1. Capturing Carbon Dioxide with Metal-Organic Frameworks
Nicole “Missy” Oostendorp
Dr. Maslowsky Ph.D.
My name is Nicole Oostendorp, I am a biochemistry major working under dr. Maslowsky on capturing CO2 with Metal Organic Frameworks

2. Metal-Organic Frameworks
Porous Crystals
Lattice-like
Metals connected by organic molecules
Pores can store gases
MOFS are an extensive class of porous crystals in which organic molecules called struts link metal-containing clusters
Well-ordered, lattice-like crystals that form a cage structure
The lattices are usually made up of copper, zinc, cobalt, or in this case potassium connected by organic molecules
Due to there cage stucture MOFs form roomy pores that can store gases like hydrogen and carbon dioxide that can remain trapped there within the MOF
This is a representation of the MOF I will be making where the gray is C, the O is red, and the K are the blue. The yellow circle is showing the pore.
K ions???

3. Metal-Organic Frameworks
Interactions between the gas molecules and the pore walls makes them good candidates for gas storage
How exactly do they work?
Ion-Induced Dipole interactions
Weak attractions
Reversible binding
The interactions that occur between the gas molecules and the pore walls of the MOF are what makes them good candidates for gas storage.
CO2 is nonpolar
Gas molecules are able to be absorbed due to and ion-induced dipole force. Which consists of an ion and a non-polar molecule interacting where the charge of the ion causes a distortion of the electron cloud on the non-polar molecule giving it a dipole
They are weak interactions, which lead to the MOFs having reversible binding capabilities

4. Uses of Metal-Organic Frameworks
Gas storage
Transportation
Gas/Vapor Separation
Drug Storage
Delivery
Catalysis
Luminescence
Environmental
Trap unwanted gases
Transportation in the since that they can be potential used in hydrogen powered cars. As of now hyrdrogen is being stored in pressure tanks which pose safety issues (combustion). MOFs can be in place because they can easliy absorb the H and completely release is.
But in the case of my research I’m going to talk about environmental issues

5. Significance of Metal-Organic Frameworks
Environmental implications
Figure taken from the EPA
MOFS are very important and growing in popularity because they have extensive environmental implications. This graph shows the increasing amount of CO2 levels in the atmosphere over the last 100 years and the levels will keep increasing due to the increasing amount of burning of fossil fuels, like coal.
MOFs can be used in places that burn these fossil fuels to potentially help trap the co2 being produced there
Store in the ground or in oil wells that have been depleted, resell
Extract co2 from it and reuse without getting it in the air
a form a cellulose and can be easily disposable

6. Research Goals Creating MOFs from renewable and nontoxic sources
Determine whether MOFs are able to store CO2 using color changes and Infrared Spectrometry
Modifying the resulting procedure for use as an experiment for a non-majors science class
So my goals for this research are to create MOFs from renewable and nontoxic sources
And then use these MOFs I have made to find the best conditions for CO2 capture within them moderating it using color changes and IR
And then lastly to develop easy to do lab procedures for Dr. Maslowsky to use in his global warming class with non-science majors.
Making the MOFs with nontoxic and renewable materials allows for a move “green” method of capturing CO2 and doesn’t present any further environmental hazards

7. Associated Problems
To date MOFs composed of nonrenewable materials and transition metals
Made with harmful and toxic solvents
Using natural and renewable products
Asymmetry challenge
Associated problems with making MOFs to date is they have been mainly composed of nonrenewable materials and different transition metals made with harmful and toxic solvents
AND using and renewable products pose a problem due to the inherent asymmetry of their building units, which are not susceptible to crystallization in the form of highly porous frameworks.

8. Resolution Gamma-Cyclodextrin
So using Gamma-Cyclodextrin which is a polysaccharide provides a solution to this problem because it is composed of eight asymmetrical glucose residues arranged in a ring that is symmetrical. Using this as a starting material will help provide the symmetry needed to produce a highly porous MOF

9. Synthesis of Metal-Organic Frameworks
Gamma-cyclodextrin
Potassium benzoate
Dissolved in H2O
Potassium benzoate is the potassium salt of benzoic acid. it is completely edible and usually used in food preservatives.
So first we start out by dissolving gamma-cyclodextrin and potassium benzoate into water in a small beaker. Several different water to compound ratios of this were done in order to get the highest yield.
This is a representation of the Polysaccharide MOF I will be making where the gray is C, the O is red, and the K are the blue

10. Synthesis Cont. Placed in ethanol and covered IR 30 Trials
Time and condition variation
Filtration
Water vs. Ethanol IR
This is then placed into a larger beaker containing ethanol and then covered and let set for 3 days to a week until crystals are formed.
Ethanol is used to reduce the solubility of the materials used and speeds up the kinetics of the reaction.

11. Methyl-Red Indicator Methyl-Red used to color crystals IR
Dichloromethane
20 Trials
Time variations
Filtration
Ethanol vs. Dichloromethane IR
Used a methyl red dichloromethane solution to dye the crystals to a yellow color, which is indicative of a CO2 deficient system.

12. Carbon Dioxide Treatment
Exposed the crystals to CO2 via two methods
HCl and Sodium Bicarbonate
Dry Ice IR

13. Metal-Organic Framework growth
Optimized the % yield of the crystals
Smallest amount of water possible
95% ethanol and wash
Changing the reaction conditions effected the yield
0.025 g to 1.9 g of product
Allow crystals to grow for at least 3 days.

14. Methyl Red Treatment
Needs to sit in solution for at least 2 days. Longer doesn’t hurt it though
Talk about different washes
Literature reading did not indicate what was used for the washes. So I used both ethanol and dichloromethane. Found that using the ethanol resulted in the crystal being an orange or even sometime red color. When using the dichloromethane and letting the crystals sit in the filtration funnel for a minute made the crystals the desired yellow color
It appeared that using the ethanol wash made it harder for the crystals to absorb the CO2….Why???
CO2 treatment did cause color change (as can be seen in the pictures), but found that the dry ice worked better than HCl and sodium bicarbonate method.

15. Infrared Spectrum of Carbon Dioxide Gas

16. Infrared Spectrum of metal-organic framework

17. Infrared Spectrum with Methyl Red prior to CO2 Treatment
After dyeing the crystals and letting them sit for a couple days I observed a slight color change going from a light yellow-orange color to an orange. This led me to take this IR to see if there was any noticeable CO2 present in the system. Which there was indicated by this slight peak.

18. Infrared Spectrum with CO2
IR of crystals after 15 min exposer to CO2. I found that either methods of CO2 exposer produce about the same peak in the spectrum

19. Infrared Spectra Zoomed in

20. Infrared Spectrum after 20 minutes

21. Infrared Spectrum after 2 days

22. Infrared Spectrum after 7 days
So this spectrum shows that after 7 days theres still a very small peak at the CO2 region, all these IR show that my MOFs were able to pick up the CO2 and after week the CO2 left the system

23. Conclusion The growth of the MOFs was optimized
The extent to which CO2 binds in the system was explored
Methyl Red IR
Reversible binding capabilities
I was able to optimize the growth and yield of the crystals by using the highest proof of ethanol and the littlest amount of water need to dissolve the starting compounds. I discovered that it takes 3 days to a week to get maximum growth.
I was then able to explore the extent to which CO2 binds in the system qualitatively using the Methyl Red indicator.
Also was able to use a more quantitative method to see the CO2 absorbance over time by taking the IRs which allowed me to see that the MOFs can uptake the CO2 and that they have reversible binding capabilities. But even after a couple of days, the CO2 was still present

24. Work to be done Further investigate IR Mass Production
Commercialization
Further investigate the use of IR by Inspecting the finger print region to see if the CO2 binding causes any changes

25. Acknowledgments Dr. Edward Maslowsky Dr. Christina Edwards
Loras College
My Family

26. Sources
Fellman, M. (2010). Edible Nanostructures. Northwestern University Newscenter.
Gassensmith, J. J. (2011). Strong and Reversible Binding of Carbon Dioxide in a Green Metal-Organic Framework. Journal of American Chemical Society,
Greenway, A. (2014). In situ Synchrotron IR Microspectroscopy of CO2 Adsorption on Single Crystals of the Functionalized MOF Sc2(BDC-NH2)3**. Wiley Online Library,
Kuppler, R.J. (2009). Potential application of metal-organic frameworks. ScienceDirect,
Smaldone, R. (2011). Metal-Organic Frameworks from Natural Products. Wiley Online Library,