog sediment and a box sample
and with the sludge and I want you to
just focus on the cathode what ended up
on the cathode and you can see this big
black bar in both cases and that black
bar is Mathon Oh bacterium and if you
look at the seed for these two samples
you see almost no madonna bacterium you
have a little bit in the bog sample but
really almost no detectable Matano
bacterium in the sludge and yet in both
cases we ended up with almost
exclusively nathanael bacterium we
thought well maybe it's the material we
used and so we went back and we tried
all sorts of things
magnetite nickel molybdenum and and all
these other things and you can see these
are open circuit controls that means we
didn't put any current through the
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system but this was with the cathode set
at minus 600 millivolts these are almost
all black except for that one which I'll
get back to in a second but this one is
different
this one is with platinum we have
platinum which is an excellent hydrogen
evolution catalyst we end up with
methanol brevibacterium DUP with
methanol bacterium so when we have a
good hydrogen catalyst we get something
different than when we don't have a good
hydrogen catalyst now I've left out this
one orange bar right well turns out even
though you set up duplicates sometimes
they don't always replicate each other's
performance and in this case this
reactor did not perform very well it
actually was pretty bad at making
methane and interestingly it also did
not have a lot of methane or bacterium
so what's going on here you know we have
these electro gens electro troves you
know we we know some of these electro
gens make nanowires we have these
electro troves with antigens in one case
and you know how specific is this
interaction
you know in enzyme catalysis they talk
about lock and key right so the question
is what do we have here plug in socket I
mean that's it resistible come on right
because this has this is pretty specific
and if you're you know if you're a
microbe in the US this works but if
you're in the UK it doesn't work so well
there and if you're in Europe there's no
connection right that's not a specific
lock and key
but maybe the methanogens have figured
that out and they have this sort of
universal adapter for all these donors
or maybe it's all Universal donor
Universal acceptor and not very specific
we don't we don't know so we want to
know and and so we're interested in
these mechanisms and the the first
question to simplify this is our
bacteria needed between the methanogens
and the electrode right do we have to
have a bacterium here or is it just
hydrogen bubbling off here and everybody
uses it well we don't think that's
really true we don't see so far any sort
of correlation between bacteria on that
cathode and the same thing we saw with
the methanol bacterium so we're gonna
say no bacteria not needed so that
leaves us with some alternatives one is
its hydrogen just bubbling off here but
our abiotic rates are very low so we
don't think it's that so maybe it's
nanowires
but so far when we've looked at these
cultures it's not like we see these
nanowires all over the place like we do
with geo bacter so we're not thinking
it's that so that leaves us right now
with sort of two different hypotheses
one it's a hydrogenase it's two
hydrogenases linked up together sending
those electrons along our second
hypothesis is it's fairy dust okay
because if this one fails we don't know
what else where else to go right so it's
some sort of magical fairy dust which is
making this work let's see which one it
is my money is on the hydrogen's
so we did some work with Alfred's
Foreman at Stanford University and what
Alfred did in his lab was he got him a
fountain caucus mera pollute us this was
before we knew it was a methanol
bacterium but he got this metallic
caucus but the really neat thing was he
was able to get this meth Ana caucus
with all the hydrogen ace genes deleted
so here's the way that these archaea
make methane through these pathways and
there are several hydrogenases some in
the pathways some for other reasons and
in this particular microbe they took it
and they deleted all those hydrogenases
which means it's growing on it can grow
on four mate but it can't use hydrogen
in any of these other pathways and so
the idea is okay can it make methane
from an electrode and and it can't do it
if it's just using hydrogen it doesn't
have hydrogenase okay so here's the
abiotic rate of methane production while
there's no methane coming off okay
abiotic Lee there's nothing there and
look look look
methane it's there so this thing doesn't
have hydrogenases so how can it be
making methane if it needs hydrogenases
to do this
it can't now hydrogen will come off this
electrode at this - 600 millivolts it's
coming off a little bit and you raise
you make it more negative and more
hydrogen's coming off and this thing's
the more negative it goes it starts to
grow a little faster but doesn't seem to
be hydrogen or maybe we missed a
hydrogenase it's possible so where does
that leave us I said my money was on the
hydrogenase I lost
that's why engineers don't make good
5
gamblers we we don't like to gamble
so really we're down a fairy dust now in
the case of the methanol caucus mera
pollute Asst Alfred told me he's just
gotten a paper except at the EM bio it
should be out shortly and he will tell
you
a little bit more about fairy dust with
the Nathanael caucus than I can tell you
because his experiments to tell you
about so stay tuned for the fairy dust
okay so what about making use of these
things in reactors and let's get back to
the electrode jens and making
electricity this is these are some of
the reactors that are being built around
the world from benchtop two thousand a
thousand liters in these cases you know
what what is going to make this
technology go forward and you know
what's going to go what's going to make
it go forward is an easy application
wastewater treatment and taking that
wastewater and making electricity so I'm
here to tell you that microbial fuel
cells cannot alone cannot be used for
wastewater treatment okay
there they can do this they're gonna
need some help and I'm going to tell you
why they need some help
but the MFCs we can do this the
challenges were the cost of the
materials maintaining our stable reactor
populations and the second part of that
is we got to treat the wastewater and
produce a high-quality effluent so let's
focus first on this materials issue
there have been a couple studies done it
says we need to make electrodes for less
than $100 or 100 euros per square meter
these are you know okay they don't
they're not exactly the same but close
enough and so we have to do that can we
do that well here's where we were about
five or six years ago take wastewater
put your anode in that's usually carbon
cloth or carbon paper and then the
bacteria will be able to grow on that
you don't need to do anything else to
the anode you put the cathode in that
cathode can use oxygen but we don't have
to bubble air into the water so we want
it to be exposed to the air but if it's
exposed to the air it can leak water
through the electrode so you got to put
something on the outside it's kind of
like why you wear a gore-tex jacket
right you don't want water coming in
here we don't want water going
so we got to put a diffusion layer on
there and we have to move this electrode
close to the cathode because that
reduces ohmic resistance in the system
we don't want them to touch so we might
want to have a barrier there against
connections between the two electrodes
and our cathode typically when we made
these had a platinum catalyst and an Fe
own binder and the Platinum cost about
as much as the binder and so if you put
this all together you were looking at
$2,000 a square meter mm is more than a
hundred a lot more and so this says
there's no way this is going to work
so what we've been doing and others have
been trying to drive the cost of these
materials down we got the anode down to
probably about $20 a square meter the
cathode may be about the same you know
so we're looking at maybe 40 $50 a
square meter for materials that's not as
produced and we've actually even made
some other improvements we think we can
get this down a little bit lower so how
do we do that well the first thing is if
you have all these electrodes how do you
put them into the tank or into the
reactor so take the idea of two of these
little cube reactors together with a
little air space between the cathodes
and expand that up and you can have a
flow of wastewater a flow of air flow of
waste water you know you can have a
whole series of these all connected up
like I sort of showed in that cartoon
earlier so that you create these modules
of electrodes so the idea is you mass
manufacture the modules and you throw
them in a tank okay so what are these
modules made out of the anodes it turns
out we use graphite fiber brushes we
need something that's electrically
conductive non-corrosive has a lot of
surface area per volume and it's easy to
manufacture and these can be made by
machines their brush machines I can do
this they have a huge amount of surface
area and the size of the fibers actually
is a good match to the size of the
bacteria
so the anode as brushes is pretty good
and in fact the stability of these as an
anode is good as well because this is an
experiment we did over a hundred days
and these are the voltage produced again
over these multiple cycles over a
hundred days and these brushes stayed
very stable but these flat electrodes
which are placed close to the cathode
failed and they failed because the
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cathodes were contaminating the anodes
with oxygen so they they started
breathing oxygen instead of using the
electrode so engineering how many
electrodes do you put it do you make
them big do you make them little do you
make them wide short so we you know we
did some experiments and and with these
different electrodes per area and when
we did that we changed the size of the
electrode but that also changes the
distance between the electrode and the
cathode and so the question is do we
need to keep that distance the same or
do we move it away and and so forth and
so we found was the big brushes did
better than these little brushes in this
position but if we move this brush
closer than it did better than the big
brush and so this is just the two
brushes in the different close spaced
and not close spaced and you can see we
produce a lot more power when we put it
closer that's a good electrochemistry
effect not a biology effect so the
answer is make a lot of small brushes
place them close to the cathode except
it didn't work it worked here when we
use the acetate and well buffered
solutions when we used wastewater we
found tremendous instability in this
electrode because this is one and this
is another one made exactly the same way
and you don't want to go out and build
one wastewater treatment plant and then
build another and have them work
differently you want them to work the
same so this will work the idea works
under well controlled systems but under
not well controlled systems this is the
anode potential and the good one and
this is the craziness that goes on in
the bad one so basically it's not stable
the bacteria on the anode get corrupted
by having too much oxygen now the cathode
was a trickier thing the cathode was
typically made out of platinum and so we
were thinking about replacements for
platinum and I was at a conference in in
France and these guys from Belgium come
up and they go we have a great
replacement for platinum I'm like great
what is it
they said activated carbon that's really
good yeah tell me about that later I
gotta go now no no no no no no really
this will work this will work and you
know they were right it actually did
work activated carbon is actually not a
bad catalyst for oxygen reduction as
long as the current densities aren't
that high which they aren't in our
systems it's a good oxygen reduction
catalyst well that's cool and so this is
platinum and carbon cloth and a fiown
really expensive this is cost pennies so
environmental engineers love to play
around with activated carbon because we
absorb things on to it we regenerate it
we burn it we recycle it you know so
we're like all right we get to play with
activated carbon so we took all these
carbons and we evaluated them for their
ability for oxygen reduction and I've
highlighted two here because they're the
two best ones okay I want you to
remember these ones B 1 P 2 P 1 P 2 ok B
1 and P 2 did the best up here and these
are just this is these are power curves
with different catalysts made out of all
these different materials and we did you
don't care about the details the
important thing was that we could show a
correlation between strong acid groups
on those carbons and the power we got
look at that correlation it's beautiful
isn't it ok which ones did I ask you
remember
where's b1 well everybody knows if you
don't like the result don't put it on
the graph now you can't do that okay
this is probably our best material and
it doesn't fall on that line we haven't
figured it out
and that's good news and it's bad news
the bad news is we didn't figure it out
the good news is we can write some more
grants and try and figure it out so
that's a mystery we don't understand
that the other thing we want this carbon
to do is last a long time we don't want
to build a wastewater treatment plan and
have it go south very quickly so these
are power density curves with different
activated carbons treated different ways
and versus platinum here's the Platinum
right at the beginning here's the
Platinum after 16 months nothing left no
activity really at all that's like bare
carbon but our activated carbon isn't
doing too well either so we cleaned it
this shows the time course over several
other one here's the Platinum falling
off really fast and here's the slow
decay these other ones we just did a
dilute acid wash of the cathode and we
restored the activity to nearly the
original one so that says okay this
right now this activated carbon isn't
going to work forever but we can
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regenerate it and maybe we can figure
out ways to prevent it from fouling so
that's another avenue of research that
we're looking at we want to be able to
manufacture these cathodes really
inexpensively and so a student in my lab
came up the idea of putting activated
carbon in with a PVDF polymer now PVDF
is used to make membranes by what's
called a water and a phase inversion or
a water immersion process it's really
easy to do it's really cheap and it it
could lower the cost of these electrodes
down to about fifteen dollars a square
meter and we also looked at how well it
resisted water pressure so some of these
get up to around a meter of water
pressure before we saw some leakage so
that's good that means we could make you
know an electrode that's about a meter
high and you know you want to make them
that because they're not electrically
conductive
over those long distance so you probably
make them smaller and more like you know
like pains on a window you can make the
window big but it's got a lot of panes
in it it works well with the acetate it
works well with wastewater just as well
as our other materials so we think we
have that one soft okay we got the
materials for the anode the cathode
we're all ready to go now here's here's
the next challenge we have to treat the
wastewater and get the co D out now
there's actually oxygen leakage in here
and some of that oxygen is leaking in
and it's being used by microbes that
grow on the cathode so we're actually
removing some of this but just feeding
microbes air that's not really what we
want to do now some of that oxygen that
leaks in goes into our circuit but
that's a small percentage less than 10%
about 5% the rest of its going to leak
in and could be used by the microbes in
there although we have a disconnect we
don't see when we have current we
actually don't see as much being lost to
oxygen and so this is the rate that an
open circuit reactor would be consuming
that CO D this is the rate when we have
current so you can see with current we
can consume that Co D much faster and
that actually reduces our loss to the
background processes as well so we can
remove the CO D we can take it away from
the aerobic microorganisms and we can
make electricity and the faster we make
electricity the better off we are so
here we are with acetate or waste water
this is time this is current we're
making electricity making electricity
the co D is going down so it's a little
batch reactor and it's consuming up the
co D it's dropping dropping dropping
dropping okay but you'll see what
happens here is that you know it's going
along and then all of a sudden it
plummets the same thing happens with the
waste water it goes along and then it
plummets when it's plummets when that
making electricity anymore
you want to make electricity but you
want to keep doing that until the co D
is gone
and in fact you don't do that when you
have about a hundred 150 milligrams per
litre of CO D left electricity
generation stops you can see that a
little bit better here when you graph it
on the basis of Co D and current it's
coming down coming here boom it just
falls off coming along coming along boom
falls off so what that means is we can't
get the co D down to the levels that we
need to discharge that wastewater into
the environment and that's why MFCs
alone cannot accomplish wastewater
treatment they need help
one interesting reason why this crash
occurs is we think it has to do with
this electric field now I teach a course
in transport and I always teach about
advection and diffusion I never teach
this third term because there's no
electric fields that I generally worry
about in nature but here there's an
electric field and what that electric
field does you stick two electrodes in
water and ions migrate to those
electrodes okay you have an anode and a
cathode that a that are at different
potentials the the acetate and
negatively charged things are being
pushed to the anode and positively
charged species to the cathode and that
accelerates the flux of organics to this
anode and if you make some mathematical
simplifications here which are only
slightly accurate I massaged it a little
bit but you come up with something that
says you know this could have about a
factor of 10 impact on the effective
diffusion coefficients in these
electrical fields and so when they they
run out of food the electrical field
starts to collapse as the electrical
field starts to collapse you don't drive
food to the electrodes and it all just
8
stops and so this process becomes
something like a trickling filter you
can remove C OD down to about 100 and if
you let it go even after you don't
generate electricity it kind of gets
down to about 30 or 40 milligrams per
liter but that's it and that's not
enough still to discharge it
so we originally thought well what we do
with trickling filters to make them work
like activated sludge as we we put on
the solids contact process and it works
as well as activated sludge and we could
do that to a microbial fuel cell put on
the solids contact it's basically
settling out solids and and sending them
in a loop to contact with the liquid or
we could hope that something else gets
invented and this guy at Stanford Perry
McCarty who has retired still works and
unfortunately still comes up with great
ideas because it's just not fair to the
rest of us I mean why this guy can
retire and still come up with great
ideas he came up with this thing called
the anaerobic membrane fluidized bed
reactor and what that is is a way to
polish the effluent from his process but
we looked at it to polish the effluent
from our MFC and here's how the AFM BR
works it's really a lot of hollow fiber
membranes with some activated carbon you
can see the tube here and you're pulling
the waste water you pump it in here and
you pull it through these fibers you can
see these activated carbon particles
bashing up against these hollow fibers
and when they do that they help to scour
the membrane and so what you can do is
drop down the co d that's very little
organic matter now here it's absorbed to
the to the activated carbon it's being
degraded the activated carbon is
smashing against the fibers it's
preventing fouling and you can treat the
wastewater and remove the co D so that
was our thought we set up some MFCs to
test this I won't go really into the
details of this other than to say some
had a protective cloth separator over
the cathode to try and keep it from
fouling the other one didn't and the one
that had the separators after five
months was working much better than the
ones that didn't have that cloth so we
learned we need to keep something on
that cathode to try and keep back
biological growth right on that cathode
but with this setup so we have to train
of MFCs so it goes into this one into
the second one and then out goes into
this first one to the second one and
then out and then into the afm be our a
for our for our HRT and these two and
only a one-hour HRT hydraulic retention
time and that reactor and what you can
see is that we could produce an effluent
with these two reactors of less than
twenty milligrams per liter in total
solids less than a milligram per liter
because it's been filtered and we don't
need a clarifier so we produces
high-quality effluent suitable for water
reuse we removed about half of the co D
in these MFCs and the rest in the AFM BR
and the amount of electricity we
produced in the MFCs was about equal to
the electricity consumed in the AFM BR
the fouling we got a little bit of
fouling this is how much back a sort of
pressure took to pull to put across that
membrane we got a little rise quickly
but even over a couple of months very
little change in the transmembrane
pressure and Perry McCarty has told us
they've run their reactors for two years
without having to chemically clean that
membrane which is amazing because a lot
of these reactors need chemical cleaning
after just a few weeks to a couple of
months we're continuing to go on in
these designs and I'll go through this
really quickly just to give you a sense
of what it looks like
this was brushes very close to cathodes
with separators this is having more
cathode per brush we found that
independent of how we set this up the
actual variable that we needed was the
hydraulic retention time the co D
removal in this is really set by the HRT
in these systems this to cathode setup
actually produces more electrical power
but in terms of wastewater treatment
it's about HRT it's about the hydraulic
retention time in that system that's the
predominant variable so now we've looked
at our generation to generation one
would be that three electrode reactor
generation two
you can see banks now of these anodes
and a bank of a cathode so the idea is
you have a module of anodes a cathode
module there's one cathode on this side
one cathode on that side another round
of anodes the ideas you drop these
modules of anodes and cathodes into the
reactor and when you do that you can
start to do something really interesting
this is a reactor that's you know you
9
can see is not very big you know it's
the size of a couple of books you could
take this out to a remote area and find
a source of waste water and then with
that you could wait for it charge your
cell phone and so a lot of places that
need Sanitation also needs cell phone
chargers so we are working on that
concept we are this is a sort of the
generation 3 now this is multiple anodes
and multiple cathodes so kind of stay
tuned for that we're actually running
this at a wastewater treatment plant
because we pump it right from the plant
into our reactor now I have my
two-minute end and and I'll finish up
almost on time you never thought
somebody could get through 77 slides in
50 minutes did you I might have gone a
little quickly so I just you know 10
years ago people said you're crazy this
sounds crazy you know what are you doing
and and I said oh we're gonna have some
fun with this and I want to tell you
something else we're having fun with and
that's salinity gradient energy wherever
the ocean wherever freshwater flows into
the ocean the energy that's dissipated
is like energy equivalent to that fresh
water going over a dam 250 meters high
that's the Hoover Dam and we can also
generate
salinity gradients at industrial sites
we can use things like ammonium
bicarbonate which you can distill out of
water at 50 60 degrees C and create
salty solutions and so the technologies
to do this the best one is pressure
retarded osmosis we've been playing
around with reverse electrodialysis a
lot there's a new technology was
invented just a few years ago called
capacitive mixing which is the opposite
of capacitive deionization and I won't
go into that another one we came up with
hydrogel expansion but this is the one I
wanted to do one slide on because all
these are being looked at to capture the
salinity gradient energy and the fact is
is that most of these are only producing
about one to at most a few watts per
square meter of electrode one watt
that's like a Christmas tree light bulb
per square meter square meter of a love
electrode or square meter of membrane
the membrane cost one hundred a thousand
dollars a square meter you can't have
one watt per membrane area doesn't work
so we work we tried to come up with an
idea that might be a little bit
different than some of those and Fong
Jeong who just recently left my lab said
I think I have this idea and of course
didn't happen that fast but I like to
oversimplify here but she came back says
I think I can get 115 watts per square
meter I said ok I'm listening
and she got up to 240 watts per square
meter of electrode and it's based on an
idea of distilling ammonia out of water
and REE injecting it into this system so
the idea is to take waste heat and use
it as a simple distillation process you
make some solutions this side has no
ammonia that size has ammonia you create
a battery you discharge it at that power
density when it stops you take the
ammonia out and you put it in the other
side and so that's that's kind of the
newest crazy and wild idea so if you
want to invite me back for seminar in
ten years I'll tell you how it worked
out so conclusions we have these
fascinating microorganisms out there
that I that we're really enjoying
studying we're understanding a lot about
the elect
Jen's we don't probably know nearly
enough about the electro tropes but we
know we can use these electric Jen's and
microbes to accomplish wastewater
treatment at least generate electricity
with inexpensive materials and then if
we give them a little help with this
post treatment process an AFM BR or
other technology certainly would work as
well we can treat the wastewater so
we're at this final stage you know of
MFCs you know it's a it's been well
people say that every new technology
goes through this these three stages the
first stage is it can't be done so ten
years ago when I wrote a proposal to NSF
and I said I'd like to turn a wastewater
treatment plant into a power plant they
said it can't be done and they rejected
my proposal but they did give me a
little bit of money and and they said
well you got to prove you can do it
okay so we went and we showed yes we can
make electricity from wastewater and
then that you get that second stage of
the idea well okay it's possible but
it's it's too expensive it's just it's
never gonna work
too expensive nefi own platinum well not
gonna work and then you go and you build
these reactors and you start charging
cell phones and you know everybody says
oh yeah I said it was a good idea all
10
along I wasn't one of those naysayers oh out for two years but the signs are that
no and in in water technologies we've we've had more citations per paper in
had a few examples are Oh membranes for the past year than esnt has so keep our
water desalination you want to fingers crossed and with that say thank
desalinate water with a membrane are you you and if you have time to be happy
crazy answer any questions you see people
that'll never work they're way too upstream basically defecating in the
expensive or MBRs you want to stick a river you have all manner of of garbage
membrane in a tank of wastewater are you floating past you some of those
crazy that's a stupidest I mean I I said mattresses sometimes dead rats
it was a good idea all along
maybe MFCs are the next one there are
some companies trying to do that there
too that got out early here are some
companies trying to play catch-up and
haven't heard much out of these guys in
a while and I want to acknowledge my
research group I've tried to get him to
smile they wouldn't smile I said okay
wave at me
they all smiled look at that think you
know pretty good so they're waving at you
thank my sponsor my current sponsors
syrup that's environmental restorations
through Department of Defense I actually
have some funding for the methanogens
work through Stanford money through NREL
and do II and just recently on these
thermal batteries NSF my collaborators
around the world who are also working to
develop these technology at cows who's
funded a lot of work for me at in
Belgium at Newcastle and in China you
know this has been a very large and
collaborative effort now I couldn't come
here without putting in at least the
last minute plug for yes and tea letters
I'm the editor well officially the
deputy editor of esnt letters it's meant
to be a very rapid turnaround format for
shorter papers so the limit is three
thousand words if you submit it for a
regular research paper five thousand for
a short review you typically will get
your reviews back in two weeks and you
will get that back with a notification
of except minor revision or reject and
if it's rejected you can be allowed to
resubmit at your leisure or not but the
average time to publication is about a
little over a month so it's a very rapid
publication form any tenure-track
faculty going up for tenure thinking
they need to get some publications that
out fast might rethink this journal and
of course establish a earlier in your
career a shorter timeline but we've been
very pleased with the papers we
published we are we don't know what the
impact factor is because you have to be
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