High-Valent Metal Tetrapyrroles for Surface-Supported Catalysis

用于表面支持催化的高价金属四吡咯

• 批准号: 220520320
• 负责人: Privatdozent Dr. Florian Klappenberger
• 金额: --
• 依托单位: Institut für Halbleiter- und Festkörperphysik
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2013
• 资助国家: 德国
• 起止时间: 2012-12-31 至 2016-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/220520320?language=en
• 关键词: Valent; Metal; Tetrapyrroles; Surface; Supported

The macrocycle of tetrapyrroles provides one of nature’s most versatile coordination sites for catalytically active metal ions. Metallocorroles and porphyrins are the best known members of this class of naturally abundant catalytic molecules. The facile access, robustness, and easily tunable properties have established metallotetrapyrroles as key components in advanced systems like catalysts, therapeutics, in‐vivo biomarkers, or dye‐sensitized photovoltaic cells. Their characteristic ability of stabilizing metal ions in high oxidation states such as +III, +IV and +V bestows them selective catalytic activity for reactive pathways prospective for novel applications such as, e. g., tumor elimination via Mn(III), Fe(III), Au(III) or Ga(III) and atherosclerosis prevention. Recent liquid‐phase investigations have indicated a high potential of metallocorroles for small‐molecule activation (e. g. O2 and CO2). The chemistry of corroles remained largely undeveloped for decades because of severe synthetic obstacles that were overcome not before the late 1990s and, so far, literally all studies have been conducted in liquid phase. Thus, the fundamental knowledge on the electronic properties, conformation and functionality of corroles supported on solid surfaces remains to be explored.Our proposal concerns the investigation, characterization and development of corrole‐based agent systems supported by technologically relevant metal and semiconductor surfaces (Au, Si) for improved small‐molecule activation. We focus on well‐selected metallocorroles that are regarded as prospective catalytic molecules for the selective O2 and CO2 reduction in the liquid phase. As a reference for comparison, we will simultaneously investigate the related porphyrin complexes. An improved catalytic performance is aspired by employing well‐defined surface templates that assist not only the desired stabilization of high‐valent central metal ions, but act as prospective technological platforms, as well. We shall comprehensively characterize the elementary properties and processes that determine specific catalytic activities. Our proposal is an interdisciplinary feedback‐oriented collaboration between four complementary research groups from Austria and Germany with dedicated expertise in experimental and theoretical physics as well as synthetic and analytic chemistry. Based on already existing collaborations, we perform concerted experimental multi‐technique investigations (low temperature scanning tunneling microscopy; photoelectron‐, X-ray absorption, magnetic‐resonance‐ and optical spectroscopy; electrochemistry) in combination with state‐of‐the‐art model calculations from first principles. Our long term vision is a control of functionalized metallocorroles and ‐porphyrins supported on technologically relevant surface templates for selective small‐molecule activation.

大环四吡咯为催化活性金属离子提供了自然界最通用的配位位点之一。金属卟啉和卟啉是这类天然丰富的催化分子中最著名的成员。金属四吡咯的易得性、稳健性和易于调节的性质使其成为催化剂、治疗剂、体内生物标志物或染料敏化光伏电池等先进系统的关键组分。它们稳定处于高氧化态如+III、+IV和+V的金属离子的特性能力赋予它们对反应途径的选择性催化活性，所述反应途径有望用于新的应用，如，e.例如，在一个实施例中，通过Mn（III）、Fe（III）、Au（III）或Ga（III）消除肿瘤和预防动脉粥样硬化。最近的液相研究表明，金属腐蚀物对小分子活化具有很高的潜力（例如，G. O2和CO2）。由于在20世纪90年代末之前没有克服严重的合成障碍，因此几十年来，corroles的化学基本上没有得到开发，到目前为止，几乎所有的研究都是在液相中进行的。因此，关于固体表面支撑的可咯的电子性质、构象和功能的基础知识仍有待探索。我们的建议涉及研究、表征和开发技术相关的金属和半导体表面（Au，Si）支撑的可咯基试剂系统，以改善小分子活化。我们专注于精心挑选的金属腐蚀物，这些金属腐蚀物被认为是液相中选择性O2和CO2还原的潜在催化分子。作为比较的参考，我们将同时研究相关的卟啉配合物。通过采用明确定义的表面模板来改善催化性能，这些模板不仅有助于高价中心金属离子的所需稳定化，而且还可作为未来的技术平台。我们将全面表征决定特定催化活性的基本性质和过程。我们的建议是来自奥地利和德国的四个互补研究小组之间的跨学科反馈导向合作，这些研究小组在实验和理论物理以及合成和分析化学方面具有专门知识。基于现有的合作，我们进行协调一致的实验多技术研究（低温扫描隧道显微镜;光电子，X射线吸收，磁共振和光学光谱;电化学）结合最先进的模型计算从第一原理。我们的长期愿景是控制功能化的金属络合物和卟啉，支持技术相关的表面模板，用于选择性的小分子活化。

项目成果

Manipulation resolves non-trivial structure of corrole monolayer on Ag(111)

操纵解决了 Ag(111) 上咔咯单层的非平凡结构

• DOI: 10.1088/0957-4484/27/2/025704
• 发表时间: 2016
• 期刊: Nanotechnology
• 影响因子: 3.5
• 作者: Aldahhak;Serrano;Schöfberger;Schmidt;Müllegger
• 通讯作者: Müllegger

Complex supramolecular interfacial tessellation through convergent multi-step reaction of a dissymmetric simple organic precursor.

• DOI: 10.1038/nchem.2924
• 发表时间: 2018-01
• 期刊: Nature chemistry
• 影响因子: 21.8
• 作者: Yi‐Qi Zhang;M. Paszkiewicz;P. Du;Liding Zhang;Tao Lin;Zhi Chen;S. Klyatskaya;M. Ruben;A. Seitsonen;J. Barth;F. Klappenberger

Identifying On-Surface Site-Selective Chemical Conversions by Theory-Aided NEXAFS Spectroscopy: The Case of Free-Base Corroles on Ag(111).

• DOI: 10.1002/chem.201705921
• 发表时间: 2018-05
• 期刊: Chemistry
• 作者: H. Aldahhak;M. Paszkiewicz;E. Rauls;F. Allegretti;S. Tebi;A. Papageorgiou;Yanmei Zhang;Liding Zhang;Tao Lin;T. Paintner;R. Koch;Wolf Gero Schmidt;J. Barth;W. Schöfberger;S. Müllegger;F. Klappenberger;U. Gerstmann