Laser Ablation Synthesis of Gold Selenides by using a Mass Spectrometer as a Synthesizer: Laser Desorption Ionization Time‐of‐Flight Mass Spectrometry

Abstract

Methods for the rapid construction of new chemical motifs have the potential to accelerate the development of nanoscience. The synthesis of new chemical entities by laser ablation has been systematically demonstrated by using mixtures of gold and selenium. The compounds generated are detected by time-of-flight mass spectrometry and, for selected compounds, the structure is investigated by using density functional theory optimization. In total, 67 new gold selenide clusters have been synthesized, demonstrating an unsuspected richness in gold chemistry. Chemical species generated in the gas phase might inspire new routes for the synthesis of novel compounds in the solid state.

Colloidal and Deposited Products of the Interaction of Tetrachloroauric Acid with Hydrogen Selenide and Hydrogen Sulfide in Aqueous Solutions

“…The assignment of the Au 4f components is not straightforward, particularly, since AuSe contains two sorts of Au atoms, the oxidation state of which is a matter of dispute [35][36][37][38][39][40][41][42][43][44][45]. The Au 4f 7/2 peaks at 84.0-84.4 eV reported for gold-gold selenide [39][40][41], gold-CdSe [44,45]), adlayers of Se or alkyl selenides at Au [45][46][47][48][49]59], etc., originate from Au 0 surfaces but not AuSe phases. In nanostructured AuSe with admixture of Au [42], the values of 83.7 eV and 84.9 eV have been found, along with Se 3d 5/2 line at 54.5 eV, and ascribed to Au 0 and Au + , respectively; nevertheless, the authors assert the mixed valence state of gold (Au + Au 3+ Se 2 ).…”

“…It is known from chemistry textbooks (for example [38]) that direct interaction between aqueous gold complexes and selenide ions results in precipitation of unstable gold selenides with unclear compositions. Preparation of nanoscale materials containing gold selenide have been described in a few publications [17,[39][40][41][42][43][44][45]. Nath and co-workers [39] have synthesized "AuSe nanoalloys" via fusion of elemental Au and Se nanoparticles in a micellar solution, typically with an excess of Au NPs.…”

“…Nath and co-workers [39] have synthesized "AuSe nanoalloys" via fusion of elemental Au and Se nanoparticles in a micellar solution, typically with an excess of Au NPs. Prokeš et al [40] have used mixed dispersions of gold nanoparticles and elemental selenium, or Se powder suspended in HAuCl 4 solutions in various proportions as precursors for laser ablation, and detected in gas phase, by using mass-spectrometry, numerous gold-selenide nanoclusters Au m Se n leaning to compositions with Au/Se = 2 and Au/Se = 1. Machogo et al [42] have recently reported the preparation of AuSe nanostructures mixed with metallic nanogold and unreacted Se by the reaction of HAuCl 3 ·3H 2 O with elemental Se in oleylamine.…”

Gallium selenide clusters generated via laser desorption ionisation quadrupole ion trap time‐of‐flight mass spectrometry

“…Selenium clusters were generated via LDI in both positive and negative reflectron ion mode. The mass spectra of selenium showed higher intensity in positive ion mode ( n = 2–8) than in negative ion mode ( n = 2–7), in agreement with the literature . Only Ga 2 + clusters were detected.…”

“…Laser pulses are also used to produce nano‐compounds such as quantum dots in liquid solutions . The possibility of using laser desorption ionisation (LDI) associated with time‐of‐flight mass spectrometry (TOF‐MS) has already been shown for the generation and study of inorganic materials such as gold selenides, As 2 Ch 3 (Ch = S, Se, and Te) chalcogenides, and transition metal clusters…”