Silicon nanowires as photoelectrodes for carbon dioxide fixation.
Silicon nanowires as photoelectrodes for carbon dioxide fixation.
复制标题
DOI：
10.1002/anie.201202569
复制
发表时间：
2012-07-02
影响因子：
16.6
通讯作者：
Wang, Dunwei
中科院分区：
文献类型：
--
作者：
Liu, Rui;Yuan, Guangbi;Joe, Candice L.;Lightburn, Thomas E.;Tan, Kian L.;Wang, Dunwei
自然光合作用收集太阳光中的能量来为化学反应提供动力，并使用二氧化碳作为碳源。由于光作为一种能源是免费且丰富的，因此类似于光合作用的化学反应具有重大的基础和实际意义。[1-2] 事实上，这一研究目标已经吸引了大量的努力。对转化二氧化碳的光化学反应的大多数关注主要集中在转化为燃料上。[3-4]如何从光合作用中学习并设计反应路线来合成有用的有机化合物受到了相对平淡的考虑。[5]受光合作用暗反应机制的启发，并使用 p 型硅纳米线作为光电阴极，我们证明可以很容易地进行高度特异性的反应，通过芳香酮的光还原，然后固定 CO2 来产生 α-羟基酸。该反应由太阳光提供动力，与自然光合作用非常相似，但与其电化学类似物不同。本次交流中检查的两种底物的羧化产物是非甾体抗炎药 (NSAID)、布洛芬和萘普生的前体。[6]在自然界中，光合作用分两个不同的阶段进行：光反应和暗反应。在光促进阶段，光子中的能量被收集并储存在 NADPH（烟酰胺腺嘌呤二核苷酸磷酸）和 ATP（5'-三磷酸腺苷）等化学物质中，随后用于隔离二氧化碳以合成复杂的糖单体。卡尔文循环（暗反应）的核心是将核酮糖-1, 5-二磷酸 (RuBP) 转化为中间体 β-酮酸（方案 1），最终裂解为 3-磷酸甘油酸 (3PG)，这是糖的核心构建模块。 [7]通过不直接还原 CO2，该工艺避免产生各种氧化态的 C，并获得高选择性的关键优势。 [8]这种化学启发我们提出一种利用光作为直接能源、二氧化碳作为碳源进行羧化反应的策略。如方案 1 和 2 所示，我们的反应路线与自然光合作用非常相似，但与寻求直接光还原 CO2 的现有方法不同。它解决了由于多电子转移过程的性质而直接光还原 CO2 所固有的选择性差的关键挑战。我们的策略有潜力满足比燃料更复杂的合成目标所需的选择性要求，为以前从未研究过的各种光动力化学反应打开了大门[9-12]。
Natural photosynthesis harvests the energy in solar light to power chemical reactions and uses CO2 as the carbon source. Because light as an energy source is free and abundant, chemical reactions similar to photosynthesis have major fundamental and practical implications.[1-2] Indeed, significant efforts have been attracted to this research goal. The majority of attention for photochemical reactions that transform CO2 have focused primarily on conversion into fuels.[3-4] How to learn from photosynthesis and devise reaction routes for the synthesis of useful organic compounds receives relatively underwhelmed considerations.[5] Drawing inspiration from the mechanisms found in dark reactions of photosynthesis and using p-type Si nanowires as a photocathode, here we show that highly specific reactions can be readily carried out to produce α-hydroxy acids by photoreduction of aromatic ketones, followed by CO2 fixation. Powered by solar light, this reaction is in close resemblance to natural photosynthesis, and different from its electrochemical analogues. The carboxylation products of two of the substrates examined in this communication serve as precursors to nonsteroidal anti inflammatory drugs (NSAID), ibuprofen and naproxen.[6]In nature, photosynthesis is carried out in two distinct stages: light and dark reactions. During the light promoted stage, the energy in photons is harvested and stored in chemicals such as NADPH (nicotinamide adenine dinucleotide phosphate) and ATP (adenosine-5′-tiphosphate) are subsequently used to sequester carbon dioxide for the synthesis of complex sugar monomers. At the heart of the Calvin cycle (dark reactions) is the conversion of ribulose-1, 5-bis-phosphate (RuBP) into an intermediate β-keto-acid (Scheme 1), which ultimately fragments to 3-phosphoglycerate (3PG), the core building block for sugars.[7] By not directly reducing CO2, this process avoids producing C in a variety of oxidation states and gains a critical advantage of high selectivity.[8] This chemistry inspires us to propose a strategy to perform carboxylation reactions using light as a direct energy source and CO2 as a carbon source. As shown in Schemes 1 and 2, our reaction route is in close resemblance to natural photosynthesis but different from existing approaches that seek to directly photoreduce CO2. It solves a critical challenge of poor selectivity inherent to the direct photoreduction of CO2 due to the nature of the multielectron transfer processes. Our strategy has the potential to meet the selectivity requirement necessary for more complex synthetic targets than fuels, opening up doors to a wide range of light-powered chemical reactions [9-12] that have not been previously studied.
登录
查看更多内容
影响因子：
56.9
作者：
Boettcher, Shannon W.;Spurgeon, Joshua M.;Lewis, Nathan S.
通讯作者：
Lewis, Nathan S.
影响因子：
64.8
作者：
Tian, Bozhi;Zheng, Xiaolin;Lieber, Charles M.
通讯作者：
Lieber, Charles M.
影响因子：
21.8
作者：
Yoon, Tehshik P.;Ischay, Michael A.;Du, Juana
通讯作者：
Du, Juana
影响因子：
64.8
作者：
LIEBER, CM;GRONET, CM;LEWIS, NS
通讯作者：
LEWIS, NS
DOI：
10.1073/pnas.0907176107
发表时间：
2010-05-11
影响因子：
11.1
作者：
Bar-Even, Arren;Noor, Elad;Milo, Ron
通讯作者：
Milo, Ron