Department of Chemical and Biological Engineering, University of Colorado Boulder, Boulder, CO 80303, USA.
Department of Molecular Biology and Biochemistry, University of California, Irvine, Irvine, CA 92697-3900, USA.
ChemSusChem. 2023 Oct 20;16(20):e202300981. doi: 10.1002/cssc.202300981. Epub 2023 Aug 7.
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.
酶促费托（FT）过程由氮钒（V）酶催化，可以在环境条件下将一氧化碳（CO）转化为更长链的碳氢化合物（>C2），尽管该过程需要高成本的还原剂和/或依赖 ATP 的还原酶作为电子和能源。我们使用可见光激活的 CdS@ZnS（CZS）核壳量子点（QD）作为 V 氮酶催化组分（VFe 蛋白）的替代还原当量，首次报道了 CZS：VFe 生物杂化系统，该系统能够实现有效的光酶 C-C 偶联反应，将 CO 加氢转化为难以用传统无机光催化剂实现的烃类燃料（高达 C4）。表面配体工程优化了 QD 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％）、ATP 独立、光子到燃料的产生，实现了>900 的电子周转数，与 V 氮酶将 CO 转化为烃类的自然 ATP 偶联转化相比提高了 72％。通过辐照条件可以控制产物的选择性，较高的光子通量有利于（长链）烃类的生成。CZS：VFe 生物杂化物不仅可以通过利用廉价、可再生的太阳能在工业 CO 去除方面找到用于高附加值化学品生产的应用，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。
