4.6 Article

Functionalized gold-nanoparticles enhance photosystem II driven photocurrent in a hybrid nano-bio-photoelectrochemical cell

Journal

JOURNAL OF MATERIALS CHEMISTRY A
Volume 9, Issue 32, Pages 17231-17241

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d1ta03350f

Keywords

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Funding

  1. Deutsche Forschungsgemeinschaft (DIP) [LU315/17-1]
  2. Israeli Ministry of National Infrastructures, Energy and Water Resources [218-11-044]
  3. Grand Technion Energy Program (GTEP)
  4. Technion VPR Berman Grant for Energy Research
  5. European Union's Horizon 2020 research and innovation programme under the Marie Skodowska-Curie grant [798409-HMST-PC]

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The combination of market-grade spinach PSII with gold nanoparticles modified with cystamine-2,6-dichlorobenzoquinone (PSII-AuNPCys-DCBQ) results in high photocurrent values and stability, showing enhanced performance of PSII in converting solar energy to electrical current. The quinone-modified gold nanoparticles play a dual role in harvesting and transferring excitation energy to PSII, as well as improving electron transfer to the graphite anode, leading to significant enhancement in anodic photocurrent.
The use of photosystem II (PSII) in hybrid bio-photoelectrochemical cells for conversion of solar energy to electrical current is hampered by PSII's narrow absorption cross-section and the generally poor electrical connection between isolated complex and different anode materials. Here, we merge isolated market-grade spinach PSII with 25 nm cystamine-2,6-dichlorobenzoquinone (cys-DCBQ) modified Au-nanoparticles (PSII-AuNPCys-DCBQ) to obtain one of the highest reported photocurrent values to date (35 mA cm(-2) mg(-1) chlorophyll), retaining the native oxygen evolution properties of PSII. More than 80% of the PSII in solution assembles stably onto the AuNPCys-DCBQ. Spectroscopic studies show strong functional association in these hybrid particles. Mechanistic investigations reveal a dual role of the quinone-modified AuNPs, harvesting and transference of the excitation energy to PSII (resulting in similar to 10-fold enhancement of anodic photocurrent in the 500-550 nm irradiation range) and simultaneously improving the electron transfer from PSII into the graphite anode (by almost 6-fold over the entire visible range of light).

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