PROTEINFUNCTIONALIZED HEMATITE PHOTOELECTRODE FOR SOLAR WATER SPLITTING

1STEP FURTHER TOWARD ARTIFICIAL PHOTOSYNTHESIS

P.P.Wyss1,6,D.K.Bora1,2,K.GajdaSchrantz1,3,E.A.Rozhkova4,J.Ihssen5,U.Pieles6,E.C.Constable2,T.Graule1,A.Braun1
1LaboratoryforHighPerformanceCeramics,EMPA,berlandstrasse 2DepartmentofChemistry,UniversityofBasel,CH4056Basel 3 EnvironmentalChemistryResearchGroup,Dep.ofInorg.andAnal.Chem.,UniversityofSzeged,Dm 4Centerfor

129,CH8600Dbendorf
PE

tr 7,H6720Szeged

PC

Nanoscale Materials,Argonne NationalLaboratory,Argonne IL60439 5LaboratoryforBiomaterials,EMPA,Lerchenfeldstrasse 5,CH9014St.Gallen 6UniversityofAppliedSciences,NorthwesternSwitzerland,Mattenstrasse 22,CH4059Basel

AP

Thylakoid membrane

PS II

PS I

Phycobilisome

Integration of lightharvesting proteins on semiconductor surfaces can improve the performance of photoelectrodes. Phycocyanin captures light in cyanobacteria and funnels it to the reaction center for photosynthesis. A way to immobilize Phycocyanin on a nanostructured hematite surface to obtain higher photocurrent with long term stability is reported.

Semiconductor Film Preparation: A glass wafer with a conductive fluorine doped tin oxide (FTO) layer was dip coated in a precursor solution consisting of oelic acid and FeNO3 and then annealed at 500C for 30 to create a nanostructured hematite thin film electrode. Films were characterized with SEM (Fig. 1., 2.), XRD, EDX, Linear Voltammetry, Profilometry and UV/VIS spectroscopy. Surface Functionalization: Surfaceexposed hydroxyl groups react with 1,1 carbonyldiimidazol (CDI) and form a relatively stable imidazolyl carbamate. This conjugate can further react with accessible primary amine groups of phycocyanin (PC) (Fig. 1.) Phycocyanin immobilization: Tyrosinase catalyzes the reaction from Ltyrosinase into melanin. When there is a mixture of PC and L tyrosine, tyrosinase can integrate PC due to surface exposed tyrosine side chains into the melanin structure (Fig. 2., Fig. 3.) which will then react with the activated hematite surface.
Figure 2. Selforganized PCmelaninstrains onhematite (SEM) Figure 1. ScanningElectron Micrograph of nanostructured hematite film(red background)with crosslinked phycocyanin network (green)

Photoelectrochemical Performance: Linear voltammetry under dark and light conditions was performed to determine the performance of the hematite films (Fig. 4). The sample operates as the working electrode in a three electrode system using 5 mM Phosphate buffer salin pH 7.2 as electrolyte.

300

PristineHematite

CurrentDensity[A/cm2]

250

200

PCMelaninimmobilizedon Hematite

150

2fold increase
100 50

0 100 300 500 700 900

Potentialvs.Ag/AgCl,[mV]
Figure 4.Current density ofpristine hematite and enhancementofcurrent densitywithPCmelanincoating

To prove functionality of immobilized proteins, PC was exchanged with laccase. After cross linking with hematite, 45 mU/cm2 of surfaceassociated activity was determined using ABTS substrate (Fig. 5.).
Figure 5.Hematite filmwith immobilized laccase converting ABTS

ABTS 420nm

Figure 3. Preparation route of PCconjugated hematite surface trough CDI mediated reaction

CONCLUSION We can double the photocurrent of hematite by phycocyanin crosslinking functionalization. The current density was followed by applying voltage with and without sunlight. When applying a voltage of 200 mV over 24 hours to test the stability of the created protein film, the current density of the water splitting system even increased. Proof of concept for immobilization is achieved by exchanging phycocyanin with laccase and subsequent confirmation of ABTS oxidation with the surface bound enzyme. ACKNOWLEDGEMENT FinancialsupportbySNF#206021121306,BfE #152316101883and#153613102809,Sciex#10.013andEUFP7NanoPEC #227179
1Contact:krisztina.gajdaschrantz@empa.ch