A Raman calibration for the quantification of SO42−groups dissolved in silicate glasses: Application to natural melt inclusions

Morizet, Yann; Gennaro, Emanuela; Jégo, Sébastien; Zajacz, Zoltán; Iacono-Marziano, Giada; Pichavant, Michel; Carlo, Ida Di; Ferraina, Clément; Lesne, Priscille

doi:10.2138/am-2017-6100

Cited by 13 publications

(17 citation statements)

References 89 publications

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“…Raman spectra in Figure 2d were measured to further characterize the existence of SO 4 2− groups. [ 25 ] Raman peaks located at 242, 308, and 353 cm −1 can be ascribed to the F 2g , F 1u , A 1g modes of ZIS, respectively. [ 26,27 ] After annealing in air, the ZIS‐O sample exhibits an additional peak located at 990 cm −1 compared with ZIS, which can be ascribed to the SO stretch of SO 4 2− .…”

Section: Resultsmentioning

confidence: 99%

Incorporation of Sulfate Anions and Sulfur Vacancies in ZnIn₂S₄ Photoanode for Enhanced Photoelectrochemical Water Splitting

Gao

Meng

et al. 2021

Advanced Energy Materials

116

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friendly properties. [6] However, due to its severe bulk carrier recombination, unfavorable carrier transportation, and sluggish surface OER dynamics, the PEC performance of bare ZnIn 2 S 4 photoanode is still not satisfactory.Various strategies have been developed to enhance the PEC performance of ZnIn 2 S 4 , such as morphology engineering, constructing heterojunctions, and coating surface co-catalysts, etc. [7][8][9] Among them, decorating surface cocatalysts has been considered as an effective strategy to promote surface water oxidation kinetics of pristine ZnIn 2 S 4 . However, the integration of water-oxidation cocatalysts with PEC photoanodes has been limited to metal-based materials, such Co-Pi, FeCoO x , and FeOOH. [10][11][12][13][14][15] The cocatalysts containing metallic ions tend to be toxic and expensive, which could limit their further applications. In addition, these cocatalysts may cause light absorption attenuation and increased charge recombination due to the large thickness/dimension of cocatalysts and additional interface defects between cocatalysts and photo anodes. Recently, nonmetallic anionic groups, such as phosphate (PO 4 3− ), selenate (SeO 4 2− ), and sulfate (SO 4 2− ), have emerged as alternatives to boost water oxidation ability. [16][17][18] These nonmetallic groups could optimize the electronic structure of active sites, regulate the adsorption of intermediates to reduce OER overpotential, and promote the surface carrier transfer. Particularly, the SO 4 2− group can break the adsorption-energy scaling relation between OH* and OOH* (reaction intermediates) and decrease the OER overpotential. [17] Accordingly, engineering ZnIn 2 S 4 with SO 4 2− groups is a promising strategy to improve its surface reaction kinetics. However, the introduction of nonmetallic anionic groups usually relies on a direct mixing method or external addition, which leads to weak chemical interaction and thus decreases the effectiveness and durability of the resultant materials. [17] In contrast, in situ introducing SO 4 2− anionic groups into ZnIn 2 S 4 to induce strong bonding between anions and metal atoms is expected to remarkably facilitate solar water oxidation.As a kind of intrinsic defect for metal sulfide, sulfur vacancies (S v ) have the ability to adjust the electronic structure of metal sulfide, leading to optimization of the adsorption free energy and also improvement of the conductivity. [19,20] S v can be divided into bulk S v and surface S v according to their spatial Severe charge recombination and slow surface water oxidation kinetics seriously limit the practical application of ZnIn 2 S 4 photoanodes for photo electrochemical water splitting. Herein, an in situ strategy to introduce sulfate (SO 4 2− ) anions and controlled bulk sulfur vacancies (S v ) into a ZnIn 2 S 4 photoanode is developed, and its PEC performance is remarkably enhanced, achieving a photocurrent density of 3.52 mA cm −2 at 1.23 V versus reversible hydrogen electrode (V RHE ) and negatively shifted onset potential of 0....

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Section: Resultsmentioning

confidence: 99%

Incorporation of Sulfate Anions and Sulfur Vacancies in ZnIn₂S₄ Photoanode for Enhanced Photoelectrochemical Water Splitting

Gao

Meng

et al. 2021

Advanced Energy Materials

116

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“…Spectroscopic studies were achieved to establish calibrations from Raman spectra in crystallized materials (e.g., these works). Many studies on amorphous materials based on the investigation of CO 2 and S behaviors in a silicate melt have led to subsequent calibrations (e.g., these works). Calibrations to quantify the H 2 O in melts by Raman spectroscopy have been proposed by these works .…”

Section: Introductionmentioning

confidence: 99%

Particular H₂O dissolution mechanism in iron‐rich melt: Application to martian basaltic melt genesis

Larre

Morizet

Bézos

et al. 2019

J Raman Spectroscopy

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Martian basalts are different from Earth by their iron‐rich abundance with 18 wt% FeOtot in average for Mars upper crust. The H2O dissolution mechanism in this atypical melt composition is not well understood. We have synthesized H2O‐bearing martian basaltic glass analogs (10 < FeOtot < 16 wt%) under high pressures (0.5–1.5 GPa) and temperatures (>1500°C) conditions. We used Raman and Fourier transform infrared spectroscopies to investigate the effect of H2O as well as the high FeOtot content on the molecular structure of Fe‐rich glasses. Increasing Fe content appears to inhibit the dissolution of H2O in the melt. In fact, it appears that Free OH groups are formed at relatively low H2O content in Fe‐rich melts (1 wt%), whereas they only appeared at high H2O content (~6.5 wt%) for Fe‐poor glasses. We suggest that the Free OH are bonded to Fe2+ cations in the melt forming isolating clusters of Fe (OH)2. Such configurations are suspected to induce an increase in the melt polymerization. The presence of free hydroxyls dissolved in the melt is likely to have a major impact on the genesis of aqueous fluid phase at the surface of Mars.

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“…The protocol to simulate Raman peaks is described fully in previous investigations and is used routinely for the quantification of volatiles species in silicate glasses (Mysen and Virgo 1980 a , b ; Mercier et al , 2009; Morizet et al , 2013 a , 2017). First, we have fixed the peak position and widths (Gaussian and Lorentzian), leaving only the peak area optimised.…”

Section: Methodsmentioning

confidence: 99%

“…Relevant interpretations of Raman spectra in this study will require the acquisition of laboratory data under similar analytical conditions of the on-board Raman spectrometer. Although Raman spectroscopy is nominally non-quantitative with relevant calibration, it can be used for quantifying S at low concentrations (thousands of ppm) owing to the high Raman activity of S-bearing molecular groups (Morizet et al , 2017).…”

Section: Introductionmentioning

confidence: 99%

“…Previous studies have focused on the quantification of volatile species (H 2 O, CO 2 and SO 4 2− ) in silicate glasses with application to Earth volcanism (Zajacz et al , 2005; Mercier et al , 2009; Le Losq et al , 2012; Morizet et al , 2013 a , b , 2017). However, up to now, only the quantification of individual mineral species in polymineralic mechanical mixtures have been addressed using Raman spectroscopy (Kontoyannis et al , 1997; Jehlicka et al , 2009; Noguchi et al , 2009; Kriskova et al , 2013; Culka et al , 2014).…”

Section: Introductionmentioning

confidence: 99%

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Quantitative Raman calibration of sulfate-bearing polymineralic mixtures: a S quantification in sedimentary rocks on Mars

Larre

Morizet

Guillot‐Deudon

et al. 2018

MinMag

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The NASA 2020 Mars mission is a Curiosity-type rover whose objective is to improve the knowledge of the geological and climatic evolution of Mars and to collect rock samples for return to Earth. The new rover has a payload of seven instruments including the SuperCam instrument which consists of four tools including a Raman spectrometer. This Raman device will be non-destructive and will analyse the surface remotely in order to determine the mineralogy of rocks and, by extent, to detect and quantify major elements such as sulfur. Sulfur has been detected as sulfate (Ca,Mg,Fe-sulfates) in sedimentary rocks. This element is difficult to quantify using the laser ablation tool of the ChemCam instrument on-board the Curiosity rover.We propose a Raman calibration to constrain the sulfur abundance in polymineralic mixtures. We acquired Raman signatures on binary and ternary mechanical mixtures containing Ca and Mg sulfates, mixed with natural silicate minerals supposed to be relevant to basaltic-sedimentary rocks at the surface of Mars: olivine, clinopyroxene, orthopyroxene and plagioclase. Using the Voigt function to process the Raman spectra from samples extracted from our mixtures allows us to calculate the initial proportions of our preparations of Ca and Mg sulfates. From these simulations, calibration equations have been provided allowing us to determine sulfate proportions (CaSO4 and MgSO4) in a mixture with basaltic minerals. With the presented calibration, S can be quantified at a lower limit of 0.7 wt.% in Martian soil.

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A Raman calibration for the quantification of SO₄²⁻groups dissolved in silicate glasses: Application to natural melt inclusions

Cited by 13 publications

References 89 publications

Incorporation of Sulfate Anions and Sulfur Vacancies in ZnIn₂S₄ Photoanode for Enhanced Photoelectrochemical Water Splitting

Incorporation of Sulfate Anions and Sulfur Vacancies in ZnIn₂S₄ Photoanode for Enhanced Photoelectrochemical Water Splitting

Particular H₂O dissolution mechanism in iron‐rich melt: Application to martian basaltic melt genesis

Quantitative Raman calibration of sulfate-bearing polymineralic mixtures: a S quantification in sedimentary rocks on Mars

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A Raman calibration for the quantification of SO42−groups dissolved in silicate glasses: Application to natural melt inclusions

Cited by 13 publications

References 89 publications

Incorporation of Sulfate Anions and Sulfur Vacancies in ZnIn2S4 Photoanode for Enhanced Photoelectrochemical Water Splitting

Incorporation of Sulfate Anions and Sulfur Vacancies in ZnIn2S4 Photoanode for Enhanced Photoelectrochemical Water Splitting

Particular H2O dissolution mechanism in iron‐rich melt: Application to martian basaltic melt genesis

Quantitative Raman calibration of sulfate-bearing polymineralic mixtures: a S quantification in sedimentary rocks on Mars

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A Raman calibration for the quantification of SO₄²⁻groups dissolved in silicate glasses: Application to natural melt inclusions

Incorporation of Sulfate Anions and Sulfur Vacancies in ZnIn₂S₄ Photoanode for Enhanced Photoelectrochemical Water Splitting

Incorporation of Sulfate Anions and Sulfur Vacancies in ZnIn₂S₄ Photoanode for Enhanced Photoelectrochemical Water Splitting

Particular H₂O dissolution mechanism in iron‐rich melt: Application to martian basaltic melt genesis