(AV17493-2) Nanochemistry: A Fantastic Voyage

(AV17493-2) Nanochemistry: A Fantastic Voyage

October 16, 2019 0 By Stanley Isaacs


how about these are produced today it’s
actually not quite simple it’s quite complicated this flow chart shows you
all the steps that’s needed to produce biodiesel you need to draw your sample
you cannot put water or West sample in there even though water oil is
immiscible with water often time you need to do an esterification reaction
followed by this translation reaction I just mentioned to you another very big
step is that you need to do water wash one gallon is about diesel often time
requires up to a gallons of water to wash the product why do you need so much
water for and why do you need water to the first place it’s because the
catalyst that is now commercially available is this chemical called sodium
ethoxide and this is a homogeneous chemical what it means is that it goes
into methanol and stays in the methanol it dissolves itself in methanol so
obviously no one want to put this corrosive strongly basic things into
your car engine in order to remove that you need to use some acid you do acid
and base neutralization you form some salt then you use water to wash them
away that’s why you need so much water to get a pure about diesel all this is
layers of additional cost to this operation another problem is that you
have a catch-22 that is to say the biodiesel is biodegradable that ester
bond sometimes very easy to get hydrolyzed the more water you use to
wash those get the callous away the easier you decompose your end product
okay so therefore you know the shelf-life of the biodiesel it’s
actually not very long and also the methanol contains a lot of water so you
have to use a lot of energy to flash your methanol to recycle those
additional methanol for another round of reduction so here comes another issue
that is right now the growth of the biodiesel plant in the Midwest as many
of you know start to plot hell the reason is that so far almost all the
United States biodiesel plan relies on soybean
as the fee stop if you look at the stock soybean is not very oily in fact it’s
actually a protein that should produce more protein than oil so if you look at
this one hackers of the soybean give you only four hundred forty six liters
this is a chart that I got from a European Journal so therefore all units
are leaders and Hector’s but if you look microalgae z– the amount of the oil per
unit area its orders of magnitude higher than that if I allow me to translate all
these number to you is that us right now use about 970 million acres of for crops
and grazing if we want to use the soy produce biodiesel to meet the current
transportation needs on the diesel fuel we need sixteen point four trillion
acres to be able to produce an up-bow diesel to just overcome the
transportation needs so everybody knows if you compare this number with this
number this is a pipe dream okay however if you use algae only twenty million
acres of the land is needed and we don’t need these for a prime land any you know
backyard retention ponds or you know rivers or whatever coastal area there
are marine algae so this is a great opportunity meaning that only 2.2
percent of the existing cropping area is needed to be able to produce enough of
the fuel so a lot of people actually jumps into this area now there is a
tremendous amount activity particularly in the private sector pursuing using
algae as the alternative fuel source what are the issues well some of the
issues related to how do you get the fat out so well some people think this is a
easy problem because you just pick the right kind of algae there are you know
more than 40 different kinds of algae out there just fresh water
we’re not even counting the marine algae and some of them are high-fat containing
meaning if you look at the bottle caucus brownie this is the one that
typically exist in a colder climate you could actually get 25 to 75 oil meaning
the the neutral lipid per unit weight meaning the dry weight of this algae so
that’s looks very very promising to me that means a tiny little one gives you
this much fat well you know and if you look at the structure of these guys
they’re quite clever you know so at first I thought that well why do they
want to produce that much fat what are you gonna put it turns out they put it
in their backyard so this is the cell membrane they form the colony and they
have salt wall so they put the fat right between the cell wall and the cell
membrane so that’s their pantry so every toe they don’t you know occupy any sort
of space inside of the house but when they need feel they go out and then get
some so that’s really cool here comes the problem so everybody every algae
producer tells you that well the amount of the fat we could give you is so
promising but essentially in order for these micro organism to survive they
produced not just the fatty acid or the triglyceride to make biodiesel they
produce a varieties different kind of neutral compounds they all these are
hydrocarbons that is to say you have steroids
well our football player eats a lot of Destry I mean it builds muscle since you
know steroids yeah good okay and then so the so suffice to say what we’re looking
at here only a small fractions of the chemicals that produced from these
microorganisms are suitable for fuel applications take-home message is that
we got an alphabet soup how do we get only the letter A out for in this case
we add letter B because we want biodiesel so now how do we do that this
is a big challenge so if I summarize this only those short chain meeting last
10 20 carbons non branched hydrocarbons are economical fee stuff for fuel
production because they burn well the current oil extraction has a problem it
often time you order to get these lipid out you have to kill the bug you have a
catch-22 so in order to get the thing you have to grow them after you spend
all the ever growing them you have to kill them
to get what you want well this is not so bad if these things grow fast but the
real problem is that there is no efficient and economical refinery method
to isolate only those feel related chemical from this alphabet soup another
problem is that the current commercial catalyst the sodium methoxide is basic
we’ve got the fatty acid you’ve got the base you’ve got no reaction meaning that
this is the reason why most of our diesel producer in the States are using
soybean because it doesn’t contain the fatty acid why couldn’t they use the
Mickey D’s baby fry oil as a feedstock because they contain a lot of fat free
fatty acid the free fatty acid would destroy the sodium methoxide forming
soap then you don’t have the conversion to biodiesel so therefore you have to do
this additional step called the esterification reaction first to convert
this free fatty acid impurity into your product biodiesel and this is reaction
typically catalyzed by an acid catalyst then you have this FFA free oil than you
do your trance education reaction by doing using a base as a catalyst so the
dream will be can we make a catalyst that could serve both as the acid and
base if you could do that because you can save a step and do one step
conversion from these waste oil feedstock to biodiesel and it turns out
so we got the extraction we got the refinery problem we have the catalyst
problem so let me first tell you what our visions of the solution of the
refinery one what we did we make those tiny little spongebob that I show you
before instead of it being a silica we now made it of a pure carbon so this is
almost I you take those carbon nanotubes you bundle them up into a spherical
particle surface area is more than a thousand square meter program now when
we put the algae inside a little test tube we sprinkle these carbon particles
they went immediately to those algae culture almost all colony got hit
meaning they have a high affinity toward those hydro phobic oil species that
exist in around the algae colony so we could use this to sequester and extract
the fat from even a hexane we put the hexane on
the algae culture then we actually can extract some of the hydrocarbon into the
hexane then we sprinkle our carbon sponge ball into this organic solvent
here containing those alphabets you know hydrocarbons then we actually filter the
particle it turns out our particle has a great selectivity it only absorbed these
guys because of the opening and the unique structure and the hydrophobic
natures of these particle is it likes carbon-14
it likes to 15 it likes the 16 and the 18 and these turns out to be gray
chemical for fuel production so you got the oleic acid you got a permit egg you
got so on and so forth these fatty acids they are weakly
absorbed so we can also absorb these guys as well the some of the large one
like the c20 and c22 they are actually waxy they are not suitable for biodiesel
production or having no affinity because they’re simply molecular Li too large to
be sequester and go inside the pores or particle so our particle can contribute
to this area to actually if economically extract the right kind of chemical out
of this alphabet soup from any microorganism the other problem as I
mentioned is the catalysis problem so we have been working pretty hard in trying
to create a solid that could do both of the acid and the base catalyzed reaction
to convert this these FFA containing feedstock to biodiesel our initial
thinking list well we have the pore structure how about we put the base
inside we put the acid on the outside so the acid can catalyze this conversions
of free fatty acid about diesel then the oil can go inside that the basic domain
and give you the biodiesel and the glycerol ok so this was our initial idea
but it turns out what we did was we just simply put an inorganic species again
I’ll skip this to chemical what we did is we take something as simple as
calcium site which is a naturally produced
mineral mixed with the surfactant and the silicate crosslinker we make a
material our initial idea is to embed these basic calcium oxide as the basic
catalyst into this amorphous silica wall just like the tiny little marble
embedded to the wall and these will be the basic site to convert the
triglyceride to biodiesel so when we saw the performance of this catalyst called
the MCS one we were quite happy with his performance you could actually see that
the amount of callus with oil very very low less than 8% and the amount of
methanol to oil also very low meaning that you don’t have to use a lot of
chemical for this reaction temperature very mild boiling methanol open-air
conversion is quantitative and you can actually reaction times more the last 10
2 hours you can actually recycle this catalyst more than 20 times so if you
compare our results with the existing only two solid catalysts in the in the
world one produced in France the other one produced in India and now been
recently they trying to commercialize certain states they need high
temperature high pressure and their amount of the chemical it’s much higher
and so the newer time came here and then did the story on this on this enormous
catalyst so we’re quite happy with this performance and we were also pretty
surprised in terms of the recyclability as I mentioned you can actually recycle
this more than twenty times you didn’t see any deactivation careless this is
not too surprising because there’s a soybean oil it doesn’t have a whole lot
of free fatty acid however when we use the chicken fat we saw this callus even
though we’re only using 8% and this fatty acid contains 15% in some cases
even 25 this callus survives so how come that 25% of fat did not destroy that
tiny little amount of catalyst if our callus is actually basic so these are
the fundamental question that we asked ourselves we know the cadmium calcium
oxide is basic so you can actually do the transportation reaction oil
converting the triglyceride to biodiesel but what we didn’t understand was that
silica we don’t have any acidic group here meaning that the free fatty acid
should have destroyed the calcium oxide but it didn’t so what would be the
species that responsible for the esterification reaction meaning the
conversion of free fatty acid to biodiesel that was the puzzle to us
until one day Jaime Forney wake one of my former graduate student took
the following two spectrums I will not bore you with the chemistry but simply
to ask you to pay one attention please look at the number meaning the degree
and where the peak shows up to your left this is our starting material we take
the commercial available calcium outside we try to embed this – – – silica
surface silica is not crystalline so will not show any peak this is our
product before we activate it into a callus so I think everybody could tell
the position of the peaks are completely different between the left and the right
that is to say our initial hypothesis was completely wrong we did not have a
material that contains any crystalline of calcium oxide in the structure so
there is no Christian domain in cyma – so what could our material be can this
be some kind of new material that’s formed with these elements meaning
calcium silicate turns out what’s out there that is actually mixed oxide well
cement so turns out if you take a look at the Portland cement 60% of Portland
cement or a trees does the so-called tri calcium silicates the other 15 is the
die calcium silicate both these two will undergo hydrolysis they will give you
the SoCo hydrated layer what people call the CSH layer okay so same thing will
happen to die callousness okay turns out this is nano chemistry this
has a 1.4 nanometer Tobermory crystalline structure that
looks something like this okay so the light gray representing the calcium
oxide layer the dark gray tetrahedra are at the silicates so if I turn this 90
degree you can see the better you have a slab of a calcium oxide cover with only
one layer of calcium okay on top and below then this unit
repeats itself like lasagna layer on layer so calcium’s are over here
silicates are over here notice one interesting thing is that the teeth
meaning the silica tetrahedra are not touching each other there’s a gap filled
with water and other counter ions so what happened was our spectrum looks
very similar to these hydrated cement okay so I told my student this is a
concrete result okay so well if it turns out this is the precursor of our
catalyst upon the calcination we see some changes
of this guy some of the peaks disappear some of the peak remains so without
going into the detail chemistry sorry I have to skip the saza and marthis is
actually a lot of effort for Markovski my dear friend that spent a lot of
effort to get these spectrums but I didn’t have time to go through it just
tell you what happened turns out what we did was to take these lasagna structure
and start squeezing them so that to the point the teeth of the silicate start to
touch each other and connect so if I could point out if you look at one of
these tetrahedra it’s connected to of two of its own kind so we could call it
Q two when they connect with another one then you create a new type of silicon
that’s called Q 3 so it turns out when we investigated the more of the Q 3 you
form the more chaotic active your material becomes okay so again this is
data from Markovski he did the calcium silicon spin counting silicon 20:19
counting turns out the ratio in our most active material to calcium over silicon
the calcium is the majority silicon is the minority the ratio is one point
seven we move from here to here you move from with active bodies of calais to
sand okay and the more of the calcium and silicon ratio you go their activity
decreased this turns out to be there deal ratio okay so we’re still
investigating and trying to understand an atomic-level why this is okay but
suffice to say with this some Cermak insertion analysis there are surface
acidic size so by having calcium marry with silica you have both of the acid
and base okay so the children inherit the trace from both parents know by
using that we could actually eliminate 50% of the current biodiesel production
process so that we don’t need water washing because our callus is solid
nothing goes into the product we don’t need to do a certification we could do
one part reaction okay our product is not toxic we could recycle the catalyst
over over again with that we were very happy we decide to you know we were also
lucky that a venture capital firm in California Menlo Park California decided
gave us initially six point seven million and now up to twelve million so
we form a company called Catalan so I was telling Mike that my heart was
broken when I found out cata Rin was taken because that initially I
want to say catalyst and Lin Lin is my last name so we have to compromise and
now see a TI a lion but that’s we decide to pronounce it Catalan anyway so so now
we build a pilot plan over at the the bio energy conversion center out in
Nevada how many of you know how to pronounce that work but took me two
years to figure out it’s not Nevada its Nevada you know so anyway now Carolyn is
fully staffed so right now we have 20 employee in the company this is myself
and Carla and young were my former postdoc that joined the company Jennifer
was the the the brave student that took those powder x-ray to figure out that
something to do with cement she joined the company as well Wayne
Turner is the VP for operation that would accrue from Dow Chemical
he was the site manager for Fadel 35 years CEO is very light in heart from
and Dave Sam who was the salesmen director at GW grace and recently joined
the Cal and the rest we have a basketball team all of these guys are
six four and above so I look like a midget here but anyway so this is our
product we have now produced I was quite happy we now produce a ton of this guy
so now we are selling this thing to around the world pilot plan is done its
we just recently switched from the batch mode to continuous flow there are a
fixed bed reactor so now the startup is gonna be next week so with that I’d like
to thank the funding agency and the students so we in the group we have a
blue team we have a red team the Blues are the bio team the Reds are the
catalysis team and I like to thanks markussi for the collaboration also come
one for the collaboration on the plant cells and many many friends and students
I owe my gratitude to them funding agency should never forget about them
even though they never give you enough money so so with that I thank you for
your attention and my apology for a long lecture thanks yes yes yes in fact in the case that I show
you okay the first cartoon I show you is the hope that we want to put the
antibody that’s a site directing agent but all the data that I shown you did
not contain any antibody on the outside so but we did use some cell membrane
molecular recognition for example the like the folic acid okay
recognizing the cell membrane protein and that is actually on the exterior
side of the protein what we found is in those cases the particle gets small
swallowed by the by the cells but they tend to get trapped inside and ozone for
very long period of time because of that strong binding with with the lipid
bilayer so the mechanism for those the the the entering the cell membrane
penetrations we have investigated that turns out right now we saw pinocytosis
we saw clathrin-mediated endocytosis those are all protein assisted and those
cytosis so what we found there are several factor one can play and one
thing i did not show today is that you could even we publish a paper last year
if you could change the shape of the particle okay from severe co2 rod
certain type of cells like to swallow the severe co certain cell certain type
of cell light to swallow the rod and why i don’t know it’s very interesting and
perhaps if you think about a lot of the viruses are at your satirical shapes and
a lot of bacterias are rot so is there any sort of evolutionary reason behind
it don’t know but it’s interesting for us to continue investigating yes we which we tried that turns out
again the morphology plays a big role here you could actually get some
sequestration but you don’t have selectivity you cut you throw the
activated charcoal into alphabet soup you come out with a activate the
charcoal cover with alphabet soup that’s what we saw yes of course yes correct absolutely no the reason why with you
you use the camera so far so so the reason why we use cadmium sulfide as the
first demonstration is that the chemist sulfide quantum dot so it’s
photoluminescent and the reason why we use that is because then we can study
the the diffusion profile you know how the cap diffuses away from the from the
from the me so porous silica and so I got that question a lot and then you
know the interesting thing is that as I show you literally you just need
something that’s slightly larger than the pores those can be the cap right
anything that can block them from leaking out will work