Laser ablation synthesis of new gold phosphides using red phosphorus and nanogold as precursors. Laser desorption ionisation time‐of‐flight mass spectrometry

Abstract

Gold phosphides show unique optical or semiconductor properties and there are extensive high technology applications, e.g. in laser diodes, etc. In spite of the various AuP structures known, the search for new materials is wide. Laser ablation synthesis is a promising screening and synthetic method. Generation of gold phosphides via laser ablation of red phosphorus and nanogold mixtures was studied using laser desorption ionisation time-of-flight mass spectrometry (LDI TOFMS). Gold clusters Au(m)(+) (m = 1 to ~35) were observed with a difference of one gold atom and their intensities were in decreasing order with respect to m. For P(n)(+) (n = 2 to ~111) clusters, the intensities of odd-numbered phosphorus clusters are much higher than those for even-numbered phosphorus clusters. During ablation of P-nanogold mixtures, clusters Au(m)(+) (m = 1-12), P(n)(+) (n = 2-7, 9, 11, 13-33, 35-95 (odd numbers)), AuP(n)(+) (n = 1, 2-88 (even numbers)), Au(2)P(n)(+) (n = 1-7, 14-16, 21-51 (odd numbers)), Au(3)P(n)(+) (n = 1-6, 8, 9, 14), Au(4)P(n)(+) (n = 1-9, 14-16), Au(5)P(n)(+) (n = 1-6, 14, 16), Au(6)P(n)(+) (n = 1-6), Au(7)P(n)(+) (n = 1-7), Au(8)P(n)(+) (n = 1-6, 8), Au(9)P(n)(+) (n = 1-10), Au(10)P(n)(+) (n = 1-8, 15), Au(11)P(n)(+) (n = 1-6), and Au(12)P(n)(+) (n = 1, 2, 4) were detected in positive ion mode. In negative ion mode, Au(m)(-) (m = 1-5), P(n)(-) (n = 2, 3, 5-11, 13-19, 21-35, 39, 41, 47, 49, 55 (odd numbers)), AuP(n)(-) (n = 4-6, 8-26, 30-36 (even numbers), 48), Au(2)P(n)(-) (n = 2-5, 8, 11, 13, 15, 17), A(3) P(n)(-) (n = 6-11, 32), Au(4)P(n)(-) (n = 1, 2, 4, 6, 10), Au(6)P(5)(-), and Au(7)P(8)(-) clusters were observed. In both modes, phosphorus-rich Au(m)P(n) clusters prevailed. The first experimental evidence for formation of AuP(60) and gold-covered phosphorus Au(12)P(n) (n = 1, 2, 4) clusters is given. The new gold phosphides generated might inspire synthesis of new Au-P materials with specific properties.

Clusters of Monoisotopic Elements for Calibration in (TOF) Mass Spectrometry

“…Clusters of monoisotopic elements provide simple spectra with many monoisotopic peaks covering the mass range of interest with regular mass spacing. In this work, we discuss the calibration of mass spectra by clusters of red phosphorus, which is already established in our laboratory [6,[10][11][12][13][14][15][16], and compare it with calibration by gold clusters generated directly on the target by laser desorption ionization (LDI)-MS of various materials, including gold foil [17], various types of gold nanoparticles (AuNPs), chloroauric acid (HAuCl 4 ), a mixture of 2-(4-hydroxyphenylazo) benzoic acid and HAuCl 4 [18], and polyvinylpyrrolidone-stabilized AuNPs [19]. Gold clusters provide simple and fast determination of accurate mass compared with common calibration standards, such as peptides or proteins.…”

Use of flower‐like gold nanoparticles in time‐of‐flight mass spectrometry

“…Generally, laser radiation induces breakdown of any AuNPs to smaller clusters. Because gold is monoisotopic, such clusters have already been proposed to be used for calibration in MS . The formation of Au m + clusters ( m up to 100) by LDI of 2‐(4'‐hydroxybenzeneazo)benzoic acid/HAuCl 4 mixture and Au m + clusters ( m up to 200) by LDI of polyvinylpyrrolidone‐stabilized AuNPs has already been demonstrated …”

Laser ablation synthesis of carbon–phosphides from graphene/nanodiamond–phosphorus composite precursors: Laser desorption ionisation time‐of‐flight mass spectrometry

“…Mass spectrometry has been used to synthesize a range of clusters, e.g. new gold phosphide clusters using nanogold and red phosphorus as precursors, gold–arsenides, gold–carbides, and arsenic–phosphides …”