Yamauchi Yasuhiro, Hoshimoto Yoichi, Kawakita Takahiro, Kinoshita Takuya, Uetake Yuta, Sakurai Hidehiro, Ogoshi Sensuke
Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan.
Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871, Japan.
J Am Chem Soc. 2022 May 18;144(19):8818-8826. doi: 10.1021/jacs.2c02870. Epub 2022 May 3.
Chemisorption on organometallic-based adsorbents is crucial for the controlled separation and long-term storage of gaseous molecules. The formation of covalent bonds between the metal centers in the adsorbents and the targeted gases affects the desorption efficiency, especially when the oxidation state of the metal is low. Herein, we report a pressure-responsive nickel(0)-based system that is able to reversibly chemisorb carbon monoxide (CO) at room temperature. The use of -heterocyclic carbene ligands with hemi-labile -phosphine oxide substituents facilitates both the adsorption and desorption of CO on nickel(0) via ligand substitution. Ionic liquids were used as the reaction medium to enhance the desorption rate and establish a reusable system. These results showcase a way for the sustainable chemisorption of CO using a zero-valent transition-metal complex.
基于有机金属的吸附剂上的化学吸附对于气态分子的可控分离和长期储存至关重要。吸附剂中的金属中心与目标气体之间形成共价键会影响解吸效率,尤其是当金属的氧化态较低时。在此,我们报道了一种基于镍(0)的压力响应体系,该体系能够在室温下可逆地化学吸附一氧化碳(CO)。使用带有半不稳定氧化膦取代基的杂环卡宾配体通过配体取代促进了CO在镍(0)上的吸附和解吸。离子液体用作反应介质以提高解吸速率并建立可重复使用的体系。这些结果展示了一种使用零价过渡金属配合物可持续化学吸附CO的方法。