Arbelo Yunieski, Bleiner Davide
Swiss Federal Laboratories for Materials Science and Technology (Empa), Überlandstrasse 129, CH-8600, Dübendorf, Switzerland.
Rapid Commun Mass Spectrom. 2019 Jul 30;33(14):1196-1206. doi: 10.1002/rcm.8463.
Species with ionization energies beyond what is accessible using state-of-the-art lab sources are affected by poor detection limits in ordinary mass spectrometry setups, whose throughput is also often limited. Extreme ultraviolet (XUV) photoionization mass spectrometry, in combination with linear time-of-flight (TOF), is necessary for the sensitive detection of high ionization energy compounds at trace level. XUV photoionization is available at beamlines, although with limited access. A tabletop setup may fill such a gap.
A self-developed tabletop system, based on a plasma discharge with extreme ultraviolet emission (λ = 5-50 nm) coupled to a TOF mass spectrometer, was used in this study. Simultaneous validation measurements with a reference electron ionization quadrupole mass filter were carried out. An in-house developed hollow toroidal coil (HTC) induction detector was used for concomitant photoelectron detection.
Straightforward XUV mass spectra without fragmentation, thanks to the single-photon ionization, were acquired. The measurements with the reference quadrupole were in agreement with the spectra acquired by XUV-TOF. The resolution obtained for N was at least factor of 2 higher than that measured with the reference quadrupole. Initial energy distributions of photoelectrons were retrieved by cross-correlation that gave access to the photoionization distribution.
The system allows XUV single-photon ionization of elements and molecules with IE >10 eV that are of fundamental interest e.g. for water splitting and catalysis research. The demonstrated performance is now suitable for a prototype platform.
对于电离能超出使用最先进实验室光源所能达到范围的物种,普通质谱设置中的检测限较差会对其产生影响,而且其通量通常也有限。极紫外(XUV)光电离质谱结合线性飞行时间(TOF),对于痕量水平的高电离能化合物的灵敏检测是必要的。虽然在光束线处可获得XUV光电离,但使用受限。桌面装置可能会填补这一空白。
本研究使用了一个自行开发的桌面系统,该系统基于产生极紫外发射(λ = 5 - 50 nm)的等离子体放电并与一台TOF质谱仪相连。使用参考电子电离四极质量过滤器进行了同步验证测量。使用内部开发的空心环形线圈(HTC)感应探测器进行伴随光电子检测。
由于单光子电离,获得了无碎片的直接XUV质谱。参考四极杆的测量结果与XUV - TOF获得的光谱一致。对于N获得的分辨率比用参考四极杆测量的至少高2倍。通过互相关检索光电子的初始能量分布,从而获得光电离分布。
该系统允许对电离能大于10 eV的元素和分子进行XUV单光子电离,这些元素和分子在例如水分解和催化研究等方面具有根本重要性。所展示的性能现在适用于一个原型平台。