Water splitting by visible light: a nanophotocathode for hydrogen production.
Water splitting by visible light: a nanophotocathode for hydrogen production.
复制标题
可见光分解水：用于制氢的纳米光电阴极。
DOI：
10.1002/anie.200906262
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发表时间：
2010
期刊：
影响因子：
--
通讯作者：
Nann T
中科院分区：
文献类型：
--
作者：
Nann T
高效生产太阳能燃料是满足未来无化石燃料能源需求的必要条件。通过太阳能分解水得到的氢作为清洁能源载体显然是有吸引力的，并且已经有许多尝试来构建用于光氢生产的可行的分子和生物分子装置。[1]在这种装置的构造中的常见方法是利用三（联吡啶）钌、锌卟啉或相关分子材料作为光敏剂，与系留或游离电催化剂或酶系统结合。[2-4]除了成本之外，此类系统还具有寿命有限的缺点，这可能至少部分归因于光激发态自由基阴离子形式的有机N-供体配体的固有反应性和光降解途径。[5，6]在本文中，我们表明，廉价且环境友好的无机集光纳米阵列可以与含有丰富元素的低成本电催化剂组合。该系统为光电化学制氢提供了一个稳定的平台。该器件是通过首先逐层构建交联磷化铟（InP）纳米阵列，然后掺入铁硫电催化剂而构建的。与[FeFe]-氢化酶的亚位点相关的铁-硫羰基组装体已被证明在黑暗条件下在100 - 1000之间的电势下电催化质子还原为二氢。7和101。4 V，相对于非水电解质中的标准甘汞电极（SCE）。[7，8]在这些组件中，我们选择了[Fe 2S 2（CO）6]，其具有潜在地能够结合到铟上的硫桥，作为固态组件中质子光电化学还原的催化剂，并且还原电位为100。90 V vs SCE。通过该系统，我们能够实现超过60%的光电化学效率，这是该领域的重大突破。首先，我们发现[Fe_2S_2（CO）_6]可以猝灭InP纳米晶的发光。然后，我们通过傅里叶变换红外光谱（FTIR）表明，一个三维阵列的InP纳米晶体和子网站可以组装在一个支持金衬底。此后，我们表明，该组件支持在水性电解质中的大量光电流，最后，InP-催化剂阵列在制备规模上产生氢，并且在pH 7下，在质子还原的暗平衡电势的显著正的电势偏置下。根据我们先前公开的方法制备了InP纳米晶体，其为具有600 nm处的发射带和600 nm处的全宽的5 nm颗粒。半峰宽（FWHM）为约80 nm。[9，10]使用十六烷基胺（HDA）和长链脂肪酸（硬脂酸和十一烷酸）的锌盐作为表面配体将这些纳米晶体分散在甲苯中。在无氧条件下，在简单的氢化酶亚位点类似物[Fe 2S 2（CO）6]的存在下，分散在甲苯中的InP纳米颗粒的荧光缓慢淬灭。这种猝灭指示亚位点与InP光敏剂的结合。图1显示了
Efficient production of solar fuels is an imperative for meeting future fossil-fuel-free energy demands. Hydrogen that is derived from the splitting of water by solar energy is clearly attractive as a clean energy vector, and there have been many attempts to construct viable molecular and biomolecular devices for photohydrogen production.[1] A common approach in the construction of such devices is the utilization of tris (bipyridine) ruthenium, zinc porphyrin, or related molecular materials as photosensitizers in conjunction with a tethered or free electrocatalyst or enzymic system.[2–4] Apart from cost, such systems suffer from having limited lifetimes, which may be attributed at least in part to the intrinsic reactivity of the organic N-donor ligands in the radical anion form of the photoexcited state and photodegradation pathways.[5, 6] Herein we show that an inexpensive and environmentally benign inorganic light harvesting nanoarray can be combined with a low-cost electrocatalyst that contains abundant elements. This system provides a stable photoelectrochemical platform for hydrogen production. The device is constructed by first building-up a cross-linked indium phosphide (InP) nanocrystal array layer by layer and then incorporating an iron–sulfur electrocatalyst. Iron–sulfur carbonyl assemblies related to the subsite of [FeFe]-hydrogenase have been shown to electrocatalyze the reduction of protons to dihydrogen under dark conditions at potentials between À0. 7 and À1. 4 V versus the standard calomel electrode (SCE) in non-aqueous electrolytes.[7, 8] Of these assemblies, we chose [Fe2S2 (CO) 6], which has sulfide bridges that are potentially capable of binding to indium as a catalyst for photoelectrochemical reduction of protons in a solid-state assembly, and a modest reduction potential of À0. 90 V versus SCE. With this system, we were able to achieve a photoelectrochemical efficiency of more than 60%, which is a major breakthrough in this field. First, we show that [Fe2S2 (CO) 6] can quench the luminescence of InP nanocrystals. Then, we show by Fourier-transform infrared spectroscopy (FTIR) that a three-dimensional array of InP nanocrystals and the subsite can be assembled on a supporting gold substrate. Thereafter, we show that this assembly supports a substantial photocurrent in an aqueous electrolyte, and finally that the InP-catalyst array produces hydrogen on the preparative scale and at a potential bias significantly positive of the dark equilibrium potential for proton reduction at pH 7.InP nanocrystals were prepared according to our previously published procedure as 5 nm particles with an emission band at 600 nm and a full width at half maximum (FWHM) of about 80 nm.[9, 10] These nanocrystals were dispersed in toluene using hexadecylamine (HDA) and the zinc salts of long-chain fatty acids (stearic and undecanoic acid) as surface ligands. The fluorescence of InP nanoparticles in dispersion in toluene is slowly quenched in the presence of the simple hydrogenase subsite analogue,[Fe2S2 (CO) 6], under oxygenfree conditions. This quenching is indicative of the binding of the subsite to the InP photosensitizer. Figure 1 shows the
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影响因子：
46.2
作者：
Gloaguen F;Rauchfuss TB
通讯作者：
Rauchfuss TB
DOI：
--
发表时间：
2002
期刊：
影响因子：
--
作者：
G. Y. Kolbasov;V. Kublanovskii;T. A. Taranets;K. Litovchenko
通讯作者：
K. Litovchenko
InP纳米晶的合成及电化学性能
DOI：
--
发表时间：
2006
期刊：
影响因子：
--
作者：
Sandeep Kumar;R. Thomann;T. Nann
通讯作者：
T. Nann
关于 [Fe2E2(CO)6]2- (E = S, Se) 中前沿轨道的结构证据：氧化还原活性二硫属元素配体
影响因子：
4.6
作者：
T. D. Weatherill;T. Rauchfuss;R. A. Scott
通讯作者：
R. A. Scott