Deconvoluting Charge Transfer Mechanisms in Conducting Redox Polymer-Based Photobioelectrocatalytic Systems
Deconvoluting Charge Transfer Mechanisms in Conducting Redox Polymer-Based Photobioelectrocatalytic Systems
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DOI：
10.1149/1945-7111/ac84b2
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发表时间：
2022-08-01
影响因子：
3.9
通讯作者：
Minteer，Shelley D.
中科院分区：
文献类型：
--
作者：
Weliwatte，N. Samali;Simoska，Olja;Minteer，Shelley D.
生物催化剂和电极之间的差的电化学通信是生物电催化效率的普遍限制。已经开发了大量的聚合物库来修饰生物催化剂-电极界面以减轻这种限制。因此，导电氧化还原聚合物（CRP）是具有高结构和功能可调性的通用工具。虽然CRPs中的电荷传输特性很好，但对CRPs在决定性复杂的光生物电催化系统中促进电荷传输机制的理解仍然非常有限。这项研究是一个全面的分析，解剖复杂的动力学的光生物电极的基本块的基础上合理的假设，提供了一个机制概述的电荷转移过程中的光生物电催化。我们定量比较两个生物杂交的无金属无分支CRP（聚二羟基苯胺）和光生物催化剂（完整的叶绿体），利用两种沉积策略（“混合”和“分层”沉积）形成。上级的光生物电催化性能的“分层”的生物杂交相比，“混合”的对应物是合理的速率（D应用程序），热力学和动力学障碍（H，E a），频率的分子碰撞（D 0）在电子传输过程中跨沉积，和速率和电阻异质电子转移（K 0，R CT）。我们的研究结果表明，主要的电子转移机制的生物杂化材料，构成无分支的CRP，是热激活的分子内和分子间的电子跳跃，而不是一个非热激活的极化子转移模型典型的分支CRP或导电聚合物（CP）的生物杂化材料在文献中。这项工作强调了CRP结构和沉积策略之间的微妙的相互作用，在调整聚合物-催化剂界面，和分支/非分支结构分类的CRP在bioelectrocatalysis上下文中的意义。
Poor electrochemical communication between biocatalysts and electrodes is a ubiquitous limitation to bioelectrocatalysis efficiency. An extensive library of polymers has been developed to modify biocatalyst-electrode interfaces to alleviate this limitation. As such, conducting redox polymers (CRPs) are a versatile tool with high structural and functional tunability. While charge transport in CRPs is well characterized, the understanding of charge transport mechanisms facilitated by CRPs within decisively complex photobioelectrocatalytic systems remains very limited. This study is a comprehensive analysis that dissects the complex kinetics of photobioelectrodes into fundamental blocks based on rational assumptions, providing a mechanistic overview of charge transfer during photobioelectrocatalysis. We quantitatively compare two biohybrids of metal-free unbranched CRP (polydihydroxy aniline) and photobiocatalyst (intact chloroplasts), formed utilizing two deposition strategies (" mixed" and" layered" depositions). The superior photobioelectrocatalytic performance of the" layered" biohybrid compared to the" mixed" counterpart is justified in terms of rate (D app), thermodynamic and kinetic barriers (H≠, E a), frequency of molecular collisions (D 0) during electron transport across depositions, and rate and resistance to heterogeneous electron transfer (k 0, R CT). Our results indicate that the primary electron transfer mechanism across the biohybrids, constituting the unbranched CRP, is thermally activated intra-and inter-molecular electron hopping, as opposed to a non-thermally activated polaron transfer model typical for branched CRP-or conducting polymer (CP)-containing biohybrids in literature. This work underscores the significance of subtle interplay between CRP structure and deposition strategy in tuning the polymer-catalyst interfaces, and the branched/unbranched structural classification of CRPs in the bioelectrocatalysis context.