Modelling of the cathodic and anodic photocurrents from Rhodobacter sphaeroides reaction centres immobilized on titanium dioxide.

Modelling of the cathodic and anodic photocurrents from Rhodobacter sphaeroides reaction centres immobilized on titanium dioxide.
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DOI:
10.1007/s11120-018-0550-8
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发表时间:
2018-10
影响因子:
3.7
通讯作者:
Gibasiewicz K
Gibasiewicz K
中科院分区:
生物学3区
文献类型:
--
作者:
Białek R;Swainsbury DJK;Wiesner M;Jones MR;Gibasiewicz K

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作为利用太阳能的许多新技术之一,人们对开发基于来自光合生物如细菌红细菌(Rba)的反应中心(RC)的光电化学电池感兴趣。sphaeroides在这份报告中探索的电池架构是类似的染料敏化太阳能电池,但与天然色素蛋白质复合物,而不是人工染料传递电子到介孔层的二氧化钛。Rba。通过工程化的膜外肽标签将类球形RC结合到沉积的TiO 2上。以TMPD(N,N,N′,N′-tetramethyl-p-phenylenediamine)为电解质,这种生物杂化光活性电极产生的输出是阴极和阳极光电流的净乘积。为了解释所观察到的光电流,提出了一个动力学模型,该模型包括(1)归因于电子从RC初级电子供体(PT)的三重态注入到TiO 2导带的阳极电流,(2)归因于光氧化的RC初级电子供体(P+)被TiO 2的表面状态还原的阴极电流,以及(3)导电玻璃(FTO)基板上TMPD/TMPD+的氧化/还原导致的瞬时阴极和阳极电流尖峰。该模型解释了在打开或关闭照明后出现在该系统中的光电流尖峰的起源,根据实验条件出现净正或负稳定光电流的原因,以及所构建的电池的整体效率。该模型可以用作指导,用于改善所提出的系统的光电流效率,以及在适当的调整后,其他生物混合光电极。本文的在线版本(10.1007/s11120-018-0550-8)包含补充材料,可供授权用户使用。
As one of a number of new technologies for the harnessing of solar energy, there is interest in the development of photoelectrochemical cells based on reaction centres (RCs) from photosynthetic organisms such as the bacterium Rhodobacter (Rba.) sphaeroides. The cell architecture explored in this report is similar to that of a dye-sensitized solar cell but with delivery of electrons to a mesoporous layer of TiO2 by natural pigment-protein complexes rather than an artificial dye. Rba. sphaeroides RCs were bound to the deposited TiO2 via an engineered extramembrane peptide tag. Using TMPD (N,N,N′,N′-tetramethyl-p-phenylenediamine) as an electrolyte, these biohybrid photoactive electrodes produced an output that was the net product of cathodic and anodic photocurrents. To explain the observed photocurrents, a kinetic model is proposed that includes (1) an anodic current attributed to injection of electrons from the triplet state of the RC primary electron donor (PT) to the TiO2 conduction band, (2) a cathodic current attributed to reduction of the photooxidized RC primary electron donor (P+) by surface states of the TiO2 and (3) transient cathodic and anodic current spikes due to oxidation/reduction of TMPD/TMPD+ at the conductive glass (FTO) substrate. This model explains the origin of the photocurrent spikes that appear in this system after turning illumination on or off, the reason for the appearance of net positive or negative stable photocurrents depending on experimental conditions, and the overall efficiency of the constructed cell. The model may be a used as a guide for improvement of the photocurrent efficiency of the presented system as well as, after appropriate adjustments, other biohybrid photoelectrodes. The online version of this article (10.1007/s11120-018-0550-8) contains supplementary material, which is available to authorized users.
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