Song Wentao, Liu Yong, Wu Yao, Wang Cheng, Liu Zhourui, Liu Yinan, Zhang Xinyue, Cao Lei, Li Bowen, Song Bo, Cao Bin, Yao Yingfang, Mao Xianwen, He Qian, Zou Zhigang, Liu Bin
Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore, Singapore.
Department of Material Science and Engineering, College of Design and Engineering, National University of Singapore, Singapore, Singapore.
Nat Commun. 2025 Jul 21;16(1):6708. doi: 10.1038/s41467-025-62062-9.
Biotic-abiotic hybrid systems show significant promise for solar-to-chemical conversion by integrating intracellular biocatalytic pathways with artificially synthesized semiconductors. However, due to intricate interfacial connection and ubiquitous heterogeneities between microorganisms and materials, it remains challenging to achieve atomically precise interface contact and elucidate electron transport mechanism at the single-/sub-cell levels for efficient solar energy transformation. Herein, we report a general design of facilitating direct electron transfer pathway through constructing single-atom bridges across biotic-abiotic interfaces to enhance solar-to-chemical conversion. Specifically, using CN/Ru-Shewanella hybrid system as a demonstration, we discover that single-atom bridges promote effective charge separation and reduce electron transfer barriers at the biohybrid interfaces. Moreover, operando single-cell photocurrent technique and theoretical calculations further quantitatively unravel that CN/Ru-Shewanella with a unique Ru-N interfacial structure exhibits a 11.0-fold increase in direct electron uptake compared to CN-Shewanella. In contrast to Shewanella and CN-Shewanella, CN/Ru-Shewanella shows 47.5- and 14.2-fold improvement for solar-driven H production, respectively, achieving a remarkable quantum yield of 8.46%. This work, further supported via proteomic analysis and CN/Cu-Shewanella biohybrids, highlights the universal strategy of single atoms mediating direct electron uptake and provides insights into atomic-level charge dynamics in microbe-semiconductor biohybrids towards solar energy utilization.
通过将细胞内生物催化途径与人工合成半导体相结合，生物-非生物混合系统在太阳能到化学能的转化方面显示出巨大的潜力。然而，由于微生物与材料之间复杂的界面连接和普遍存在的异质性，在单/亚细胞水平上实现原子精确的界面接触并阐明电子传输机制以实现高效的太阳能转化仍然具有挑战性。在此，我们报告了一种通用设计，即通过在生物-非生物界面上构建单原子桥来促进直接电子转移途径，以增强太阳能到化学能的转化。具体而言，以CN/Ru-希瓦氏菌混合系统为例，我们发现单原子桥促进了有效的电荷分离，并降低了生物混合界面处的电子转移势垒。此外，原位单细胞光电流技术和理论计算进一步定量揭示，具有独特Ru-N界面结构的CN/Ru-希瓦氏菌与CN-希瓦氏菌相比，直接电子摄取增加了11.0倍。与希瓦氏菌和CN-希瓦氏菌相比，CN/Ru-希瓦氏菌在太阳能驱动产氢方面分别提高了47.5倍和14.2倍，实现了8.46%的显著量子产率。这项工作通过蛋白质组学分析和CN/Cu-希瓦氏菌生物混合体得到进一步支持，突出了单原子介导直接电子摄取的通用策略，并为微生物-半导体生物混合体中原子级电荷动力学在太阳能利用方面提供了见解。
