Homogeneous hydrocarbon oxidation using nitrous oxide as a sustainable feedstock

使用一氧化二氮作为可持续原料进行均相烃氧化

• 批准号: 2881399
• 金额: --
• 依托单位: University of Warwick
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2023
• 资助国家: 英国
• 起止时间: 2023 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2881399
• 关键词: Homogeneous; hydrocarbon; oxidation; using; nitrous

Nitrous oxide (N2O) is a potent greenhouse gas, with a half-life of 114 years in the atmosphere and global warming potential 300 times greater than carbon dioxide, and the dominant ozone depleting substance emitted in the 21st century. As an abundant and sustainable resource, the use of N2O as an oxidant in chemical manufacture is an attractive prospect, liberating environmentally benign dinitrogen N2, but encumbered by the robust triatomic formulation of this gas. Whilst application of heterogenous catalysts under extreme conditions does permit reactions with N2O to be performed, such systems are energy intensive, unselective and ultimately not commercially viable. This project will seek to establish the science underpinning the activation of N2O by homogeneous transition-metal complexes with the ultimate objective of translating these findings into impactful catalytic applications. Using group 9 and 10 metal complexes supported by robust mer-tridentate 'pincer' ligands, the formation and onward reactivity of intact M-N2O adducts will be leveraged to gain fundamental understanding of how N2O can be most effectively exploited in chemical synthesis, with the prospect for generating reactive terminal oxo/oxyl derivatives rigorously examined in particular. The resulting structure-property and structure-activity relationships generated from these studies will be harnessed to enable the rational design of new catalysts and achieve step-changes in performance for transformations employing N2O as a selective hydrocarbon oxidant. The upgrading of methane to methanol is one notable and industrially coveted transformation that will be targeted, with world demand for methanol approaching 100 million metric tons annually (MMSA data).Building upon ongoing experimental work in the Chaplin group and drawing parallels with the chemistry of the early transition elements, this proposal will systematically investigate the activation of N2O using group 9 and 10 group metal pincer complexes, that is hypothesised to result in the formation of reactive terminal oxo/oxyl derivatives. Using a synergistic combination of experimental (with Chaplin) and computational (with Krämer) approaches, group 9 and 10 metal catalyst targets will be investigated to establish structure-property and structure-activity relationships underlying the coordination and activation of N2O. These findings will be harnessed to propel subsequent catalyst design, with the most promising leads rigorously examined experimentally.

一氧化二氮（N2O）是一种潜在的温室气体，在大气中的半衰期为114年，全球变暖的潜力比二氧化碳大300倍，并且在21世纪发出的主要臭氧耗尽物质。作为一种丰富而可持续的资源，将N2O用作化学制造的氧化物是一个有吸引力的前景，可以使环境良性的Dinitrogen N2释放，但由于这种天然气的强大三型三室配方而束缚。尽管在极端条件下的异源催化剂的应用确实允许与N2O进行反应，但这种系统是能源密集型，不可选择的，最终在商业上不可行。该项目将旨在建立基于均质过渡金属复合物激活N2O的科学，其最终目标是将这些发现转化为有影响力的催化应用。使用强大的Mer-Trentate“ Pincer”配体支持的第9组和10个金属配合物，将利用完整的M-N2O加合物的形成和反应性，以获得对如何在化学合成中最有效地探索N2O的基本了解，并在化学合成中最有效地探索，并具有生成的生成性末端氧末端氧末端氧化氧化氧化剂/氧基衍生物的严格性，并具有严格的严格性。由这些研究产生的结构 - 培训和结构活性关系将得到利用，以实现新催化剂的合理设计，并实现使用N2O作为选择性碳氢化合物氧化物的转化的逐步变化。将甲烷升级为甲醇是一种著名且具有工业垂涎的转型，其目标是每年对甲醇的需求接近1亿吨（MMSA数据）。在卓别林组正在进行的实验工作的基础上，并与早期过渡元素的化学相似，该提案将使用9和10组金属钳子复合物系统地研究N2O的激活，这是可以假设的，从而导致反应性末端氧气/氧基衍生物的形成。将研究实验（卓别林）和计算方法的协同组合，将研究第9组和10组金属催化剂目标，以建立结构 - 培训和结构活性关系，以协调N2O的协调和激活。这些发现将被利用以推动随后的催化剂设计，并进行了最有希望的铅实验检查。