GC-MS exploration of photochemically generated species of Os, W and Ru from reductive and oxidative media

Vyhnanovský, Jaromír; Musil, Stanislav; Oliveira, Richard Macedo de; Forczek, Sándor T; Sturgeon, Ralph E.

doi:10.1039/d1ja00448d

Cited by 10 publications

(4 citation statements)

References 53 publications

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“…In relatively older studies, formation of Ir(CO) 4 H was reported when water containing IrCl 3 was used for the preparation of other iridium carbonyls and detected as a very volatile compound, 51 including the direct evidence by Whyman, 52 who used IR spectroscopy to investigate reactions of Ir 4 (CO) 12 under various pressures of CO and H 2 and found no evidence for formation of Ir 2 (CO) 8 . 53 To the best of our knowledge, successful GC−MS detection of any iridium carbonyl has not yet been achieved (including our most recent attempts), 54 and there is also no MS spectrum available in the NIST database. 55 Hence, identification of the product of PVG may be challenging despite its relatively good stability based on experience generated in this study.…”

Section: Figures Of Meritmentioning

confidence: 99%

Highly Efficient Photochemical Vapor Generation for Sensitive Determination of Iridium by Inductively Coupled Plasma Mass Spectrometry

et al. 2023

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Herein, we describe the highly efficient photochemical vapor generation (PVG) of a volatile species of Ir (presumably iridium tetracarbonyl hydride) for subsequent detection by inductively coupled plasma mass spectrometry (ICPMS). A thin-film flow-through photoreactor, operated in flow injection mode, provided high efficiency following optimization of identified key PVG parameters, notably, irradiation time, pH of the reaction medium, and the presence of metal sensitizers. For routine use and analytical application, PVG conditions comprising 4 M formic acid as the reaction medium, the presence of 10 mg L–1 Co2+ and 25 mg L–1 Cd2+ as added sensitizers, and an irradiation time of 29 s were chosen. An almost 90% overall PVG efficiency for both Ir3+ and Ir4+ oxidation states was accompanied by excellent repeatability of 1.0% (n = 15) of the peak area response from a 50 ng L–1 Ir standard. Limits of detection ranged from 3 to 6 pg L–1 (1.5–3 fg absolute), dependent on use of the ICPMS reaction/collision cell. Interferences from several transition metals and metalloids as well as inorganic acids and their anions were investigated, and outstanding tolerance toward chloride was found. Accuracy of the developed methodology was verified by analysis of NIST SRM 2556 (Used Auto Catalyst) following peroxide fusion for sample preparation. Practical application was further demonstrated by the direct analysis of spring water, river water, lake water, and two seawater samples with around 100% spike recovery and no sample preparation except the addition of formic acid and the sensitizers.

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Section: Figures Of Meritmentioning

confidence: 99%

Highly Efficient Photochemical Vapor Generation for Sensitive Determination of Iridium by Inductively Coupled Plasma Mass Spectrometry

et al. 2023

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“…To date, mainly low molar mass organic acids, primarily formic and acetic acid, have been employed for this purpose as their photolysis yields strongly reducing radical species (H • , R • , and CO 2 •– ) and aquated electrons (e (aq) – ). , These subsequently interact with the ionic analytes to ultimately form volatile free atoms (Hg 0 ), hydrides, carbonyls, or alkylated derivatives, depending on the element and photochemical medium used. Oxidative conditions have also been advantageously used for the PVG of volatile OsO 4 from dilute peroxide, nitric acid, or pure water. − …”

Section: Introductionmentioning

confidence: 99%

“…Oxidative conditions have also been advantageously used for the PVG of volatile OsO 4 from dilute peroxide, nitric acid, or pure water. 3 − 5 …”

Section: Introductionmentioning

confidence: 99%

Efficient Photochemical Vapor Generation from Low Concentration Formic Acid Media

Jeníková,

Vyhnanovský,

Hašlová

et al. 2024

Anal. Chem.

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Herein, we report on surprisingly efficient photochemical vapor generation (PVG) of Ru, Re, and especially Ir, achieved from very dilute HCOOH media employing a thin-film flow-through photoreactor operated in flow injection mode. In the absence of added metal ion sensitizers, efficiencies near 20% for Ir and approximately 0.06% for Ru and Re occur in a narrow range of HCOOH concentrations (around 0.01 M), significantly higher than previously reported from conventionally optimized HCOOH concentrations (1–20 M). A substantial enhancement in efficiency, to around 9 and 1.5%, could be realized for Ru and Re, respectively, when 0.005 M HCOONa served as the PVG medium. The addition of metal ion sensitizers (particularly Cd2+ and Co2+) to 0.01 M HCOOH significantly enhanced PVG efficiencies to 17, 2.2, and 81% for Ru, Re, and Ir, respectively. Possible mechanistic aspects occurring in dilute HCOOH media are discussed, wherein this phenomenon is attributed to the action of 185 nm radiation available in the thin-film flow-through photoreactor. An extended study of PVG of Fe, Co, Ni, As, Se, Mo, Rh, Te, W, and Bi from both dilute HCOOH and CH3COOH was undertaken, and several elements for which a similar phenomenon appears were identified (i.e., Co, As, Se, Te, and Bi). Although use of dilute HCOOH media is attractive for practical analytical applications employing PVG, it is less tolerant toward dissolved gases and interferents in the liquid phase due to the likely lower concentrations of free radicals and aquated electrons required for analyte ion reduction and product synthesis.

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“…Photochemical vapor generation (PVG) is utilizing generated radicals and aqueous electrons by photodecomposition of low-molecular-weighted organic compounds for converting elements into semivolatile/volatile species, which is regarded as an alternative sample introduction technique in atomic spectrometry. − Over the past two decades, many efforts have focused on expanding the range of PVG elements and increasing the yield of analytes. − Great progress has been made in improving the hardware design of PVG reactors and gas–liquid separators (GLSs) and photochemical mechanisms. ,− Recent research has demonstrated that transition metals (including Fe, Co, Ni, Cu, Cd, Mn, and V) in PVG systems can increase the efficiencies of elements, with improvements ranging from 1.1 to 30,000 folds. − As a result, PVG-based methods can provide better performance for element detection in terms of analytical sensitivity and tolerance to interferences from sample matrices. Furthermore, synergistic effects were observed between different transition-metal ions, including Cu(II) and Co(II) for Mo detection, Fe(II) and Mn(II) for Te(IV) detection, and Co(II) and Cd(II) for the detection of Re, Ru, Ir, and Os. − Similar effects were found with ferric ions and nano-TiO 2 for Te detection and with Cu(II) and Cl – for Ge detection .…”

Section: Introductionmentioning

confidence: 99%

Sensitive Determination of Arsenic by Photochemical Vapor Generation with Inductively Coupled Plasma Mass Spectrometry: Synergistic Effect from Antimony and Cadmium

Deng,

Dong,

Chen

et al. 2023

Anal. Chem.

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A novel method for the determination of trace arsenic (As) by photochemical vapor generation (PVG) with inductively coupled plasma mass spectrometry measurement was developed in this study. The synergistic effect from antimony (Sb) and cadmium (Cd) was found for the photochemical reduction of As for the first time. Effective photochemical reduction of As was obtained in the system containing 10% (v/v) acetic acid, 5.0 mg L −1 Sb(III), and 20.0 mg L −1 Cd(II) with 100 s UV irradiation. Analytical sensitivity of As(III) was comparable with that of As(V) under the tested conditions, making direct determination of total As feasible. Compared to the pneumatic nebulization method, analytical sensitivity of the developed method was enhanced about 50 folds. The PVG efficiency was estimated up to be 99 ± 3%. The limit of detection (LOD) (3σ) was found to be 2.1 ng L −1 for As, which was improved about 30-fold compared to that using direct sample introduction solution nebulization. Considering the sample dilution prior to analysis (usually one-fold), the LOD was actually enhanced about 15 folds. The relative standard deviations of seven replicate measurements of 1.0 μg L −1 As(III) and As (V) standard solutions were 2.3 and 2.9% for As(III) and As(V), respectively. The proposed method was successfully applied for the detection of As in certified reference materials of sediments (GBW07303a and GBW07305a), as well as three water samples. The mechanism of the PVG system was investigated by using gas chromatography mass spectrometry, electron paramagnetic resonance, and X-ray photoelectron spectroscopy. (CH 3 ) 3 As along with (CH 3 ) 3 Sb were synthesized under UV irradiation. Besides, volatile species of Cd were also found. The result obtained in this study is useful for developing efficient "sensitizers" in PVG and understanding the transformation of As in the presence of hydride/cold vapor forming elements in the photochemical process.

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GC-MS exploration of photochemically generated species of Os, W and Ru from reductive and oxidative media

Abstract: The volatile synthetic products of photochemical vapor generation (PVG) of Os(IV) and W(VI) have been confirmed by GC-MS. Osmium tetroxide has been identified as the species generated from an oxidizing...

Cited by 10 publications

References 53 publications

Highly Efficient Photochemical Vapor Generation for Sensitive Determination of Iridium by Inductively Coupled Plasma Mass Spectrometry

Highly Efficient Photochemical Vapor Generation for Sensitive Determination of Iridium by Inductively Coupled Plasma Mass Spectrometry

Efficient Photochemical Vapor Generation from Low Concentration Formic Acid Media

Sensitive Determination of Arsenic by Photochemical Vapor Generation with Inductively Coupled Plasma Mass Spectrometry: Synergistic Effect from Antimony and Cadmium

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