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

化学制造过程中的加氢反应通常使用负载型金属催化剂进行。这些催化剂用于大型商品过程，如炔烃加氢，以及制药和农用化学品部门通常遇到的较小规模的精细化学合成。多相催化中的一个“圣杯”是发展选择性加氢反应的结构/活性关系。在这里，目标是了解细分的金属颗粒(尺寸通常为2-20 nm)的某些结构方面如何促进进入特定的化学途径。然后，这种知识/意识使得能够通过选择性地对金属微晶的特定位置下毒等技术来操纵反应概况。实施这种催化剂优化策略的一个主要障碍是可用于定义金属微晶的形态(表面结构)的技术数量有限。一种这样的技术是化学吸附探针分子的红外光谱。在过去的10年里，Lennon小组开发了红外光谱(透射式和漫反射式)的应用来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]。然后采用催化剂调节策略来选择性地“淬灭”某些活性中心。这类工作的例子是巴豆醛[3]和3-丁炔-2-酮的选择性加氢[4]。左边的图是用来表示特定的“边缘”位置对2-丁酮加氢为2-丁醇的独特活性[4]。该项目将由列侬教授和吉布森博士共同监督。它将于2018年10月开始，并将使用一系列高规格的FTIR光谱仪来表征一些加氢脱氧催化剂。然后将在与农用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对催化剂的性能进行评估。然后，这两组测量的相关性将使结构/活性关系得以提出。催化剂的改性策略将有利于影响催化剂的选择性。对于那些表现出严重失活的催化剂，将采取再生程序，以便继续投产。总体而言，该项目将为学生提供开发与工业相关的多相催化反应系统的坚实基础，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/或化学物理专业的高素质毕业生。每年约15,000英镑的免税津贴。为期3.5年，并提供所有大学学费的支付。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.