So welcome everybody again. Wolfgang Schoefberger is here from the organic chemistry department at JKU. Maybe you can share your screen and make a short introduction to yourself if you would like to. Wolfgang Schöfberger Okay, thanks, Martin. Thanks for tuning in. Lectures for future, scientists for future, up austria and i copied just this program into and martin has arranged a quite good program for this semester so keep or stay tuned to this i find it very fascinating, all these topics here. So quite a range of topics. Yes, my name is Wolfgang Schöfberger. I'm associate professor here at JKU Linz. And we deal with the topic of, amongst others, about utilization of co2 from and i named this talk today from climate killer to new resources um so my research fields i will describe a little later. First to the content of the talk. So first of all, I want to say a few words on sustainable chemistry. Some research projects I will introduce to you. Then I will talk about some general facts about global warming. And in the end of the talk, I will give you a detailed view on electrocatalytic conversion of CO2 into some usable chemicals. So CO2 valorization is the key word. But first, I want to make some promotion of the JKU. So I have here some pictures. promotion of the JKU. So I have here some pictures. On the left here you'll see the Somnium, the rooftop of the TNF tower. Here quite a nice view to Linz city. On the right the new library. Then the Kepler Hall where some conferences and some other stuff will be held. There's a gym in the basement also. And on the left you on the JKU campus. In this lit factory, new types of tool processes and systems are to be developed and tested. And there we will also be included in the future. And here you see some a map of the campus. So JKU has approximately 20 000 students and three thousand approximately for technical scientists or natural scientists. And here you have the scientists. And here you have the science park. There are new buildings built. It is not only three, but I think five or six already. I don't know. Here director sits and the library as you have seen and on the pond you have a coffee coffee shop and here on this tower there is this somnium what you have seen before and behind this tall building you have the technicum where some also some pilot plants are built. There will be another Technicum in a few years. This gives you a glimpse of how labs are look like in our TNF tower here TNF tower here and on the left you have the Open Innovation Center. Here just a quick view into the Open Innovation Center where some pilot plants or other plants are built. Then I said that I will give you a few words on sustainable chemistry. So we are in the process of discussing sustainable chemistry teaching module. It's a really difficult discussion because some colleagues are not against it, but it's a discussion to implement. But I think it's very important to to make such as at least a study module for interested students so uh i named this also bio-privileged molecules a new paradigm for bio-based chemical development and I since I'm 16 years already at the JKU and I know my colleagues already a little but anyways I want to implement such a study plan and we had some discussions already how to do this but I want to give you an idea why I want to implement this with some colleagues. Because the existing economy is, as you know, dependent on fossil resources. So actually, the whole industrial chemistry or technical chemistry is based on two resources, natural gas and liquid petroleum, NAFTA. steam cracker to basic compounds like ethylene, propylene, putadiene, benzene, and other byproducts. And this can be done, as I said, from gas or liquid in the steam cracker. So basically, you have these several chemicals, ethylene, propylene, benzene, xylene, methanol, glycerol. And from this you build the tree, which is a bad metaphor for these fossil resources but anyways you have these compounds made of these simple compounds okay so this is the existing way how to to synthesize more complex called molecules from basic molecules. And now I want to discuss a little bit about these bio privileged molecules. What does it stand for? Bio privileged molecules are defined as biology derived chemical species that can be efficiently converted to diversity to a diversity of chemical products, including both novel molecules and drop in replacements. And this paradigm was is not new and it has been discussed over the last several decades. And if you're interested, you can read about it in this paper and published in green chemistry by keeling and shanks and uh what they present is a way to identify molecules from biomass to convert biologically or chemically to valuable products. So you make from this gray tree, as a metaphor, a partially or a full green tree where the chemicals are extracted or isolated from the biomass. So biology and chemistry can interact to identify molecules. So to identify the sweet spot of branches of the tree to diversify to different products. So here in this array of molecules, which are interesting basic compounds, there need to be a sweet spot somewhere to identify molecules derived from biomass to synthesize further on interesting more complex molecules. And one of them is triacetic acid lactone. This is this one in the center. And in this star image you see we can synthesize out of this TAAL molecule an array or different compounds, like, for example, sorbic acid or lactones or acetyl acetone or high-value products like the chirally hydrogenated TAL molecule or progestone, a natural antimicrobial or other kinds of molecules. There are also other, there is also another class of compound, this is this muconic acid. And this is a very interesting molecule because you can react this to adipic acid, or hexanediol, or hexamethylamine, or other drop-in chemicals, or novel species like this trans-3-hexene di-oic acid, for example. So these are fully isolated from the biomass and could replace later on parts of the common industrial derived molecules from fossil resources. So let's go now to the CO2 side. How can we utilize CO2 or convert CO2? And there is a very good book and you can take a look at it. It's called Carbon Dioxide as Chemical Feedstocks. So how can we convert now CO2 to interesting molecules? And you see the dollar signs here. These are the real interesting molecules. ammonia to urea, CO2 with hydrogen, as you know, to methanol or with epoxides to carbonates, cyclic carbonates or polycarbonates. And there are a huge vast of different chemical reactions where CO2 can be incorporated into other molecules. Okay, so now to the example of CO2. How can we flue gas, so purified flue gas with electrocatalytic process with CO2 then to other compounds and I will talk about this later. So to chemical feedstock or via coupling over biotechnology to sustainable food supply or long-term energy storage for transportation and living. And here the cycle is closed. So the energy should come from renewable energies for sun or wind power plants. And so now to my research fields here at JKU. You know this power to x. So we synthesize catalysts power to x so we synthesize catalysts for heterogeneous bracket open photo bracket closed electrocatalysis and important or important fields or topics are water oxidation chemistry oxygen reduction chemistry hydrogen evolution in future we might go also in the direction of nitrogen conversion and today i will talk about the co2 activation and conversion the second project what we we are doing is we synthesize catalysts for biomass valorization. So what does this mean? We extract from biomass, for example, fatty acids, esters, oils, terpenes, and activate the CO2. And we keep it reacting with epoxide, for example. And we synthesize then um cyclic carbonates and from this cyclic carbonate a colleague of mine christoph topf is hydrogenating in his group with metal and see at carbon uh carbon systems yes as support catalyst catalysts via hydrogenation to the di-alcohols or poly-alcohols. Okay, so a future project here at the JKU campus will focus also on this strategy. I mentioned it briefly already. So we get from industrial resources flue gas, purified flue gas. We reduce this in the electrolyzer to formate. This is the formic acid molecule here and methanol. And this aqueous methanol or formate solution is then put into a bioreactor and yeast inside and the yeast is specially designed that it deals or it grows with methanol or formate across format, aqueous format solution. And then you can, the yeast is growing and this yeast can then be isolated, dried and can be used as animal feed or, and then biochemicals also can be extracted from it. Okay. So now to some general facts about global warming. So the essential core statement of climate research have been confirmed so well in recent decades that they are now generally accepted as facts by climate researchers. These key messages include the following. The concentration of CO2 in the atmosphere has risen sharply since around 1850 from the value of 280 to 420 ppm. Humans are responsible for this increase primarily through the burning of fossil fuels and building up industry on this, and secondly through the deforestation of the forests. CO2 is a climate-affecting gas that changes the radiation budget of the Earth. An increase in the concentration leads to a warming of the temperature close to the surface. As you know, if the CO2 content of the air doubles, the global mean temperature rises by 2 to 4 degrees Celsius. The most likely value is around 3 degrees. And since 1900, the global temperature has been risen by around 0.8 degrees Celsius. Temperature of the past 10 years were the warmest globally since measurements began in the 19th century and probably for at least a millennium. The majority of this warming is due to the The majority of this warming is due to the increased concentration of CO2 and other anthropogenic gases. Okay, so we have a problem. So this doesn't come now. Now I have a problem. Okay, so we have several greenhouse gases, CO2, CH4, methane, N2O, and fluorinated carbons. And here you have the climate impact. So CO2 has the lowest climate impact, but it has a 12 time in the atmosphere of around 1000 years. Methane is much lower 12 time in the atmosphere. And N2O 120 years and the fluorinated hydrocarbons around 1.5 to 260 years. So now a few things about CO2 emissions per year. So globally, there are around 37.1 gigatons CO2 emitted. And here you have the biggest emittance, 8 gigatons industry, 3.4 buildings, other sectors, Other sectors, 4.2, traffic, 6.6 gigaton, energy, economy, 14 gigatons. So you see which are the highest emittance here for CO2. And here, the comparison between the six biggest emittance next to, also compared to Germany, 5.1 gigatons in the USA, 10.9 in China, 3.5 in the EU, 800 megatons in Germany, 2.5 in India, 1.3 in Japan. So you see this and this is per human being 16 tons in US, 10.4 in Japan, 12.3 tons in Russia, 9.6 roughly 10 in the EU or Germany. So there's also change in different countries in the EU and 7.2 already in China. and 7.2 already in China. So, here, the mix in CO2 emission in Germany. I won't read it, you can do it by yourself. I will show you now how CO2 is transferred over the globe from seasonal change, a short video. This is carbon dioxide, or CO2, in the Earth's atmosphere. It is derived from a synthesis of observed and simulated data. Reds and yellows show regions of higher-than-average CO2, while blues show regions lower than average. The pulsing of the data is caused by the day-night cycle of plant photosynthesis at the ground. As CO2 is lifted away from the surface, it is rapidly spread around the world by high altitude winds. The high concentrations are from the build-up of CO2 during the northern hemisphere winter, when photosynthesis is not active and CO2 is produced by plant decay. By July, photosynthesis in the vast vegetation regions north of the equator draws massive amounts of CO2 out of the atmosphere, resulting in low carbon dioxide across the entire northern hemisphere. resulting in low carbon dioxide across the entire northern hemisphere. The growth and decay of vegetation in northern lands caused the seasonal change in atmospheric carbon dioxide seen here between March and July. While seasonal changes in vegetation growth control CO2 on monthly timescales, human activities govern long-term carbon dioxide trends. So now there are a lot of past conferences and in one of the last conferences, several countries negotiate the climate change goal and 1.5 degrees celsius of global warming was discussed and fixed not every country took part on it but a 1.5 degrees celsius of global warming was discussed. And there's an easy model. This is the bathtub model where you very easily see what the calculations are. So you have emissions which go into this bathtub and the bathtub is filled with CO2 in the atmosphere. And you have some net removals by the vegetation, by the oceans. And for this 1.5 degrees Celsius global warming, so this gamma goal, you have 500 gigatons left to fill the bathtub. Okay. So this sounds like a big amount, yeah, but we have 39 gigatons 2020 have 39 gigatons 2020 in the per year in the co2 co2 in the atmosphere 21 gigatons are left in the atmosphere. So now every year approximately 18 gigatons are going into this bathtub. And the net removal of CO2 is not enough. You see this by the growing of CO2 in the atmosphere leads then that the bathtub will overflow. So you can easily calculate this. We have roughly around 20 years time when the bathtub is filled. So now we need to reduce this U2. So not from our level right now, 20 gigatons down. And here, this graph crosses the net removal line around 2065, which is way too late, I would think. But here, the red line crosses the blue. So here, at this point, the bathtub is not increasing anymore. So the CO2 is not increasing anymore in the atmosphere. CO2 is not increasing anymore in the atmosphere. So by reducing the CO2, but we can also develop artificial strategies to remove the CO2. And then the full amount of CO2 in the atmosphere keeps the same at around 500 BPM. So here we're going to see useful product, which are carbohydrates. The reaction is driven by sunlight. CO2 goes into the leaves and oxygen as a byproduct is exhaled here. Water is needed for this process. I'll start the video. So now CO2 goes into the leaf, into pores of the leaf to be converted then in the chloroplasts. You see the nice green color of these leaves and why is the leaf green? This is because of this nice looking molecule, the chlorophyll molecule. It's a magnesium metal organic compound. It absorbs at wavelength around 400 to 450 nanometers in the violet and blue region and in the orange, yellow, orange, red region. And you'll see the complementary color, which is then resulting in a green color. That is why we see in spring and summer nice green colors everywhere. So the CO2 enters the chloroplasts now. And in the chloroplasts, there are the thylakoids. These are the thylakoids. And on the thylakoid membrane, you see this now, this membrane here, there are some big molecules. This is the ATP synthase molecule and other big molecules and some small molecules going out of the membrane. So here you see this. Fully loaded membrane here with thousands of proteins attached where the photosynthesis occurs. So what do you need for the photosynthesis? You need sunlight, the CO2, water, oxygen is produced, and in the dark reaction, glucose and sugars are produced. Okay. So, and the whole process is visualized here. The photosystem 2 protein complex. And you see here the water molecules coming to it. And what happens here? So, this is called the water splitting. So the water oxidation reaction and oxygen is produced. And protons, the H pluses are diffusing to the ATP synthase, where from ADP, you see the ATP very shortly, ATP is produced. And via energy transfer here to the photosystem one, NRTP plus is reacting with H plus in a reductive reaction to NADPH. The whole process is shown here also on the left here. Here you have the water splitting. Four electrons are going out of the water is oxidized. You have these manganese calcium cubane complex where the oxygen is produced as the byproduct and it's released throughout the thylakoid membrane to the air. the thylakoid membrane to the air. And here you see the electron transfer over these cascades to these complexes here, photosystem I and the ATP synthase. And on this background, you see the chloroblasts here under the microscope. So, Melvin Calvin then described not only the light-dependent reaction, which we have seen already, but he described the dark reaction, which is called the Calvin cycle, where the CO2 is reacted to sugars. Okay, in this process, I won't describe 1,5-biphosphate molecule. Then a reduction step is coming to this glycerin aldehyde phosphate molecule. And two molecules of glycerin aldehyde phosphate is then converted to glucose. The six molecules of CO2 and 18 ATP molecules, six molecules of ribose 1,5-biphosphate, this one, and NADH converts to just one molecule of glucose and then here six molecules of ribose 1,5-phosphate is also formed. So let's go further. So now we understand how nature is doing this. It's converting the CO2 and here we have again these 39 gigatons from energy, buildings, industry, transport, agriculture. And in total 21 gigatons are fixated, converted by the land sink or ocean sink. So what about the rest? How can we develop a strategy to convert these extra CO2? And there are some techniques which are known, separation of CO2, absorption process, chemical looping, membrane processes, absorption process, oxyfuel, for example. So there are some storage options for CO2, geological storage of CO2, mineral carbonization, methane hydrates. And there are some utilization options for CO2, like synthesis of polymers, what I have shown you already, options for CO2 like synthesis of polymers, what I have shown you already, synthesis of fuels, then synthesis of chemicals, micro algaes, electrochemical processes, artificial photosynthesis is a key word for this or the BEX which is the bioenergy with the CO2 capture and storage. with the CO2 capture and storage. So these are methods to utilize CO2. And as I've shown you, could we develop methods to valorize CO2 now? And I wouldn't stand here if we couldn't. So one can convert CO2, which is a very... You need to activate CO2 throughout the process and we do it in an electrochemical way. So CO2 can be transferred to methane, methanol, carbon monoxide, carbon monoxide and hydrogen, urea, polymers, oxalic acid or formate. And if you google this in And if you Google this in the internet, so you will find, for example, the Merck company, where they published a future insight prize. And they describe it like this. The dream product generates high energy density fuel from renewable energy water atmospheric carbon dioxide with an overall negative carbon dioxide balance so this is the goal and there's a lot of research going on right now and my lab is playing a very small part in this competition to convert CO2 in some valorized compounds. So you need to, as I said, activate the CO2 and treat this with water and by reduction with two electrons you go to carbon monoxide and here you see the market sizes of these several compounds. For example, carbon monoxide or formate, formic acid, methanol, ethylene, ethanol, or methane. And you see here on these reaction errors, they required electron number. So two electrons for CO or a formic acid, six electrons already for methanol, eight electrons for methane, 12 electrons for ethanol and ethylene. So now the question is, or you could ask me, how can we get the CO2 out of flue gas in German, Rauchgas. And there are some companies doing this already. So like the Asco company in Switzerland or Mitsubishi Heavy Industries, they built already plants, not pilot plants anymore. It's called amine washing. So you go with the flue gas into it, go with the flue gas into it. You clean the flue gas from solid particles. You're going into the absorber filled with amines, which are chemicals. You don't know. I need to know it now. But these can absorb this U2 and then regenerate it the co2 is then regener go into physical process where you can make super critical co2 out of it or and this is our strategy also to chemically convert. And we are not doing this with hydrogen in our lab or ammonia to urea or methanol. But we use water and electrons, protons and photons, if we want to do photoelectrochemical CO2 conversion and get then these interesting molecules out. So there are several strategies doing this. So you can use plasma activation, photoactivation, thermal activation, but we are focused mainly on these two parts on the photo and the electroactivation of CO2. So you need energy to activate the CO2 and on the cathode you can do that. So what are we doing in the lab? We design catalysts which are based on macro cycles. You see this cycle here of cobalamin cyanocobalamin you can buy this also at dm shop in a very diluted version here from sigma aldrich this is the only coring system in in nature so this metal cobalt, I mean, you can buy and if you dissolve this, you have an orange-red color. And this we wanted to mimic and we synthesized. And Sabrina Gronkler, my last PhD student, she is now in company. She left the GKU. now in company, she left the GKU, she synthesized actually a very similar molecule. This is called this is called COROL, very similar to the to this copalamine and I'll show you now, I hope it works, a model of this molecule. So here is the corolle, and here you have the triphenylphosphine ligand, which is not drawn on this slide here. But this is the L on the cobaltt this is this triphenylphosphine and if you dissolve the whole complex it's a metal organic complex you have also an orange red color it's in a round bottom flask the whole. So we can synthesize this in a rather high amount already. And we dissolve this in ethanol here in our lab in a three-necked round bottom flask in earth conditions. And then we put this on top of a very cheap carbon electrode. It can be carbon paper in this case or carbon felt. I'll put this to the camera again. You see it's very flexible and if you look close it has a very high surface. So the corolle can be dropped onto these carbon based electrodes shown here. And then you can do electrochemistry on that and if you go to reductive potential you see the the black curve which is under argon the curve and the red curve shows you in this region an increased catalytic current this is called the catalytic current. And the current density is drawn on the y-axis of this cycle voltammogram. The units are milliampere per square centimeter. So we treat the carbon felt or carbon paper electrode with these catalyst molecules. diffuses into these pores and reacts with the catalyst on the surface and in the pores of this catalyst support. And now here you see an animation of the process. The background here is the carbon paper under the microscope. So that's how carbon paper looks like. So now we put the molecules, the catalyst molecules And then the electric current is turned on and the CO2 is then reduced, for example, to ethanol. And throughout this process, on the left side you see a video of an H cell. So this is the first generation electrochemical cell where we did this study. And on the right you see also the H cell. And we published this work in 2019 in Nature Communications where you have this molecule here, just show you now in the camera, on top of the cathode, on top of or in also in the carbon-based material, in the carbon paper and carbon felt. And what happens? If you apply here the potential, this triphenylphosphine ligand goes off. Can you see this? And the CO2 instead of this comes to it and reacts on the cobalt in the middle, coordinates to the cobalt, and is finally reduced. CO2 is then reduced to methanol and ethanol. Okay, that's what we have published. So without any reaction with hydrogen, we can convert CO2 to C1 and C2 products. C1 means for example methanol formate compounds with only one carbon and C2 products compounds with two carbons ethanol acetic acid and so on for example. ethanol, acetic acid, and so on, for example. So how can we identify these molecules then in solution? So we put in here an internal standard, which is phenol. We know how many protons are in these molecules. And then we compare these internal standard with the developed compounds like say formic acid here. Here you have the ethanol signals in green and in red the methanol signals. Okay. And comparing these signals with the internal standard leads then to a quantification. We do this with an NMR spectrometer here. This is shown here. This is the magnet. And with different potentials here from minus 0.6 to minus 0.9, you'll see that we have different compounds developed. At lower minus values, so at minus 0.6, you have almost exclusively methanol here. And at higher reductive potentials, you have almost exclusive ethanol here. And this we sum up into a table. It looks a little bit crowded here, but you see again here we use different potentials from minus 0.5 to minus 1. And here you see the different amounts of compounds developed in this solution. In the gas phase, we could quantify approximately 30% for hydrogen and other compounds. So this was the story which we published there. And then we did another study where we changed from cobalt to manganese. from cobalt to manganese. And this complex produces at 1.5 versus silver chloride, 61% acetate, roughly 10% on methanol, and in the gas phase, CO and hydrogen. And we published this in Angewandte Chemie last year with a cover image. So what do we need for this? So we need a vast array of different techniques, array of different techniques. DNMR spectroscopy, which I've shown you for the quantification of the products here. Gas chromatograph for identifying the gaseous products. So we could get a very sensitive gas chromatograph to do this. Another thing is operando spectroscopy, so operandoando electropyromes, ESR spectroscopy. And all these techniques lead then to the reaction mechanism. And chemists are interested to describe what is going on and how it's going on. So we could really show what the process through the reductive reaction of CO2 to methanol or ethanol via six electron reduction or 12 electron reduction looks like. Okay. So a very complicated step. And luckily we have very good equipment at JKU, but not only at JKU. collaborated with friends in Rostock and in Bochum, elucidating this mechanism. So what are the next steps? In the next projects, we make new electrodes. These are called gas diffusion electrodes where you have a GDL layer, a microporous layer and inside of this microporous system you have the catalyst incorporated and gaseous CO2 comes and reacts with the catalysts then to the gaseous phase products here ethylene, CO and hydrogen and the liquid phase products. So this is the work in progress also joined with the team of Ulf-Peter Apfel in Germany at Ruhr University Bochum. Okay, and then Sun He, a future postdoc in my lab, is designing new flow cells. You see here an explosion plot of the second generation design of flow cells. Here you have the working electrode, it's getting a the next picture. This is the Nafion membrane, which is a semipermeable membrane in the center of here. This is the Nafion membrane. And And the third generation design will be the cell stack where you build multiple cells and put it together. So this leads to even increased amount of reduction product out of CO2 then. So this is the flow cell in our lab. On the left side, you have the cathode side and on the right side the anode side. This is the setup where you have here the flow cell, here a pump, a restaltic pump, for example. Here the bipotential state where the current comes from. Here the CO2 gas supply. And here we detect the current throughout the electro reduction reaction. So this is Sabrina here. This is Dominic Krisch. throughout the electro reduction reaction. So this is Sabrina here. This is Dominic Krisch. And actually, you see this now in action. Water electrolyte is pumped throughout the cathode. And the analyte is pumped to the anode side and is cycled. And in the cathode side, in the catholyte side, the reduction product is accumulating. We see here the current which is detected throughout the time. So it's a current to time plot here. And that's what we do in our lab. an FFG project, we try to scale up now this process. And then we start the full scale testing at JKU. We need to build and attract funding, a CO2 consortium here. So this will be roughly our cell then for the CO2 reduction in a PEM cell with flow field option. Here you see the flow field option where the CO2 goes into the cell exchanging with the cathode. This is made of stainless steel, can be put together already to a cell stack here. You'll see this in this graph here. Here is this electrochemical cell. And maybe in two or three years, you can visit us in the Technicum and take a look how we can upscale the CO2 reduction reaction already. So this is the target. These are the few cell designs, cell stack designs, which we're we gonna produce. And this is the goal. The sun should be the energy supply or wind energy. It converts you to the liquid phase product and hydrogen. This is my team. I want to thank especially a few person, Sabrina Gonglach, Michael Haas, Dominic Krisch, Jessica Michalke, Daniel Timmeltaler and Christoph Tropf. And my collaboration partners, Philipp Stadler, Halime Koshkun Al-Shabur Professor Marco Hapke Dr. Christoph Topf Professor Stefan Müllecker Physicist on the Semiconductor and Solid State Physics Department and the external collaboration partners are Ulf-Peter Apfel from Ruhr-Uni Bochum, Djabo Rabe from Leibniz Institute of Catalysis, and Professor Dr. Angelika Brückner, also from the same institute in Rostock. And finally, I want to thank you for your kind attention. There's one question, which is maybe the most important. Will this method save the world? Yes, sure. But I guess not alone, right? We are not alone. No, we are not. It's a huge community now focusing on exactly this problem and there are lots of different attempts and with different catalysts with copper whatever so chemists we need new chemists students interested in this so there is a lot going on and you have you can be really creative in developing new catalysts but i think in the next 10 years 15 years there will be really we are a technology behind this where we can convert CO2 directly to some useful products this is my feeling but I had already a year now of discussion with companies and the biggest problem is that the industry pays they are interested but they sit on their money and think ah yeah we will have it in a few years anyways so um we will have it in a few years anyways. So yeah, I had already very interesting discussions on that. Okay, so I think I will just close the live stream and thank you very much for today and we will have the next talk on the 12th of April. So see you again. Thanks. Bye bye.