Light Induced Carbon Dioxide Reduction by Water at Binuclear ZrOCoIIUnit Coupled to Ir Oxide Nanocluster Catalyst,Journal of the American Chemical Society

当前位置： X-MOL 学术 › J. Am. Chem. Soc. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Light Induced Carbon Dioxide Reduction by Water at Binuclear ZrOCoIIUnit Coupled to Ir Oxide Nanocluster Catalyst
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2014-07-24 , DOI: 10.1021/ja504753g
Wooyul Kim ₁ , Guangbi Yuan ₁ , Beth Anne McClure ₁ , Heinz Frei ₁

Affiliation

An all-inorganic polynuclear unit consisting of an oxo-bridged binuclear ZrOCo(II) group coupled to an iridium oxide nanocluster (IrO(x)) was assembled on an SBA-15 silica mesopore surface. A photodeposition method was developed that affords coupling of the IrO(x) water oxidation catalyst with the Co donor center. The approach consists of excitation of the ZrOCo(II) metal-to-metal charge-transfer (MMCT) chromophore with visible light in the presence of [Ir(acac)3] (acac: acetylacetonate) precursor followed by calcination under mild conditions, with each step monitored by optical and infrared spectroscopy. Illumination of the MMCT chromophore of the resulting ZrOCo(II)-IrO(x) units in the SBA-15 pores loaded with a mixture of (13)CO2 and H2O vapor resulted in the formation of (13)CO and O2 monitored by FT-IR and mass spectroscopy, respectively. Use of (18)O labeled water resulted in the formation of (18)O2 product. This is the first example of a closed photosynthetic cycle of carbon dioxide reduction by water using an all-inorganic polynuclear cluster featuring a molecularly defined light absorber. The observed activity implies successful competition of electron transfer between the IrO(x) catalyst cluster and the transient oxidized Co donor center with back electron transfer of the ZrOCo light absorber, and is further aided by the instant desorption of the CO and O2 product from the silica pores.

中文翻译：

在与氧化铱纳米团簇催化剂耦合的双核 ZrOCoII 单元上通过水光诱导二氧化碳还原

在 SBA-15 二氧化硅介孔表面上组装了一个全无机多核单元，该单元由与氧化铱纳米团簇 (IrO(x)) 耦合的氧桥联双核 ZrOCo(II) 基团组成。开发了一种光沉积方法，该方法提供了 IrO(x) 水氧化催化剂与 Co 供体中心的偶联。该方法包括在 [Ir(acac)3]（acac：乙酰丙酮化物）前体存在下用可见光激发 ZrOCo(II) 金属-金属电荷转移 (MMCT) 生色团，然后在温和条件下煅烧，每一步都由光学和红外光谱监测。SBA-15 孔中生成的 ZrOCo(II)-IrO(x) 单元的 MMCT 发色团的照明导致 (13)CO2 和 H2O 蒸气的混合物的形成，由 FT 监测-IR 和质谱，分别。使用 (18)O 标记的水导致形成 (18)O2 产品。这是使用具有分子定义的光吸收剂的全无机多核簇通过水减少二氧化碳的封闭光合作用循环的第一个例子。观察到的活性意味着 IrO(x) 催化剂簇和瞬态氧化 Co 供体中心之间的电子转移与 ZrOCo 光吸收剂的反向电子转移的成功竞争，并且通过从催化剂中立即解吸 CO 和 O2 产物进一步辅助二氧化硅孔。

更新日期：2014-07-24

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南