Edwards Emily H, Jelušić Jana, Chakraborty Saikat, Bren Kara L
Department of Chemistry, University of Rochester, Rochester, NY 14627, United States of America.
J Inorg Biochem. 2021 Apr;217:111384. doi: 10.1016/j.jinorgbio.2021.111384. Epub 2021 Feb 4.
A photochemical system utilizing the semisynthetic biomolecular catalyst acetylated cobalt microperoxidase-11 (CoMP11-Ac) along with [Ru(bpy)] as a photosensitizer and ascorbic acid as an electron donor is shown to generate hydrogen from water in a visible light-driven reaction. The reductive quenching pathway facilitated by photoexcited [Ru(bpy)] overcomes the high overpotential observed for CoMP11-Ac in electrocatalysis, yielding turnover numbers ranging from 606 to 2390 (2 μM - 0.1 μM CoMP11-Ac). The longevity of CoMP11-Ac in the photochemical system, sustaining catalysis for over 20 h, is in contrast to its previously reported behavior in an electrochemical system where catalysis slows after 15 min. Proton reduction turnover number and rate are highest at a neutral pH, a rare feature among cobalt catalysts in similar photochemical systems, which typically function best under acidic conditions. Incorporating biomolecular components into the design of catalysts for photochemical systems may address the need for hydrogen generation from neutral-pH water sources.
一种光化学系统利用半合成生物分子催化剂乙酰化钴微过氧化物酶-11（CoMP11-Ac），以及[Ru(bpy)]作为光敏剂和抗坏血酸作为电子供体，在可见光驱动的反应中从水中产生氢气。光激发的[Ru(bpy)]促进的还原猝灭途径克服了在电催化中观察到的CoMP11-Ac的高过电位，产生的周转数范围为606至2390（2 μM - 0.1 μM CoMP11-Ac）。CoMP11-Ac在光化学系统中的寿命，即持续催化超过20小时，与其先前在电化学系统中的行为形成对比，在电化学系统中催化在15分钟后就会减慢。质子还原周转数和速率在中性pH下最高，这在类似光化学系统中的钴催化剂中是一个罕见的特征，这些钴催化剂通常在酸性条件下功能最佳。将生物分子成分纳入光化学系统催化剂的设计中，可能满足从中性pH水源产生氢气的需求。
