气候变化领域集成服务门户(CCPortal): Balancing electron transfer rate and driving force for efficient photocatalytic hydrogen production in CdSe/CdS nanorod-[NiFe] hydrogenase assemblies

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DOI	10.1039/c7ee01738c
	Balancing electron transfer rate and driving force for efficient photocatalytic hydrogen production in CdSe/CdS nanorod-[NiFe] hydrogenase assemblies
	Chica B.; Wu C.-H.; Liu Y.; Adams M.W.W.; Lian T.; Dyer R.B.
发表日期	2017
ISSN	17545692
起始页码	2245
结束页码	2255
卷号	10 期号:10
英文摘要	We describe a hybrid photocatalytic system for hydrogen production consisting of nanocrystalline CdSe/CdS dot-in-rod (DIR) structures coupled to [NiFe] soluble hydrogenase I (SHI) from Pyrococcus furiosus. Electrons are shuttled to the catalyst by a redox mediator, either methyl viologen (MV2+, E0 = -446 mV vs. NHE) or propyl-bridged 2-2′-bipyridinium (PDQ2+, E0 = -550 mV vs. NHE). We demonstrate nearly equal photoreduction efficiencies for the two mediators, despite extracting ∼100 mV of additional driving force for proton reduction by PDQ2+. Femtosecond to microsecond transient absorption reveals that while electron transfer (ET) from the DIR to PDQ2+ is slower than for MV2+, in both cases the ET process is complete by 1 ns and thus it efficiently outcompetes radiative decay. Long-lived charge separation is observed for both mediators, resulting in similar net efficiencies of photoreduction. Whereas both mediators are readily photoreduced, only PDQ2+ yields measurable H2 production, demonstrating the importance of optimizing the electron shuttling pathway to take advantage of the available reducing power of the DIR excited state. H2 production in the PDQ2+ system is highly efficient, with an internal quantum efficiency (IQE) as high as 77% and a TONSHI of 1.1 × 106 under mild (RT, pH = 7.35) conditions. © The Royal Society of Chemistry.
英文关键词	Efficiency; Electron transitions; Electrons; Excited states; Nanocrystals; Nanorods; Charge separations; Electron transfer rates; Internal quantum efficiency; Photocatalytic hydrogen production; Photocatalytic systems; Pyrococcus furiosus; Soluble hydrogenase; Transient absorption; Hydrogen production; absorption; catalyst; efficiency measurement; enzyme; enzyme activity; hydrogen; reduction; separation; Pyrococcus furiosus
语种	英语
来源期刊	Energy & Environmental Science
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/190398
作者单位	Department of Chemistry, Emory University, Atlanta, GA, United States; Department of Chemistry and Biochemistry, University of Georgia, Athens, GA, United States; Department of Biochemistry and Molecular Biology, University of Georgia, Athens, GA, United States
推荐引用方式 GB/T 7714	Chica B.,Wu C.-H.,Liu Y.,et al. Balancing electron transfer rate and driving force for efficient photocatalytic hydrogen production in CdSe/CdS nanorod-[NiFe] hydrogenase assemblies[J],2017,10(10).
APA	Chica B.,Wu C.-H.,Liu Y.,Adams M.W.W.,Lian T.,&Dyer R.B..(2017).Balancing electron transfer rate and driving force for efficient photocatalytic hydrogen production in CdSe/CdS nanorod-[NiFe] hydrogenase assemblies.Energy & Environmental Science,10(10).
MLA	Chica B.,et al."Balancing electron transfer rate and driving force for efficient photocatalytic hydrogen production in CdSe/CdS nanorod-[NiFe] hydrogenase assemblies".Energy & Environmental Science 10.10(2017).