Light‐driven Transformation of Carbon Monoxide into Hydrocarbons using CdS@ZnS : VFe Protein Biohybrids
Light‐driven Transformation of Carbon Monoxide into Hydrocarbons using CdS@ZnS : VFe Protein Biohybrids
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使用 CdS@ZnS 光驱动将一氧化碳转化为碳氢化合物：VFe 蛋白质生物杂交
DOI：
10.1002/cssc.202300981
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发表时间：
2023
期刊：
影响因子：
8.4
通讯作者：
Chatterjee, Anushree
中科院分区：
文献类型：
--
作者：
Ding, Yuchen;Lee, Chi Chung;Hu, Yilin;Ribbe, Markus M.;Nagpal, Prashant;Chatterjee, Anushree
由钒(V) -氮酶催化的酶促Fisher - Tropsch （FT）过程可以在环境条件下将一氧化碳（CO）转化为长链碳氢化合物（>C2），尽管该过程需要高成本的还原剂和/或ATP依赖性还原酶作为电子和能量来源。利用可见光活化CdS@ZnS （CZS）核壳量子点（QDs）作为V -氮酶催化组分（VFe蛋白）的替代还原等量物，我们首次报道了一个CZS: VFe生物杂化系统，该系统实现了有效的光酶C - C偶联反应，将CO氢化成碳氢化合物燃料（高达C4），这是传统无机光催化剂很难实现的。表面配体工程优化了量子点与VFe蛋白之间的分子和光电耦合，实现了高效率（内部量子产率> 56%）、不依赖ATP、光子到燃料的生产，实现了>900的电子周转率，与V -氮酶将CO转化为碳氢化合物的自然ATP耦合转化相比，这一数字是72%。产物的选择性可由辐照条件控制，较高的光子通量有利于（长链）烃的生成。cfs: VFe生物杂化体不仅可以利用廉价的可再生太阳能在高附加值化工生产中的工业CO去除中找到应用，而且还将激发相关研究兴趣，以了解光生物催化系统中的分子和电子过程。
Enzymatic Fisher‐Tropsch (FT) process catalyzed by vanadium (V)‐nitrogenase can convert carbon monoxide (CO) to longer‐chain hydrocarbons (>C2) under ambient conditions, although this process requires high‐cost reducing agent(s) and/or the ATP‐dependent reductase as electron and energy sources. Using visible light‐activated CdS@ZnS (CZS) core‐shell quantum dots (QDs) as alternative reducing equivalent for the catalytic component (VFe protein) of V‐nitrogenase, we first report a CZS : VFe biohybrid system that enables effective photo‐enzymatic C−C coupling reactions, hydrogenating CO into hydrocarbon fuels (up to C4) that can be hardly achieved with conventional inorganic photocatalysts. Surface ligand engineering optimizes molecular and opto‐electronic coupling between QDs and the VFe protein, realizing high efficiency (internal quantum yield >56 %), ATP‐independent, photon‐to‐fuel production, achieving an electron turnover number of >900, that is 72 % compared to the natural ATP‐coupled transformation of CO into hydrocarbons by V‐nitrogenase. The selectivity of products can be controlled by irradiation conditions, with higher photon flux favoring (longer‐chain) hydrocarbon generation. The CZS : VFe biohybrids not only can find applications in industrial CO removal for high‐value‐added chemical production by using the cheap, renewable solar energy, but also will inspire related research interests in understanding the molecular and electronic processes in photo‐biocatalytic systems.