US 20140O38065A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2014/0038065 A1 Ramasamy (43) Pub. Date: Feb. 6, 2014 (54) PHOTOSYNTHETIC ELECTROCHEMICAL Publication Classification CELLS (51) Int. Cl. (71) Applicant: University of Georgia Research HIM I4/00 (2006.01) Foundation, Inc., Athens, GA (US) (52) U.S. Cl. CPC ................................... H0IM 14/005 (2013.01) (72) Inventor: Ramaraja P. Ramasamy, Watkinsville, USPC ........................................... 429/401; 429/532 GA (US) (22) Filed: Aug. 2, 2013 O O The present disclosure provides photosynthetic electro Related U.S. Application Data chemical cells including photosynthetic compounds and (60) Provisional application No. 61/679,118, filed on Aug. methods of generating an electrical current using the photo 3, 2012. synthetic electrochemical cells. Patent Application Publication Feb. 6, 2014 Sheet 1 of 28 US 2014/003.8065 A1 Patent Application Publication Feb. 6, 2014 Sheet 2 of 28 US 2014/003.8065 A1 Tophography Amplitude Phase Y 8:338 s 8 ra O g 3: 88: 8 x: FIG. 2 Patent Application Publication Feb. 6, 2014 Sheet 3 of 28 US 2014/003.8065 A1 FIG. 3A FIG. 3B FIG. 3C Patent Application Publication Feb. 6, 2014 Sheet 4 of 28 US 2014/003.8065 A1 FIG. 4A FIG. 4B -8 3. -08 -0.5 -0.2 0.1 0.4 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 Potential (V vs. Ag|AgCl) Patent Application Publication Feb. 6, 2014 Sheet 5 of 28 US 2014/003.8065 A1 FIG. 5A 0.30 0.20 0.15 0.10 0.05 x-Thylakoid. MWNT xx - Unmodified MWNT 100 300 500 700 900 1100 1300 Time (s) FIG. 5B «Thylakoid - MWNT - Unmodified MWNT 125 200 275 350 425 500 575 Time (s) Patent Application Publication Feb. 6, 2014 Sheet 6 of 28 US 2014/003.8065 A1 FIG.5C 140 120 100 40 O 10 20 30 40 50 60 70 80 90 FIG. 6 4. 5 213. 555 Patent Application Publication Feb. 6, 2014 Sheet 7 of 28 US 2014/003.8065 A1 FIG. 7A . POWer Oad Thylakoid-MWNT aCCase-MWNT FIG. 7B 0.40 0. 3 O 8. 0. 15 k -&- Voltage *: 8. Power x. S & r 0.00 $x8×8 *& Current Density (LA.cm) Patent Application Publication Feb. 6, 2014 Sheet 8 of 28 US 2014/003.8065 A1 i O 8 400 450 500 550 600 650 700 750 Wmax (nm) FIG. 8 Patent Application Publication Feb. 6, 2014 Sheet 9 of 28 US 2014/003.8065 A1 (a) x 82.68 gig (b) 13.8 big (c) & 6.89 kg (d) 4.13:g (e) : y-(b) s: «» ------------------ ----------------- «» Time (s) Patent Application Publication Feb. 6, 2014 Sheet 10 of 28 US 2014/003.8065 A1 FIG. 9C - O. SS (a) - 8: 100 M (b) 200 M O. FIG 9D (a) ::::::: 0.0 mV (b) is is 100 mV (c) x 200 mV (d) x : x: 3OO V Patent Application Publication Feb. 6, 2014 Sheet 11 of 28 US 2014/003.8065 A1 «Thy Controi xxy + KCN Potential (V vs. Ag|AgCl) FIG 11 88: W. W. W. W. W. W. W. Ferrieyatide * 2,8-dichixro-p-ixexact sixte: 160 . .4-8eraxxttite 0.80 o 40 Patent Application Publication Feb. 6, 2014 Sheet 12 of 28 US 2014/003.8065 A1 FIG. 12A 4-axxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxx× Thy -xx -- FECN + Thy 400 500 600 7OO 800 400 500 600 700 800 Wavelength (nm) Patent Application Publication Feb. 6, 2014 Sheet 13 of 28 US 2014/003.8065 A1 FIG. 12C xx: Para/Diduat : ... Thy+Para/Diquat 500 Wavelength (nm) FIG. 12D 33 ..., DCMU . Thy + DCMU 100 soo 600 700 800 Wavelength (nm) Patent Application Publication Feb. 6, 2014 Sheet 14 of 28 US 2014/003.8065 A1 3g 0.5 Patent Application Publication Feb. 6, 2014 Sheet 15 of 28 US 2014/003.8065 A1 009_008_002_002_002_001 {s}ºwa??. £17J,"SDI \/7),"SDI writuatinoo olid Patent Application Publication Feb. 6, 2014 Sheet 16 of 28 US 2014/003.8065 A1 ×....* £19),"5DIE xix 3 : 3 x 8 Yr tied 300 Patent Application Publication Feb. 6, 2014 Sheet 17 of 28 US 2014/003.8065 A1 FIG. 16A 8. xxxx terticit: ~ 888 orbicide EIV vs. Ag/AgCl FIG. 16B 3x f xxx x is bicide X & 8::::::::8 EIV vs. Aglagol Patent Application Publication Feb. 6, 2014 Sheet 18 of 28 US 2014/003.8065 A1 « No Paraquat Patent Application Publication Feb. 6, 2014 Sheet 19 of 28 US 2014/003.8065 A1 FIG. 18 Patent Application Publication Feb. 6, 2014 Sheet 20 of 28 US 2014/003.8065 A1 FIG. 19A O.35 , . s : 3. : Xaxatickeria } is - - - Av : * * *xistes: 388 ::: 88: 88: 833 383 : 388: 1600 Time (s) FIG. 19B 3::: 8: ; : ::: 888: 8: 838 :::::: ::: 8: Time (s) Patent Application Publication Feb. 6, 2014 Sheet 21 of 28 US 2014/003.8065 A1 FIG. 20 50 - (a) × 14 ag 88: (b) on 28 ag s 4. : f (d): (c) - w842 ig : (d) x 56 ug : & is 30 : & RN {} {{ 408 800 330 CE 2: 488 808 Time (s) (a) «32 ig 2:38x (b) x 64 pig (c) x -88 ig 2 & 8 88 & 3. Time (s) Patent Application Publication Feb. 6, 2014 Sheet 22 of 28 US 2014/003.8065 A1 x x is c x 58 x c; 8 8: 8: 88: 8: 888 : ::: 888 fire is FIG. 23 (a) « » Aiterrate iigittard dark (b) xxxx continuous sight (c) * * *satistiak 88: 88: 38 2833 28:8 ines Patent Application Publication Feb. 6, 2014 Sheet 23 of 28 US 2014/003.8065 A1 FIG. 24A 08 - s $3.3 :33: :8: SE: SS:: 8:38: 838: f:38: Wawelergittan: FIG. 24B (b) os (c) x x 388 fire (d) x 683 it (e) x x 888 in $3 Time (s) Patent Application Publication Feb. 6, 2014 Sheet 24 of 28 US 2014/003.8065 A1 sA. i s s f s{o-A--3.x s s: 3. S ofyfy Patent Application Publication Feb. 6, 2014 Sheet 25 of 28 US 2014/003.8065 A1 FIG. 26A 120 x - c. iii.it ocii ( mit 8 • Brist.1 mii) - - - - KCN 10 mM) 8 8. 38: :38 88: 38 {{ {{ {:} 88 ise is FIG. 26B 100 4.68 OOO 2 O DCMU DBMB KCN Patent Application Publication Feb. 6, 2014 Sheet 26 of 28 US 2014/003.8065 A1 FIG. 27A SS x-------------------------------------------------------------------------------------------------------------------------------------------------------------------- 38 28: i: s: 8:{ {{{: 288 ii. 38. Time (s) FIG. 27B 100 O.05 nM. O.1 mM 0.5 nM M ConCentration of DCMU Patent Application Publication Feb. 6, 2014 Sheet 27 of 28 US 2014/003.8065 A1 8: xxx, 38 8 x. it is &: x x * r 33 -: 3. kxxx-xx-xx-xx-x-xx-xx-xxx { 28 :::w 8:8 8: {:} . s : : 8 Times) FIG. 28 Patent Application Publication Feb. 6, 2014 Sheet 28 of 28 US 2014/003.8065 A1 FIG. 29A (a) x x Kix (s & (b) okcNo. mi. (c) or KCN 0.5mm (d) - KCNiemi (e) or KCN 20 ml x 8 38 X. 2: 88: 88: 8: {x :38: 38: 1600 Time (s) OO & & S. 6 O 4.O 2 O O & O.1 mM 0.5 mM O mM 20 mM Concentration of KCN US 2014/003 8065 A1 Feb. 6, 2014 PHOTOSYNTHETIC ELECTROCHEMICAL cal reactions, and the anode composite is configured such that CELLS electrons generated by the thylakoid membrane are con ducted to the anode via direct electron transfer. In some CROSS-REFERENCE TO RELATED embodiments, the thylakoid membrane is coupled to the APPLICATION anode by a matrix of nanostructured material. Such as described above. 0001. This application claims priority to copending U.S. 0006 Additional embodiments of photosynthetic electro provisional application entitled, “Photosynthetic electro chemical cells of the present disclosure include an anode chemical cells.” having Ser. No. 61/679.118, filed Aug. 3, composite having an anode in electrochemical communica 2012, which is entirely incorporated herein by reference. tion with a photosynthetic organism or a part of a photosyn thetic organism, and a cathode composite having a cathode BACKGROUND and at least one enzyme or metallic catalyst capable of reduc 0002 Plant photosynthesis provides an unmatched quan ing O. In such embodiments, the photosynthetic organism or tum efficiency of nearly 100%. In recent years, significant part thereof is capable of oxidizing water molecules and interest has evolved in mimicking and/or harnessing the pho generating electrons using light induced photo-electrochemi tosynthetic process for energy conversion and hydrogen gen cal reactions, and the anode composite is configured such that eration applications. Multiple approaches to artificial photo the electrons generated by the photosynthetic organism or synthesis exist, including light energy harvesting using part thereof are conducted to the anode via direct electron natural pigments from plants and microorganisms and using transfer. In some embodiments, the photosynthetic organism whole cell microorganisms. Scientists have explored photo or part thereof is coupled to the anode by a matrix of nano synthetic organelles such as thylakoids, chlorophyll mol structured material, as described above. In embodiments, the ecules, photosystems, and oxygen evolving complexes for photosynthetic organism can include, but is not limited to, photo-electrochemical activity. However, the challenge of cyanobacteria, green Sulfur bacteria, algae, spirulina, chlo establishing electrical communication between photosyn rella, and combinations of Such organisms. thetic reaction centers and the electrode has proven extremely 0007. The present disclosure also includes methods of difficult. Thus, to date, a photosynthetic electrochemical cell generating an electrical current with a photosynthetic elec that allows direct electron transfer between the photosyn trochemical cell.