The application of infrared spectroscopy to investigate structure/activity relationships in heterogeneously catalysed hydro-deoxygenation reactions

化学制造工艺中的氢化反应通常使用负载型金属催化剂进行。这些催化剂用于大规模的商品工艺，如炔氢化，以及通常在制药和农业化学领域遇到的较小规模的精细化学合成。多相催化中的“圣杯”是发展选择性加氢反应的结构/活性关系。在这里，目标是了解细分金属颗粒（尺寸通常为2-20 nm）的某些结构方面如何促进特定化学途径的进入。然后，这种知识/意识使得能够通过诸如金属微晶的特定位点的选择性中毒的技术来操纵反应曲线。实施这种催化剂优化策略的主要障碍是可用于限定金属微晶的形态（表面结构）的技术数量有限。在过去的10年里，Lennon小组已经开发了红外光谱（透射和漫反射）的应用，以确定一系列氧化铝负载的Pd催化剂的形态，这些催化剂对气相加氢具有活性[1，2]。催化剂调节策略随后被用于选择性地“淬灭”某些活性位点。这类工作的实例是巴豆醛[3]和3-丁炔-2-酮[4]的选择性氢化。左边的图表示某些“边缘”位点对2-丁酮加氢生成2-丁醇的独特活性[4]。该项目将由Lennon教授和吉布森博士共同监督。它将于2018年10月开始，并将利用一系列高规格FTIR光谱仪来检测多种加氢脱氧催化剂。然后将在与农业化学品和精细化学品制造行业直接相关的特定加氢脱氧反应中评估催化剂的性能。这两组测量的相关性将使结构/活性关系被提出。催化剂改性策略将用于有利地影响催化剂选择性。再生程序将用于那些表现出明显失活的催化剂，以继续运行。总的来说，该项目将为学生提供与工业相关的多相催化反应系统开发的坚实基础，以及现代催化剂表征技术的经验。该项目非常适合化学，化学和药物化学和/或化学物理的高素质毕业生。一个免税的津贴。每年一万五千英镑为期3.5年，并支付所有大学费用。资格仅限于欧盟公民。

Hydrogenation reactions in chemical manufacturing processes are typically performed using supported metal catalysts. These catalysts are used in large-scale commodity processes such as alkyne hydrogenations, as well as smaller scale fine chemical synthesis as typically encountered in the pharmaceutical and agri-chemical sectors. A "Holy Grail" in heterogeneous catalysis is to develop structure/activity relationships for selective hydrogenation reactions. Here, the goal is to understand how certain structural aspects of finely divided metal particles (dimensions typically 2-20 nm) facilitate access to particular chemical pathways. Such knowledge/awareness then enables reaction profiles to be manipulated via techniques such as selective poisoning of specific sites of the metal crystallites. A major barrier to implementing such catalyst optimisation strategies is the limited number of techniques that can be used to define the morphology (surface structure) of the metal crystallites. One such technique is infrared spectroscopy of chemisorbed probe molecules.Over the last 10 years the Lennon group have developed the application of infrared spectroscopy (transmission and diffuse-reflectance) to determine the morphology of a series of alumina-supported Pd catalysts that are active for gas phase hydrogenations [1,2]. Catalyst conditioning strategies have then been employed to selectivity "quench" certain active sites. Examples of such work would be the selective hydrogenation of crotonaldehyde [3] and 3-butyne-2-one [4]. The figure on the left is intended to signify how certain 'edge' sites are uniquely active for the hydrogenation of 2-butanone to 2-butanol [4].The project will be jointly supervised by Professor Lennon and Dr Gibson. It will commence in October 2018 and will utilise a range of high specification FTIR spectrometers to characterise a number of hydro-deoxygenation catalysts. The performance of the catalysts will then be evaluated in specific hydro-deoxygenation reactions of direct relevance to the agri-chemicals and fine chemicals manufacturing industries. Correlations of these two sets of measurements will then enable structure/activity relationships to be proposed. Catalyst modification strategies will be used to favourably influence catalyst selectivity. Regeneration procedures will be adopted for those catalysts exhibiting significant deactivation for continuing time-on-stream. Collectively, the project will provide the student with a sound grounding in the development of industrially relevant heterogeneously catalysed reaction systems, as well as experience in modern catalyst characterisation techniques.The project is ideally suited to high-calibre graduates in Chemistry, Chemistry and Medicinal Chemistry and/or Chemical Physics. A tax-free stipend of ca. £15,000 p.a. for 3.5 years and the payment of all University fees are provided. Eligibility is restricted to EU citizens only.