Control of the formation and reaction of copper-oxygen adduct complexes in multiphase streams

在SPP1740中，Herres-Pawlis小组的任务是开发量身定制的化学反应系统。研究的目标是与氧和一氧化氮反应的系统，以详细了解多相混合物的过程，如存在于反应性气泡流中。最重要的要求是可调的反应速度以及对不同测量方法的灵敏度，以便以空间和时间分辨的方式探测与气体的反应。在这里，原位光谱方法是重点，如拉曼光谱和荧光光谱。本文利用停流光谱、超聚焦混合器和泰勒气泡对六种不同的反应体系进行了动力学和理论方面的研究。第二个资助期的目标是用混合灵敏度对后续连续或平行反应的氧转移进行多维检测，并阐明传质系数的完整动力学。因此，该系统应该可以被LIF检测到，并且可以大量使用。特殊的挑战在于将系统调整到室温，而定义的Cu2O2化学通常在-80°C下进行。这只有通过复杂的配体设计才能实现。此外，必须制定配体回收策略，以满足SPP1740要求的数量。氧活化和转移动力学的表征将通过紫外/可见光谱和停止流动光谱进行，以获得固有的反应常数。与选定的工作组合作，设想在超聚焦混合器，泰勒气泡，泰勒流，一泡和二泡细胞，螺旋毛细管流反应器直至气泡柱中的多维实验：因此，所生成系统的颜色以及它们的荧光响应都被利用。为了在技术规模上应用氧合反应，需要对所有步骤进行全面的动力学分析，并对通过气液相边界层的传质有深入的了解。在这里，模拟将在所有尺寸尺度上提供帮助：密度泛函数理论将有助于模拟最有希望的系统的原子步骤，而SPP的进一步合作伙伴将模拟超级焦点混合器、泰勒气泡和毛细管流动反应器中的动力学。与第一个项目阶段相比，将研究竞争-平行和结果反应。

Within the SPP1740, the task of the Herres-Pawlis group was the development of tailored chemical reaction systems. The investigations targeted systems which react with oxygen and nitrogen monoxide for a detailed understanding of the processes in multiphase mixtures, as are present in reactive bubbly flows. Most important requirement is the tunable reaction speed as well as the sensitivity towards different measurement methods in order to probe in space- and time-resolved manner the reaction with the gas. Here, in situ spectroscopic methods are in the focus, e.g. Raman and fluorescence spectroscopy. Six different reaction systems have been developed and investigated towards their kinetic and theoretical aspects by means of stopped-flow spectroscopy, in the super focus mixer and in the Taylor bubble.The goal of the second funding period is to detect multidimensionally the oxygen transfer with subsequent consecutive or parallel reaction with mixing sensitivity and to elucidate the complete kinetics with mass transfer coefficients. Herefore, the system shall be detectable by LIF and be available in large quantities. The special challenge lies in tuning of the systems to room temperature whereby the defined Cu2O2 chemistry normally proceeds at -80°C. This is only possible by sophisticated ligand design. Additionally, strategies for the ligand recycling have to be developed in order to cover the required amounts within the SPP1740. The characterisation of the kinetics of oxygen activation and transfer will be performed by UV/Vis and stopped-flow spectroscopy in order to obtain the intrinsic reaction constants. In collaboration with selected working groups, multidimensional experiments in the super focus mixer, the Taylor-bubble, Taylor-flow, one- and two bubble cells, helical capillary flow reactors up to the bubble column are envisioned: herefore the colour of the generated systems but also their fluorescence response is utilised. A comprehensive kinetic analysis of all steps as well as a deep understanding of the mass transfer through the phase boundary layer gas-liquid is needed for the usage of the oxygenation reactions in technical scale. Here, simulation will aid in all size scales: density functional theory will help to model the atomistic steps of the most promising systems whereas further SPP partners simulate the kinetics in the super focus mixer, the Taylor bubble and the capillary flow reactor. Compared to the first project phase competitive-parallel and consekutive reactions will be studied.