Institut für Ionenphysik und Angewandte Physik, Universität Innsbruck, Technikerstraße 25, 6020 Innsbruck, Austria.
Radboud University, Institute for Molecules and Materials, FELIX Laboratory, Toernooiveld 7, 6525 ED Nijmegen, The Netherlands.
J Phys Chem A. 2023 Apr 20;127(15):3402-3411. doi: 10.1021/acs.jpca.3c01394. Epub 2023 Apr 11.
Transition metals are important in various industrial applications including catalysis. Due to the current concentration of CO in the atmosphere, various ways for its capture and utilization are investigated. Here, we study the activation of CO and HO at [NbO] in the gas phase using a combination of infrared multiple photon dissociation spectroscopy and density functional theory calculations. In the experiments, Fourier-transform ion cyclotron resonance mass spectrometry is combined with tunable IR laser light provided by the intracavity free-electron laser FELICE or optical parametric oscillator-based table-top laser systems. We present spectra of [NbO], [NbO(OH)], NbO(OH) and [NbO(OH)(CO)] in the 240-4000 cm range. The measured spectra and observed dissociation channels together with quantum chemical calculations confirm that upon interaction with a water molecule, [NbO] is transformed to [NbO(OH)] via a barrierless reaction. Reaction of this product with CO leads to [NbO(OH)(CO)] with the formation of a [CO] moiety.
过渡金属在各种工业应用中很重要，包括催化。由于目前大气中 CO 的浓度，正在研究各种捕获和利用 CO 的方法。在这里，我们使用红外多光子解离光谱和密度泛函理论计算相结合的方法研究了气相中[NbO]对 CO 和 HO 的活化。在实验中，傅里叶变换离子回旋共振质谱与腔内自由电子激光 FELICE 或基于光参量振荡器的台式激光系统提供的可调谐红外激光相结合。我们在 240-4000 cm 范围内呈现了[NbO]、[NbO(OH)]、[NbO(OH)(HO)]和[NbO(OH)(CO)]的光谱。测量的光谱和观察到的解离通道以及量子化学计算证实，与水分子相互作用后，[NbO]通过无势垒反应转化为[NbO(OH)]。该产物与 CO 的反应导致[NbO(OH)(CO)]的形成，形成了[CO]部分。
