Bridgewater College BC Digital Commons

Chemistry Faculty Scholarship Department of Chemistry

Spring 5-3-2017 Extraction of Protoporphyrin IX for Use in Dye- Sensitized Solar Cells Ken Overway [email protected]

Carleigh Studtmann Bridgewater College

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Recommended Citation Overway, Ken and Studtmann, Carleigh, "Extraction of Protoporphyrin IX for Use in Dye-Sensitized Solar Cells" (2017). Chemistry Faculty Scholarship. 8. https://digitalcommons.bridgewater.edu/chemistry_faulty_scholarship/8

This Poster Presentation is brought to you for free and open access by the Department of Chemistry at BC Digital Commons. It has been accepted for inclusion in Chemistry Faculty Scholarship by an authorized administrator of BC Digital Commons. For more information, please contact [email protected]. Extraction of Protoporphyrin IX for Use in Dye-Sensitized Solar Cells Carleigh Studtmann, Garrett George, and Dr. Kenneth Overway Department of Chemistry, Bridgewater College

0.16 0.14 0.12 400 nm Introduction Results and Discussion 0.1 280 nm Dye-sensitized solar cells (DSSC) are a possible 0.08 0.06 0.18

alternative to traditional solar energy technologies. Metal- Absorbance 0.04 free organic dyes such as porphyrins seem to be an 0.16 Emission 0.02 Excitation 0 0.14 0 2 4 6 8 10 especially promising option as a sensitizer due to their 631 Time (seconds) 0.12 characteristic Soret band and smaller Q-bands in the visible Figures 4. Chromatogram of the PPIX extract on the silica column with an spectrum. Protoporphyrin IX (PPIX) is a naturally occurring 0.1 ethyl acetate mobile phase, with the absorbance measured at 280 nm and 0.08 400 nm. porphyrin found in sources hemoglobin, chlorophyll, and Intensity brown egg shells. PPIX exhibits typical porphyrin 0.06 0.16 8 0.14 0.04 9 absorbance spectrum, and the carboxylic acid substituents 0.12 10 0.02 0.1 11 make it ideal for direct attachment to the TiO2 of the DSSC. 0.08 0 13 The purpose of this research is to extract PPIX at a high 310 410 510 610 710 0.06 Wavelength (nm) Absrobance 0.04 enough concentration from brown eggshells that it could be 0.02 st Figure 1. Fluorescence excitation and emission spectra of the 1 0 purified using a liquid chromatography fraction collector PPIX extract. Inset is the spectra from Kathiravan, et al. 350 400 450 500 550 600 650 and used as a sensitizer in a DSSC. Wavelength (nm)

Zoomed in Q-bands Figure 5. Absorbance spectra of all fractions of PPIX extract from a silica 2.5 column with a hexanes:isopropyl alcohol mobile phase. Soret Band 0.2 0.1 2 Absorbance 0 • First extraction performed with 15.5 grams of brown egg 480 580 680 Wavelength (nm) 1.5 shells and a recovery yield of 246 ppm • Second extraction performed with 224.9 grams of brown

1 egg shells and a recovery yield of 344 ppm Absorbance Conclusion 0.5 504 Q-bands • Protoporphyrin IX was successfully extracted from PPIX 0 brown egg shells based on the comparison of Experimental 300 350 400 450 500 550 600 650 fluorescence and absorbance spectra to literature Part 1: Extraction Wavelength (nm) values (Figures 1 and 2). • 2M HCl and ethyl acetate added to brown egg shells Figure 2. UV-vis absorbance spectrum of 2nd extract of PPIX • PPIX was partially purified from the extract, but until CO production stopped showing the Soret band and four Q-bands. 2 the purification process still needs to be optimized. • Filtered using Buchner funnel, filter paper, and silica 2.5 0.3 • It was discovered that PPIX is highly light sensitive • Organic layer separated, washed, and dried with 0.25 and thus undergoes self-sensitized photooxidation anhydrous sodium sulfate Sample 2 Initial 2 (Figure 3). • Ethyl acetate solvent evaporated off of sample to Sample 2 after 4 days 0.2 calculate recovery mass of PPIX 1.5 References Part II: Purification 0.15 1) Campbell, W.; Jolley, K.; et al. Highly Efficient Porphyrin Sensitizers for 1 Dye-Sensitized Solar Cells. Chemical Letters 2007, 111, 11760-11762. • PPIX extract was purified on silica column using ethyl 0.1 2) Dean, L.; Miller, T. A.; Bruckner, C. Egg-Citing! Isolation of acetate mobile phase. Various other stationary phases and Protoporphyrin IX from Brown Eggshells and its Detection by Optical 0.5 0.05 Spectroscopy and Chemiluminescence. Journal of Chemical Education 2011, non-polar mobile phases were used also. 88, 788-792. Absorbance of Initial Sample 2 • Eluent passed through 390 µL flow cell cuvette, and the 0 0 3) Imahori, H.; et al. Large pi-Aromatic Molecules as Potential Sensitizers for Absorbance Sampleof 2 after 4 days absorbance at 280 nm and 400 nm was monitored on the 300 400 500 600 700 800 Highly Efficient Dye-Sensitized Solar Cells. Accounts of Chemical Research Wavelength (nm) 2009, 42 (11), 1809-1818. Cary-50 spectrometer using a kinetics program. 4) Kathiravan, A.; et al. Protoporphyrin IX on TiO2 electrode: A spectroscopic Figure 3. The hypochromic and red-shift in the absorbance and photovoltaic investigation. Dyes and Pigments 2013, 96, 196-203. • Absorbance spectra of the fractions that absorbed spectrum of the 2nd extract of PPIX after four days of exposure to 5) Mathew, S.; Yella, A.; Gao, P.; et al. Dye-Sensitized Solar Cells with 13% significantly at 400 nm were measured to determine if light and oxygen. Shift is due to self-sensitized photooxidation. Efficiency Achieved through the Molecular Engineering of Porphyrin they contained PPIX. Sensitizers, Nature Chemistry, 2014, 6, 242-247.