Tailoring surfaces in heterogeneous catalysis for fine chemical production

多相催化是非常重要的，也是科学界研究最广泛的领域之一。然而，对于催化剂表面和系统中分子之间的相互作用如何起作用以及如何控制这些反应中所见的活性和选择性，显然缺乏知识和理解。此外，活性金属在多相催化体系中的作用通常被研究，而对载体的作用的关注相对少得多。催化剂载体对催化体系有很大的影响，因此理解载体与这些体系的其余部分的相互作用至关重要。对催化剂载体的改性已被证明在优化催化反应方面具有重要价值，并且通过更好地了解反应物和产物如何与表面相互作用，可以对这些改性进行微调并用于提供具有无限潜力的更有效的催化剂。溶剂的作用显然在设计有效的催化体系中起着很大的作用，只有通过研究溶剂分子如何与催化剂相互作用，催化剂的表面，我们可以学会利用它。核磁共振（NMR）光谱、弛豫和脉冲场梯度（PFG）-NMR是辅助非均相催化剂的设计、表征和失活的强大技术。利用核磁共振研究催化可以提供有价值的信息，以帮助设计更积极和有效的催化体系。与催化剂表面相互作用的反应物和溶剂的分子动力学对于多相催化体系的设计仍然是非常重要的，并且这些相互作用是可以通过NMR技术简单有效地研究的。事实上，它已被证明，NMR弛豫时间测量可用于确定与催化剂表面的反应物的吸附强度。（PFG）-NMR和NMR弛豫测量可用于分析和探测表面上的改性对反应物吸附的影响。通过测量客体分子在非均相催化材料的孔网络中的扩散率，可以简单地研究催化剂孔内发生的质量传递过程，该过程决定了催化反应的反应性和选择性。低场NMR技术将用于研究在本项目期间多孔材料内的吸附和扩散过程。除此之外，多孔材料将使用新的功能化技术进行功能化，或者多孔材料的孔结构将被改变。最后，催化测试（即加压容器中的氢化反应）沿着常见的固态表征技术（即孔隙率测定法、显微镜等）将用于充分解释催化材料的反应性，并将所有这些信息与我们如何影响材料表面以产生更有效的催化系统联系起来。催化反应是当今工业中发生的最常见的重要一类反应，因此，对这些反应的开发和改进的研究非常重要。然而，目前该领域的大部分工作都集中在活性金属的作用上，而催化剂载体对催化性能的影响则知之甚少。这项工作的新奇在于研究我们如何改变催化剂载体以产生更好，更有效的催化系统，这是迄今为止人们了解相对较少的事情。新的低场核磁共振技术将被用来解开催化剂载体的影响。

Heterogeneous catalysis is of great importance and is, rightly so, amongst the most widely researched fields in the scientific community. However, there is a clear lack of knowledge and understanding of how the interactions between a catalyst surface and molecules in the system work and govern the activity and selectivities seen in these reactions. Furthermore, the role of the active metal in heterogeneous catalytic systems is commonly investigated with relatively much less attention being paid to the role of the support. The catalyst support has a large influence on catalytic systems so it is vital that the interactions of the support with the rest of these systems are understood. Modifications to catalyst supports have proved to be of great value in optimising catalytic reactions and by gaining a greater understanding of how reactants and products interact with the surface, these modifications can be fine-tuned and utilised to give far more efficient catalysts with unlimited potential.Finally, the role of the solvent clearly plays a large part in designing efficient catalytic systems and only by investigating how solvent molecules interact with the surface of the catalyst can we learn to utilise this. Nuclear magnetic resonance (NMR) spectroscopy, relaxation and pulsed field gradient (PFG)-NMR are powerful techniques to aid the design of heterogeneous catalysts, their characterisation, and their deactivation. Using NMR to study catalysis can provide valuable information to aid the design of more active and efficient catalytic systems. The molecular dynamics of reactants and solvents interacting with the catalyst surface continue to be of great importance to the design of heterogeneous catalytic systems and these interactions are something that can be simply and effectively studied by NMR techniques. Indeed, it has been shown that NMR relaxation time measurements can be used to characterise the adsorption strengths of reactants with the catalyst surface. (PFG)-NMR and NMR relaxation measurements can be used to characterise and probe the effects of modifications upon a surface upon the adsorption of reactants. By measuring the diffusivity of guest molecules within the pore network of heterogeneous catalytic materials it is possible to simply investigate the mass transport processes occurring within the catalyst pores which determine a catalytic reactions reactivity and selectivity.Low field NMR techniques will be used to investigate adsorption and diffusion process within porous materials during the length of this project. In addition to this, porous materials will be functionalised using novel functionalisation techniques or the pore structures of porous materials will be altered. Finally, catalytic testing (namely hydrogenation reactions in pressurised vessels) along with common solid state characterisation techniques (i.e. porosimetry, microscopy etc.) will be used to fully explain the catalytic materials reactivity and link all this information back to how we can influence the surface of the materials to produce more efficient catalytic systems. Catalytic reactions are amongst the most common important class of reactions that take place in industry today and, as such, research into the development and improvement of these reactions is of great importance. Most of the current work in the area however, is focused on the role of the active metal and the effect of the catalyst support upon catalytic performance is much more poorly understood. The novelty of this work lies in the investigation of how we can alter a catalyst support to produce better, more efficient catalytic systems, something that up to know has been relatively poorly understood. Novel low field NMR techniques will be used to unravel the influence of the catalyst support.