Operando Studies of Palladium-Catalysed Cross-Coupling Surface Chemistry

钯催化交叉偶联表面化学的操作研究

• 批准号: EP/E046754/1
• 负责人: Adam Lee
• 金额: $ 10.26万
• 依托单位: University of York
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2007
• 资助国家: 英国
• 起止时间: 2007 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FE046754%2F1
• 关键词: Operando; Studies; Palladium; Catalysed; Cross

Pd-catalysed cross-coupling reactions represent key technologies employed within academia and industry, however the fine chemicals sector urgently needs new catalytic systems for large-scale, continuous processing. This proposal underpins the development of alternative, heterogeneous Pd-catalysed processes to meet this demand. Commercialization of such catalytic clean technologies awaits detailed knowledge of their optimal formulation and associated reaction conditions. This information in turn requires insight into both the mechanisms of such surface reactions and their associated deactivation pathways in order to control both activity and selectivity (homo- versus cross-coupling). Here we propose to obtain microscopic-level understanding of Heck and Suzuki-Miyaura chemistry over well-defined model palladium surfaces through the use of operando surface spectroscopies and mechanistic reaction probes. We have recently pioneered the application of in-situ, X-ray photoelectron spectroscopy for real-time investigations of industrially significant, surface catalysed processes including alkyne trimerisation, C-H activation and VOC destruction. These methodologies will also allow us to determine whether heterogeneously catalysed cross-coupling shares common reaction intermediates and rate-limiting steps with its more conventional homogeneous counterparts. The intellectual output from this project will be invaluable in designing a new toolbox of high performance dispersed Pd catalysts that will revolutionise organic synthetic chemistry.

钯催化的交叉偶联反应代表了学术界和工业界使用的关键技术，然而精细化学品部门迫切需要新的催化体系用于大规模连续加工。这一提议支持开发替代的多相Pd催化工艺以满足这一需求。这种催化清洁技术的商业化需要对其最佳配方和相关反应条件的详细了解。这些信息反过来又需要深入了解这种表面反应的机制及其相关的失活途径，以控制活性和选择性（均偶联与交叉偶联）。在这里，我们建议获得微观层面的理解赫克和铃木宫浦化学定义良好的模型钯表面通过使用操作表面光谱和机械反应探针。我们最近率先应用原位X射线光电子能谱技术对工业上重要的表面催化过程进行实时研究，包括炔三聚、C-H活化和VOC破坏。这些方法也将使我们能够确定非均相催化的交叉偶联是否与其更常规的均相对应物共享共同的反应中间体和限速步骤。该项目的智力成果将在设计一个新的高性能分散Pd催化剂工具箱方面发挥不可估量的作用，这将彻底改变有机合成化学。

项目成果

Redox-Controlled Crotyl Alcohol Selective Oxidation: In Situ Oxidation and Reduction Dynamics of Catalytic Pd Nanoparticles via Synchronous XANES/MS

• DOI: 10.1021/cs300445y
• 发表时间: 2012-09
• 期刊: ACS Catalysis
• 影响因子: 12.9
• 作者: Christine V. Gaskell;Christopher M. A. Parlett;M. Newton;K. Wilson;A. Lee

In - Silico Prediction of Pd-Catalyzed Cross-Coupling Processes: Dibenzylidene Acetone (dba) Ligand Control

Pd 催化交叉偶联过程的计算机预测：二亚苄基丙酮 (dba) 配体控制

• DOI: 10.1021/om700617r
• 发表时间: 2007
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: Fairlamb I

Hydrodebromination of Bromobenzene over Pt(111)

溴苯在 Pt(111) 上加氢脱溴

• DOI: 10.1021/jp070488r
• 发表时间: 2007
• 期刊: The Journal of Physical Chemistry C
• 作者: Lee A

In-situ X-ray Studies of Clean Catalytic Technologies

清洁催化技术的原位 X 射线研究

• DOI: 10.1557/opl.2011.1170
• 发表时间: 2011
• 期刊: MRS Proceedings
• 作者: Lee A

Hydrogen-bonded liquid crystals formed from 4-alkoxystilbazoles and chlorophenols

由 4-烷氧基芪唑和氯酚形成的氢键液晶

• DOI: 10.1039/d3ce00266g
• 发表时间: 2023
• 期刊: CrystEngComm
• 影响因子: 3.1
• 作者: Johnson O