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

在SPP 1740中，Herres-Pawlis小组的任务是开发定制的化学反应系统。调查的目标系统与氧气和一氧化氮反应的多相混合物中的过程的详细了解，如存在于反应性泡状流。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，原位光谱方法是焦点，例如拉曼和荧光光谱。六个不同的反应系统已经开发和研究对他们的动力学和理论方面通过停流光谱，在超聚焦混合器和泰勒bubble.The第二个资金周期的目标是检测多维的氧转移与随后的连续或并行反应与混合灵敏度和阐明完整的动力学与传质系数。因此，该系统应可通过LIF检测，并可大量使用。特殊的挑战在于将系统调整到室温，从而定义的Cu 2 O2化学通常在-80 ° C下进行。这只能通过复杂的配体设计来实现。此外，必须开发配体再循环的策略，以覆盖SPP 1740内所需的量。将通过UV/维斯和停流光谱对氧活化和转移的动力学进行表征，以获得固有反应常数。与选定的工作组合作，多维实验中的超级焦点混合器，泰勒气泡，泰勒流，一个和两个气泡细胞，螺旋毛细管流反应器的鼓泡塔的设想：因此，所产生的系统的颜色，但也利用其荧光响应。为了在工业规模上使用氧化反应，需要对所有步骤进行全面的动力学分析以及对通过相边界层气液传质的深入理解。在这里，模拟将有助于所有尺寸尺度：密度泛函理论将有助于模拟最有前途的系统的原子步骤，而SPP合作伙伴进一步模拟超聚焦混合器，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-平行和连续反应。

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.