Institute of Modern Physics, Chinese Academy of Sciences, No. 509 Nanchang Rd., Lanzhou, 730000, China.
Phys Chem Chem Phys. 2019 Mar 27;21(13):7147-7154. doi: 10.1039/c8cp07844k.
A gas-phase chemical study of rhenium carbonyls was carried out using short-lived radioisotopes produced at a heavy-ion accelerator. The Re isotopes produced in the nuclear reactions of natGd(23Na,xn)172-177Re were pre-separated with a gas-filled recoil ion separator and their carbonyls were synthesized in a mixture of inert gas and carbon monoxide. Using a low temperature isothermal chromatography apparatus, the adsorption enthalpies of Re carbonyls were derived to be ΔHads = -42 ± 2 kJ mol-1 on a Teflon® surface by fitting the external chromatograms with a Monte Carlo simulation program. A chemical yield of 25% relative to that of the transport yield for Re by a He/KCl gas-jet was achieved. The laser-ablation time-of-flight mass-spectrometric technique was employed to identify the species of Re carbonyls produced in the gas phase. The most stable species was deduced to be Re(CO)5 based on the mass-spectrometric analysis as well as quantum chemistry calculations.
采用重离子加速器产生的短寿命放射性同位素对铼羰基化合物进行了气相化学研究。通过气体填充反冲离子分离器对 natGd(23Na,xn)172-177Re 核反应中产生的 Re 同位素进行预分离，并在惰性气体和一氧化碳的混合物中合成它们的羰基化合物。使用低温等温色谱仪，通过将外部色谱图与蒙特卡罗模拟程序拟合，得出 Re 羰基化合物在特氟龙®表面上的吸附焓为ΔHads = -42 ± 2 kJ mol-1。相对于 He/KCl 气流的 Re 输运产率，实现了 25%的化学产率。采用激光烧蚀飞行时间质谱技术鉴定了气相中生成的 Re 羰基化合物的种类。基于质谱分析和量子化学计算，推断最稳定的物种为 Re(CO)5。
