Theoretical and experimental correlations between solution phase and gas phase photoredox-reactivity of molecular vanadium oxide clusters

分子氧化钒簇的溶液相和气相光氧化还原反应性之间的理论和实验相关性

基本信息

  • 批准号:
    404530119
  • 负责人:
  • 金额:
    --
  • 依托单位:
  • 依托单位国家:
    德国
  • 项目类别:
    Priority Programmes
  • 财政年份:
    2018
  • 资助国家:
    德国
  • 起止时间:
    2017-12-31 至 2022-12-31
  • 项目状态:
    已结题

项目摘要

Molecular metal oxide anions, so-called polyoxometalates (POMs) are versatile photoredox catalysts for important organic transformations including alcohol oxidations, epoxidations and C H-activations. Although POM photoreactivity is empirically well established, there is a fundamental lack of understanding of the mechanisms, which control the electronic structure of the POM photocatalyst in the excited state, the mode of charge separation upon photoexcitation and the effects of structural and chemical catalyst modification on the overall photoreactivity. Further, photochemical key processes such as substrate-catalyst pre-association and catalyst / solvent-interactions are not well understood. Knowledge-driven development of new POM-based photoredox-processes is therefore far from trivial.This project will address these challenges and aim at providing fundamental understanding of the structural and electronic features which control the photoredox-activity of polyoxovanadates (POVs). POVs are ideal POM photoredox catalyst models as they combine well-established photooxidative activity towards organic substrates (focus: alcohols as model bio-feedstock) with predictable (photo-)chemical tunability and visible light absorption. To understand the solution- and gas-phase processes which control the photooxidation steps, model reactions between selected substrates and POVs will examine substrate-catalyst pre-aggregation, photooxidation and product selectivity in solution and in the gas phase. The experimental studies will be performed using solution-phase photooxidation analyses (Streb group) as well as model studies in the gas phase using pump-probe fragmentation action spectroscopy, i.e. high-resolution electrospray ionization mass spectrometry coupled with femtosecond laser spectroscopy (Riehn group). Theoretical investigations of substrate-catalyst interactions, charge-distribution and relocalization upon photoexcitation as well as photooxidation reaction mechanisms will be performed using high-level, customized density functional theory calculations (Jacob group). The project will provide significant progress by (i) delivering tuneable visible light-active POV photooxidation catalysts; (ii) providing experimental and theoretical understanding of the photoredox-mechanism of these catalysts and (iii) demonstrate their performance for the selective conversion of model substrates into value-added products. For the priority program SPP2102, the project adds access to an important class of molecular photocatalysts as well as a unique combination of time-resolved experimental and theoretical expertise to investigate complex photoreactions in solution and the gas phase. In a potential 2nd funding phase, the project would study the theoretical prediction of high activity POV catalysts, their synthetic development and their use for the photooxidation of biogenic polyol substrates (e.g. glycols) to value-added products as carbonyls or carboxylic acids.
分子金属氧化物阴离子,即所谓的聚氧乙烯酸盐(POM)是一种多用途的光氧化还原催化剂,用于重要的有机转化,包括醇氧化,环氧化和CH-活化。虽然POM光反应性是经验上建立良好的,有一个根本缺乏了解的机制,控制激发态的POM光催化剂的电子结构,光激发后的电荷分离模式和结构和化学催化剂改性对整体光反应性的影响。此外,光化学的关键过程,如底物-催化剂预缔合和催化剂/溶剂相互作用没有得到很好的理解。因此,知识驱动的新的基于POM的光氧化还原过程的开发远非微不足道。本项目将解决这些挑战,并旨在提供控制多钒酸盐(POVs)的光氧化还原活性的结构和电子特征的基本理解。POVs是理想的POM光氧化还原催化剂模型,因为它们联合收割机了对有机底物(焦点:醇作为模型生物原料)的公认的光氧化活性与可预测的(光)化学可调性和可见光吸收。为了了解控制光氧化步骤的溶液和气相过程,所选基底和POVs之间的模型反应将检查溶液和气相中基底催化剂的预聚集、光氧化和产物选择性。将使用溶液相光氧化分析(Streb组)进行实验研究,并使用泵-探测碎裂作用光谱法(即高分辨率电喷雾电离质谱法与飞秒激光光谱法相结合(Riehn组))进行气相模型研究。将使用高水平的定制密度泛函理论计算(Jacob组)对底物-催化剂相互作用、光激发时的电荷分布和再定位以及光氧化反应机制进行理论研究。该项目将通过以下方面取得重大进展:(i)提供可调的可见光活性光氧化催化剂;(ii)提供对这些催化剂的光氧化还原机制的实验和理论理解;(iii)展示它们将模型底物选择性转化为增值产品的性能。对于优先计划SPP 2102,该项目增加了对一类重要的分子光催化剂的访问,以及时间分辨实验和理论专业知识的独特组合,以研究溶液和气相中的复杂光反应。在可能的第二个供资阶段,该项目将研究高活性多元醇催化剂的理论预测、其合成开发及其在生物多元醇底物(如乙二醇)光氧化为羰基化合物或羧酸等增值产品中的用途。

项目成果

期刊论文数量(0)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)

数据更新时间:{{ journalArticles.updateTime }}

{{ item.title }}
{{ item.translation_title }}
  • DOI:
    {{ item.doi }}
  • 发表时间:
    {{ item.publish_year }}
  • 期刊:
  • 影响因子:
    {{ item.factor }}
  • 作者:
    {{ item.authors }}
  • 通讯作者:
    {{ item.author }}

数据更新时间:{{ journalArticles.updateTime }}

{{ item.title }}
  • 作者:
    {{ item.author }}

数据更新时间:{{ monograph.updateTime }}

{{ item.title }}
  • 作者:
    {{ item.author }}

数据更新时间:{{ sciAawards.updateTime }}

{{ item.title }}
  • 作者:
    {{ item.author }}

数据更新时间:{{ conferencePapers.updateTime }}

{{ item.title }}
  • 作者:
    {{ item.author }}

数据更新时间:{{ patent.updateTime }}

Professor Dr. Timo Jacob其他文献

Professor Dr. Timo Jacob的其他文献

{{ item.title }}
{{ item.translation_title }}
  • DOI:
    {{ item.doi }}
  • 发表时间:
    {{ item.publish_year }}
  • 期刊:
  • 影响因子:
    {{ item.factor }}
  • 作者:
    {{ item.authors }}
  • 通讯作者:
    {{ item.author }}

{{ truncateString('Professor Dr. Timo Jacob', 18)}}的其他基金

Influence of dynamic operation conditions on the electrolytic hydrogen evolution
动态操作条件对电解析氢的影响
  • 批准号:
    406662882
  • 财政年份:
    2018
  • 资助金额:
    --
  • 项目类别:
    Priority Programmes
Elementary Steps in the photocatalytic Water Splitting over TiO2-based Model Electrode Systems
基于 TiO2 的模型电极系统光催化水分解的基本步骤
  • 批准号:
    220687630
  • 财政年份:
    2012
  • 资助金额:
    --
  • 项目类别:
    Priority Programmes
Structure of the Electrochemical Solid/Liquid Interface
电化学固/液界面的结构
  • 批准号:
    183253384
  • 财政年份:
    2010
  • 资助金额:
    --
  • 项目类别:
    Research Units
Elektrochemische Untersuchungen zur potential-induzierten Oberflächenfacettierung
电势诱导表面刻面的电化学研究
  • 批准号:
    92915233
  • 财政年份:
    2008
  • 资助金额:
    --
  • 项目类别:
    Research Grants
Theoretische Modellierung elektrochemischer Systeme
电化学系统的理论建模
  • 批准号:
    29303356
  • 财政年份:
    2006
  • 资助金额:
    --
  • 项目类别:
    Independent Junior Research Groups
Relativistic studies for the optimization of metal oxids to oxidize or ammoxidize small alkanes and alkenes
优化金属氧化物氧化或氨氧化小烷烃和烯烃的相对论研究
  • 批准号:
    5373691
  • 财政年份:
    2002
  • 资助金额:
    --
  • 项目类别:
    Research Fellowships
Pentacenetetrone Co-polymers as Sustainable Redox-active Electrodes Tailored Towards Deep Eutectic Solvent Electrolytes in Polymer Batteries
并五苯四酮共聚物作为可持续氧化还原活性电极,专为聚合物电池中的深共晶溶剂电解质而定制
  • 批准号:
    441209207
  • 财政年份:
  • 资助金额:
    --
  • 项目类别:
    Priority Programmes
Pulsing strategies to control reactivity and selectivity in photochemistry
控制光化学反应性和选择性的脉冲策略
  • 批准号:
    501805371
  • 财政年份:
  • 资助金额:
    --
  • 项目类别:
    Research Grants
Photoelectrochemical Nitrogen Reduction: Activity, Selectivity and Stability of Cu-based Ternary Oxide Photocathodes
光电化学氮还原:铜基三元氧化物光电阴极的活性、选择性和稳定性
  • 批准号:
    502202153
  • 财政年份:
  • 资助金额:
    --
  • 项目类别:
    Priority Programmes
Theoretical studies on the ion migration through crystalline materials
离子在晶体材料中迁移的理论研究
  • 批准号:
    452995423
  • 财政年份:
  • 资助金额:
    --
  • 项目类别:
    Research Units

相似国自然基金

TXNIP调控实验性青光眼视乳头星形胶质细胞的激活及其机制研究
  • 批准号:
    82371048
  • 批准年份:
    2023
  • 资助金额:
    49.00 万元
  • 项目类别:
    面上项目
GLS1通过α-KG调控表观遗传修饰在实验性近视巩膜重塑中的作用机制
  • 批准号:
    82371092
  • 批准年份:
    2023
  • 资助金额:
    49.00 万元
  • 项目类别:
    面上项目
多发性硬化相关microRNA和靶基因鉴定及其对Th17和Treg细胞生成及分化的作用
  • 批准号:
    81171120
  • 批准年份:
    2011
  • 资助金额:
    57.0 万元
  • 项目类别:
    面上项目

相似海外基金

Immune mechanisms of pain of the IL-23IL-17 Axis in Inflammatory Arthritis
炎症性关节炎中 IL-23IL-17 轴疼痛的免疫机制
  • 批准号:
    10861492
  • 财政年份:
    2023
  • 资助金额:
    --
  • 项目类别:
Olfactory Epithelium Responses to Human APOE Alleles
嗅觉上皮对人类 APOE 等位基因的反应
  • 批准号:
    10659303
  • 财政年份:
    2023
  • 资助金额:
    --
  • 项目类别:
Smartphone-based mindfulness intervention for reducing stressrelated CVD risk
基于智能手机的正念干预可降低压力相关的心血管疾病风险
  • 批准号:
    10593307
  • 财政年份:
    2023
  • 资助金额:
    --
  • 项目类别:
Cholinergic Mechanisms in Lewy Body Dementia
路易体痴呆的胆碱能机制
  • 批准号:
    10662018
  • 财政年份:
    2023
  • 资助金额:
    --
  • 项目类别:
Molecular mechanism of PIN1-mediated regulation of the nuclear receptor PPARy
PIN1介导的核受体PPARγ调节的分子机制
  • 批准号:
    10607310
  • 财政年份:
    2023
  • 资助金额:
    --
  • 项目类别:
Smart ventilated cage systems for next-level experimental design and monitoring of specialized animal models.
智能通风笼系统,用于下一级实验设计和专门动物模型的监测。
  • 批准号:
    10737361
  • 财政年份:
    2023
  • 资助金额:
    --
  • 项目类别:
Mechanisms Explaining the Link Between Weight Discrimination and Poor Cardiovascular Health
解释体重歧视与心血管健康不良之间联系的机制
  • 批准号:
    10705356
  • 财政年份:
    2022
  • 资助金额:
    --
  • 项目类别:
Identification and Imaging of Skeletal Muscle Response to Graded Nerve Crush
骨骼肌对分级神经挤压反应的识别和成像
  • 批准号:
    10646172
  • 财政年份:
    2022
  • 资助金额:
    --
  • 项目类别:
Synaptic changes in the medial prefrontal cortex in the development of compulsive alcohol drinking
强迫性饮酒发展过程中内侧前额叶皮层的突触变化
  • 批准号:
    10732680
  • 财政年份:
    2022
  • 资助金额:
    --
  • 项目类别:
Redox and Proteomic Stress Responses in Biliary Disease
胆道疾病中的氧化还原和蛋白质组应激反应
  • 批准号:
    10636916
  • 财政年份:
    2022
  • 资助金额:
    --
  • 项目类别:
{{ showInfoDetail.title }}

作者:{{ showInfoDetail.author }}

知道了