Atomic-level insight of sulfidation-engineered Aurivillius-related Bi_(2)O_(2)SiO_(3) nanosheets enabling visible light low-concentration CO_(2) conversion

Unraveling atomic-level active sites of layered photocatalyst towards lowconcentration CO_(2) conversion is still challenging.Herein,the yield and selectivity of photocatalytic CO_(2) reduction of the Aurivillius-related oxide semiconductor Bi_(2)O_(2)SiO_(3) nanosheet(BOSO)were largely improved using a surface sulfidation strategy.The experiment and theoretical calculation confirmed that surface sulfidation of the Bi_(2)O_(2)SiO_(3) nanosheet(S-BOSO,6.28 nm)redistributed the charge-enriched Bi sites,extended the solar spectrum absorption to the whole visible range,and considerably enhanced the charge separation,in addition to creating new reaction active sites,as compared to pristine BOSO.Subsequently,surface sulfidation played a switchable role,wherein S-BOSO showed a very high CH_(3)OH generation rate(12.78μmol g^(-1) for 4 h,78.6%selectivity)from low-concentration CO_(2)(1000 ppm)under visible light irradiation,which outperforms most of the state-of-the-art photocatalysts under similar conditions.This study presents an atomic-level modification protocol for engineering reactive sites and charge behaviors to promote solar-to-energy conversion.

Effect of ammonium sulfate on the formation of zinc sulfide species on hemimorphite surface and its role in sulfidation flotation

Effectively strengthening the surface sulfidation is essential for recovering hemimorphite by froth flotation.In this work,inductively coupled plasma optical emission spectrometer(ICP-OES)measurements,Visual MINTEQ calculation,X-ray photoelectron spectroscopy(XPS)analysis,time of flight secondary ion mass spectrometry(ToF-SIMS)analysis,and micro-flotation experiments were explored to systematically investigate the effect of ammonium sulfate((NH_(4))_(2)SO_(4))on the formation of zinc sulfide species on hemimorphite surface and its role in sulfidation flotation.The results showed that(NH_(4))_(2)SO_(4)exhibited a positive influence on hemimorphite sulfidation flotation.It was ascribed to the number of zinc components in the form of Zn^(2+)and[Zn(NH_(3))_(i)]^(2+)(i=1–4)increased in the flotation system after hemimorphite treatment with(NH_(4))_(2)SO_(4),which was beneficial to its interaction with sulfur species in solution,resulting in a dense and stable zinc sulfide layer generated on the hemimorphite surface.[Zn(NH_(3))_(i)]^(2+)participated in the sulfidation reaction of hemimorphite as a transition state.In addition the sulfidation reaction of hemimorphite was accelerated by(NH_(4))_(2)SO_(4).Thus,(NH_(4))_(2)SO_(4)presents a vital role in promoting the sulfidation of hemimorphite.

Unveil the Redox Evolution of Ore-forming Fluids using Sulfur Isotope:A Case Study of the Zhengguang Intermediate Sulfidation Epithermal Au-Zn Deposit,NE China

Oxygen fugacity(fO_(2))is a key intensity variable during the entire magmatic-hydrothermal mineralization courses.The redox state and its variations between different stages of the ore-forming fluids of intermediate sulfidation epithermal deposits are rarely deciphered due to the lack of appropriate approaches to determine fO_(2)of the fluids.Here,we reported theδ^(34)S of the sulfides from three different stages(stageⅠ,Ⅱ,Ⅲ)of Zhengguang,an Early Ordovician Au-rich intermediate sulfidation(IS)epithermal deposit,to decipher the redox evolution of the ore-forming fluids.The increasingδ^(34)S values from stageⅠpyrite(pyl,average-2.6‰)through py2(average-1.9‰)to py3(average-0.2‰)indicates a decrease of the oxygen fugacity of the ore-forming fluids.A compilation ofδ^(34)S values of sulfides from two subtypes of IS deposits(Au-rich and Ag-rich)from NE China shows that theδ^(34)S values of sulfides from Au-rich IS deposits are systematically lighter than those of Ag-rich IS Ag-Pb-Zn deposit,indicating the ore-forming fluids of the former are more oxidized than the latter.We highlight that sulfur isotopic composition of hypogene sulfides is an efficacious proxy to fingerprint the oxygen fugacity fluctuations of epithermal deposits and could potentially be used to distinguish the subtypes of IS deposits.

INFLUENCE OF Y,Ce AND La ON HIGH TEMPERATURE SULFIDATION OF Fe-25Cr-40Ni SUPERALLOY

The effects of Y,Ce and La on the sulfidation of alloy Fe-25Cr-40Ni have been investigated. The sulfidation rate of the alloys with RE more than 0.1 wt-% is lower than that of the base alloy.The addition of Y is more effective than La and Ce in lowering the sulfidation rate. Based on the analyses of the structure and composition of the sulfide seales,the sulfidation mechanism of the alloys with RE has been proposed.

Sulfidation roasting of zinc leaching residue with pyrite for recovery of zinc and iron

Zinc leaching residue(ZLR) contains high content of valuable metals such as zinc and iron. However, zinc and iron mainly exist in the form of zinc ferrite, which are difficult to separate and recover. This study proposed a new process involving sulfidation roasting, magnetic separation and flotation to recover zinc and iron in ZLR. Through sulfidation roasting of ZLR with pyrite, zinc and iron were converted into ZnS and Fe3 O4. The effects of pyrite dosage, roasting temperature and roasting time on the sulfidation of zinc in ZLR were investigated. The results showed that the sulfidation percentage of zinc reached 91.8% under the optimum condition. Besides, it was found that ball-milling was favorable for the separation and recovery of zinc and iron in sulfidation products. After ball-milling pretreatment, iron and zinc were enriched from sulfidation products by magnetic separation and flotation. The grade of iron in magnetic concentrates was 52.3% and the grade of zinc in flotation concentrates was 31.7%, which realized the recovery of resources.

Separation of arsenic and antimony from dust with high content of arsenic by a selective sulfidation roasting process using sulfur

The separation of arsenic and antimony from dust with high content of arsenic was conducted via a selective sulfidation roasting process.The factors such as roasting temperature,roasting time,sulfur content and nitrogen flow rate were investigated using XRD,EPMA and SEM-EDS.In a certain range,the sulfur addition has an active effect on the arsenic volatilization because the solid solution phase（（Sb,As）2O3）in the dust can be destroyed after the Sb component in it being vulcanized to Sb2S3 and this generated As2O3 continues to volatile.In addition,an amorphization reaction between As2O（3 ）and Sb2O（3 ）is hindered through the sulfidation of Sb2O3,which is also beneficial to increasing arsenic volatilization rate.The results show that volatilization rates of arsenic and antimony reach 95.36%and only 9.07%,respectively,under the optimum condition of roasting temperature of 350℃,roasting time of 90 min,sulfur content of 22%and N2 flow rate of 70 m L/min.In addition,the antimony in the residues can be reclaimed through a reverberatory process.

Recovery of Zn, Pb, Fe and Si from a low-grade mining ore by sulfidation roasting-beneficiation-leaching processes

To recover Zn, Pb, Fe and Si from a low-grade mining ore in the Lanping basin, Yunnan Province, China, a novel technology using the roasting with pyrite and carbon followed by beneficiation and hydrochloric acid leaching was proposed. Firstly, several factors such as pyrite dosage, roasting temperature, carbon powder dosage, holding time and particle size affecting on the flotation performance of Zn(Pb) and magnetic separation performance of Fe were simultaneously examined and the optimum process parameters were determined. A flotation concentrate, containing 17.46% Zn and 3.93% Pb, was obtained, and the Zn and Pb recoveries were 86.04% and 69.08%, respectively. The obtained flotation tailing was concentrated by a low-intensity magnetic separator. The grade of iron increased from 5.45% to 43.45% and the recovery of iron reached 64.87%. Hydrochloric acid leaching was then carried out for the magnetic separation tailing and a raw quartz concentrate containing 81.05% SiO2 was obtained. To further interpret the sulfidation mechanism of smithsonite, surface morphology and component of the sample before and after reactions were characterized by XRD and EPMA-EDS. The aim was to achieve the comprehensive utilization of the low-grade mining ore.

Cascade sulfidation and separation of copper and arsenic from acidic wastewater via gas-liquid reaction

Copper and arsenic in acidic wastewater were separated by cascade sulfidation followed by replacement of arsenic in theprecipitates by copper in the solution which was realized by recycling precipitates obtained in the first stage into the initial solution.The effects of reaction time,temperature and H2S dosage on copper and arsenic removal efficiencies as well as the effects of solid-toliquidratio,time and temperature on the replacement of arsenic by copper were investigated.With20mmol/L H2S at50°C within0.5min,more than80%copper and nearly20%arsenic were precipitated.The separation efficiencies of copper and arsenic werehigher than99%by the replacement reaction between arsenic and copper ions when solid-to-liquid ratio was more than10%at20°Cwithin10min.CuS was the main phases in precipitate in which copper content was63.38%in mass fraction.

Sulfidation mechanism of cerussite in the presence of sulphur at high temperatures

In this paper,sulfidation mechanism of cerussite in the presence of sulphur at high temperatures was investigated based on micro-flotation,X-ray powder diffractometry(XRD),electron probe microanalysis(EPMA)and X-ray photoelectron spectroscopy(XPS).The micro-flotation test results showed that flotation recovery of the treated cerussite increased to above 80%under a suitable flotation condition.It was found that the S/PbCO3 mole ratio and pH obviously affected flotation recovery.XRD analysis results confirmed that the cerussite was decomposed into massicot and then was transformed into mainly PbS and PbO·PbSO4 after sulfidation roasting.EPMA analysis results demonstrated that surface of the obtained massicot was smooth,but surface of the artificial galena was rough and even porous.Content of oxygen decreased,whereas content of sulphur increased with an increase in the S/PbCO3 mole ratio.XPS analysis results revealed that various lead-bearing species,including mainly PbS,PbSO4 and PbO·PbSO4,were generated at the surface.Formation of PbS was advantageous to flotation of the treated cerussite.Based on these results,a reaction model of the cerussite sulfurized with sulphur was proposed.

Study on Sulfidation Degree and Morphology of MoS_2 Catalyst Derived from Various Molybdate Precursors

The MoS_2 catalysts were prepared from various molybdate precursors including inorganic and organic molybdate compounds. The sulfidation degree and morphology of active phases of MoS_2 activated by various molybdate precursors in H_2S/H_2 stream at different temperatures were studied by X-ray photoelectron spectroscopy(XPS) and high-resolution transmission electron microscopy(HRTEM). The organic molybdate precursors lead to MoS_2 catalysts with higher sulfidation degree and smaller active phases to demonstrate higher catalytic activity during hydrodesulfurizaiton(HDS) of 4,6-DMDBT.

Influence of low-temperature sulfidation on the structure of ZnS thin films

ZnS thin films were prepared by sulfuring zinc thin films at different sulfuration temperatures. The crystal structure,surface morphology, defects, and optical properties of the thin films were characterized by x-ray diffraction(XRD), scanning electron microscopy(SEM), positron annihilation Doppler broadening, and UV-Vis spectrophotometer, respectively.It was found that the(200)-plane preferred orientation of the ZnS thin films changed to(111)-plane with increasing sulfidation temperature. Moreover, a number of large holes were generated at 420?C and eliminated at 440?C. The concentration of defects was lowest when the sulfuration temperature was 440?C. The optical transmission of all samples was maintained at 60%–80% in the wavelength range of 400 nm–800 nm, and the band energy of the ZnS thin films was approximately3.5 e V for all treatment temperatures except 430?C.

THE SULFIDATION/OXIDATION RESISTANCE OF TWO Ni-Cr-Al-Y ALLOYS AT 700℃

The high temperature corrosion resistance of Ni-25.9Cr-13.5Al-1.2Y-0.6Si and Ni-10.2Co-12.4Cr16.0Al-0.5Y-0.2Hf alloys was assessed in sulfidation/oxidation envi-ronments. In the environment with a sulfur partial pressure of 1Pa. and an oxygenpartial pressure of 10^(-19)Pa, both these alloys exhibited three distinct stages in theweight gain-time curve when tested at 700℃. In the initial stage, selective sulfidationof Cr suppressed the formation of the other metal sulfides, resulting in lower weightgains. In the transient stage, breakdown and cracking of Cr sulfides and insufficientconcentration of Cr at the outer zone led to the rapid formation of Ni sulfides anda rapid increase in weight. In the steady-state stage, corrosion was controlled by thediffusion of anions and/or cations, which led to a parabolic rate law.

SULFIDATION OF Co-15wt%Y ALLOY IN H_2-H_2S MIXTURES AT 600-800℃

The corrosion properties of a Co-15wt% Y alloy were studied in H_2-H_2S mixtures under a sulfur pressure of 10-3 Pa at 600-800℃ and of 10-2 Pa at 800℃ to examine the effect of Y on the resistance of pure cobalt to sulfur attack at high temperatures.The alloy is nearly single-phase.containing mostly the intermetallic compound Co17Y2 plus a little amount of the solid solution of Y in cobalt.At 600-700℃ and at 800℃ under 10-2 Pa of S2 the alloy forms multi-layered scales consisting of an outer region of pure cobalt sulfide,an intermediate region of a mixture of the sulfides of the two metals and finally an innermost layer of a mixture of yttrium sulfide with metal cobalt.At 800℃ under 10-3Pa of S2,below the dissociation pressure of cobalt sulfide, the alloy forms only a single layer composed of a mixture of metallic cobalt with yttrium sulfide.Pure Y produces only the oxysulfide Y2O2S, as a result of the good stability of this compound and of the presence of some impurities in the gas mixtures used The corrosion kinetics is generally rather complex and irregular except al 800℃under 10-3 Pa of S2.The addition of yttrium always reduces the sulfidation rate of cobalt, even though the formation of a continuous protective external layer of yttrium sulfide is never achieved.The internal sulfidation of Y in Co-15% Y is not associated with a depletion of Y in the alloy.This kind of diffusionless internal attack is typical of alloys with a very small solubility of the most reactive component Y in the base metal A.which restricts severely the Y flux from the alloy towards the alloy-scale interface.

Sulfidation of Ni, Mo-Containing Y Zeolites and Reactivity for Thiophene Hydrodesulfurization

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Controlled moderative sulfidation-fabricated hierarchical heterogeneous nickel sulfides-based electrocatalyst with tripartite Mo doping for efficient oxygen evolution

An electrocatalyst with heterogeneous nanostructure, especially the hierarchical one, generally shows a more competitive activity than that of its single-component counterparts for oxygen evolution reaction(OER), due to the synergistically enhanced kinetics on enriched active sites and reconfigured electronic band structure. Here this work introduces hierarchical heterostructures into a NiMo@NiS/MoS_(2)@Ni_(2)S_(2)/MoO_(x)(NiMoS) composite by one-pot controlled moderative sulfidation. The optimal solvent composition and addition of NaOH enable NiMoS to own loose and porous structures, smaller nanoparticle sizes, optimal phase composition and chemical states of elements, improving the OER activity of NiMoS. To achieve current densities of 50 and 100 mA cm^(-1), small overpotentials of 275 and 306 mV are required respectively, together with a minor Tafel slope of 58 mV dec^(-1), which outperforms most reported sulfide catalysts and IrO_(2). The synergistic effects in the hierarchical heterostructures expose more active sites,adjust the electronic band structure, and enable the fast charge transfer kinetics, which construct an optimized local coordination environment for high OER electrocatalytic activity. Furthermore, the hierarchical heterostructures suppress the distinct lowering of electrical conductivity and collapse of pristine structures resulted from the metal oxidation and synchronous S leaching during OER, yielding competitive catalytic stability.

FeMoAl COATING AND ITS HIGHTEMPERATURE SULFIDATION PROPERTIES

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EVOLUTION OF SULFIDE SCALES ON Fe-Mo ALLOYS DURING SULFIDATION

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High-Temperature Sulfidation of Mo-Nb Alloys

The sulfidation rates and sulfide scales of pure Mo, pure Nb, and Mo Nb alloys are studied. By comparing the rates, an alloy with best sulfidation resistance is found. In addition, the sulfidation kinetics of Mo-50 %Nb is studied in detail.

Factors Influencing the Sulfidation Rate of Fe-Mo Binary Alloys

The sulfidation rate constants of various Fe-Mo binary alloys in S2 vapor with different sulfidation parameters were collected to summarize the correlation between the sulfidation rate and alloy composition, sulfur pressure and sulfldation temperature. The octivation energies indicate that the sulfidation process of the alloys is exclusively controlled, at a given temperature, by one alloying component i.e. either Mo or Fe. The sulfidation rate declines exponentially with the increasing of Mo content in alloy. And the influence of sulfur pressure is relatively slight.

INFLUENCE OF Al ON HIGH TEMPERATURE SULFIDATION OF AN Fe-25Cr ALLOY IN H_2S-H_2 GAS MIXTURES

The effects of 5 wt.-% Al and 10 wt.-% Al on the sulfidation behaviour of the Fe-25Cralloy in H2S-H2 gas mixtures in the temperature range of 700～900 C has been studied.Thesulfidation resistance of Fe-25Cr was improved and the sulfide scale morphologies,compositionand structure of Fe-25Cr changed remarkably.The sulfidation kinetics of the alloys with alu-minium obeyed basically the parabolic law after an initial period of reaction time.The sulfida-tion mechanism of the Fe-Cr-Al alloy has been proposed.