LENS, European Laboratory for Non-linear Spectroscopy, Via N. Carrara 1, I-50019 Sesto Fiorentino, Firenze, Italy.
Phys Chem Chem Phys. 2011 Jan 28;13(4):1264-75. doi: 10.1039/c0cp01318h. Epub 2010 Dec 13.
It is shown that photoinduced reactions are observed at room temperature and pressure of few tenths of gigapascal in clathrate hydrates of CO and of model hydrocarbons under mild irradiation at 350 nm with power in the 50-610 mW range. The reactions are triggered by highly reactive OH radicals produced by two-photon excitation of the lowest electronic excited state of water having dissociative character. The formation of CO(2) is observed in all the reactions involving carbonaceous clathrate hydrates, and direct or indirect evidence for the formation of molecular hydrogen is obtained. The CO(2) produced in the reactions can be sequestered as a clathrate hydrate whose stability range seems to extend to room temperature at pressures of 0.5-0.6 GPa. Although the N(2) hydrate is stable up to 0.9 GPa under irradiation, a partial cleavage of the N-N triple bond is produced once the hydrate decomposes at 0.1 GPa.
研究表明，在室温下、几十分之一吉帕斯卡的压力下，在 CO 和模型烃类的笼形水合物中，在 350nm 波长、50-610mW 功率的弱辐照下，可以观察到光诱导反应。这些反应是由具有离解特性的水的最低电子激发态的双光子激发产生的高反应性 OH 自由基引发的。在所有涉及含碳笼形水合物的反应中都观察到了 CO2 的形成，并获得了形成分子氢的直接或间接证据。反应中生成的 CO2 可以被捕获为笼形水合物，其稳定性范围似乎在 0.5-0.6GPa 的压力下扩展到室温。尽管在辐照下，N2 水合物在 0.9GPa 下稳定，但一旦在 0.1GPa 下水合物分解，N-N 三键就会部分断裂。
