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 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.

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

ＳＵＬＦＩＤＡＴＩＯＮＯＦＣｏ－１５ｗｔ％ＹＡＬＬＯＹＩＮＨ_２－Ｈ_２ＳＭＩＸＴＵＲＥＳＡＴ６００－８００℃ＮＩＵＹａｎ；Ｆ．ＧＥＳＭＵＮＤＯ；ＷＵＷｅｉｔａｏ；ＺＥＮＧＣｈａｏｌｉｕ；Ｆ．ＶＩＡＮＩ；（ＳｔａｔｅＫｅｙＬａｂｏｒａｔｏｒｙｆｏｒＣｏ...

High-Temperature Sulfidation of Mo-Nb Alloys

Ｂｅｃａｕｓｅｏｆｔｈｅｉｎｃｒｅａｓｉｎｇｕｔｉｌｉｚａｔｉｏｎｏｆｍｅｔａｌｓａｔｈｉｇｈｔｅｍｐｅｒａｔｕｒｅｉｎｉｎｄｕｓｔｒｉａｌａｔｍｏｓｐｈｅｒｅｓｃｏｎ－ｔａｉｎｉｎｇｓｕｌｆｕｒａｎｄｉｔｓｃｏｍｐｏｕｎｄｓ，ｔｈｅｐｒａｃｔｉｃａ...

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 basealloy.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 sulfidationmechanism of the alloys with RE has been proposed.

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

ＳｕｌｆｉｄａｔｉｏｎｏｆＮｉ，ＭｏＣｏｎｔａｉｎｉｎｇＹＺｅｏｌｉｔｅｓａｎｄＲｅａｃｔｉｖｉｔｙｆｏｒＴｈｉｏｐｈｅｎｅＨｙｄｒｏｄｅｓｕｌｆｕｒｉｚａｔｉｏｎＣｕｉＪｕｎ，ＧａｏＺｉ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，ＦｕｄａｎＵｎ...

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

ＦｅＭｏＡｌＣＯＡＴＩＮＧＡＮＤＩＴＳＨＩＧＨＴＥＭＰＥＲＡＴＵＲＥＳＵＬＦＩＤＡＴＩＯＮＰＲＯＰＥＲＴＩＥＳ①ＬｉＦａｎｇ，ＨｅＹｅｄｏｎｇ，ＱｉＨｕｉｂｉｎ，ＨｕａｎｇＺｈｅｎｚｈｏｎｇ，ＺｈｕＲｉｚｈａｎｇＢｅｉｊｉｎｇＣｏｒｏｓｉｏｎａｎｄ...

EVOLUTION OF SULFIDE SCALES ON Fe-Mo ALLOYS DURING SULFIDATION

ＥＶＯＬＵＴＩＯＮＯＦＳＵＬＦＩＤＥＳＣＡＬＥＳＯＮＦｅＭｏＡＬＬＯＹＳＤＵＲＩＮＧＳＵＬＦＩＤＡＴＩＯＮ①ＬｉｕＨａｉｐｉｎｇ，ＱｉＨｕｉｂｉｎ，ＨｅＹｅｄｏｎｇ，ＺｈｕＲｉｚｈａｎｇＯｐｅｎＬａｂｏｒａｔｏｒｙｆｏｒＣｏｒｒｏｓｉｏｎａｎｄＥｒ...

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.

PROTECTION AND DAMAGE OF PREFORMED OXIDE SCALES OF Fe－25Cr－5Al AND－10Al ALLOYS DURING THEIR SUBSEQUENT SULFIDATION

ＰＲＯＴＥＣＴＩＯＮＡＮＤＤＡＭＡＧＥＯＦＰＲＥＦＯＲＭＥＤＯＸＩＤＥＳＣＡＬＥＳＯＦＦｅ－２５Ｃｒ－５ＡｌＡＮＤ－１０ＡｌＡＬＬＯＹＳＤＵＲＩＮＧＴＨＥＩＲＳＵＢＳＥＱＵＥＮＴＳＵＬＦＩＤＡＴＩＯＮ￥Ｑｉ，Ｈｕｉｂｉｎ；Ｚｈｕ，Ｒｉｚｈａｎｇ；Ｈｅ...

Sulfidation and selenidation of nickel nanoparticles

NPs using elemental sulfur,1-hexadecanthiol,thiourea,trioctylphosphine sulfide,elemental selenium,and selenourea.While maintaining mole ratios of 2 mmol sulfur/selenium precursor:mmol Ni,products with phases of Ni_(3)S_(2),Ni_(9)S_(8),NiS,NiSO_(4)·6H_(2)O,Ni_(3)S_(4),Ni_(3)Se_(2),and NiSe have been obtained.The products have voids that form through the Kirkendall effect during interdiffusion.Trends relating the chemical properties of the precursors to the phases of the products have been identified.While some precursors contained phosphorus,there was no significant incorporation of phosphorus in any of the products.An increase of the NP size during sulfidation and selenidation is consistent with ripening.The application of Ni sulfide and selenide NPs as electrocatalysts for the hydrogen evolution reaction is also demonstrated.

ARSENIC REMOVAL BY SULFIDATION SEDIMENTATION IN MAGNETIC FIELD

１ＩＮＴＲＯＤＵＣＴＩＯＮＡｓｔｈｅｗａｔｅｒｓｏｕｒｃｅｃｒｉｓｉｓｉｓｂｅｃｏｍｉｎｇｍｏｒｅａｎｄｍｏｒｅｓｅｖｅｒｅａｎｄｔｈｅｅｎｖｉｒｏｎｍｅｎｔｐｒｏｔｅｃｔｉｏｎｒｅｑｕｉｒｅｍｅｎｔｓａｒｅｂｅｃｏｍｉｎｇｍｏｒｅａｎｄｍｏｒｅｒｉ...

Impact of Sulfidation of Silver Nanoparticles on Established<i>P. aeruginosa Biofilm</i>

Silver nanoparticles (Ag-NPs), one of the most common types of nanomaterials in medical fields and consumer products, are known to have antimicrobial effects;these materials also undergo a series of chemical and biological transformations in the environment. Although the pristine form of silver nanoparticles has been studied, less is known about the impacts of the transformed Ag-NPs on biological systems. This knowledge gap hinders the progress of effectively assessing the impacts of Ag-NPs on the environment and human health. In this study, we demonstrate that the most common form of transformed Ag-NPs, sulfidized silver nano-particles (Ag2S-NPs), show less damage on established Pseudomonas aeruginosa GFP (ATCC? 10145 GFP?) biofilm than the pristine form of the nanoparticle. At a dosage of 0.625 mg/L, the total biomass in the biofilm decreased 64% after being exposed to Ag-NPs and 44% after exposure to Ag2S-NPs. Live biofilms were also interrogated. We observed high reduction in live population for biofilm exposed to Ag-NPs and relatively low reduction by Ag2S-NPs at exposure concentrations higher than 0.625 mg/L. Compared with Ag-NPs, the lower solubility of Ag2S-NPs results in less Ag+ diffusion into established biofilms. Our results suggest that the sulfidation of Ag-NPs reduces their impacts on established biofilms, indicating that the transformed Ag-NPs may have less environmental or human health risks.

Partial aging can counter-intuitively couple with sulfidation to improve the reactive durability of zerovalent iron

Sulfated zero-valent iron(SZVI)has shown promising applications in wastewater treatment.However,the rapid decline in the reactivity of SZVI with time limits its real practice.To mediate this problem,partial aging was proposed to improve the reactive durability of SZVI.Taking Cr(VI)as the target contaminant,we found that the aged ZVI(AZVI)gradually lost reactivity as aging time increased from 0.5 to 2 d.Counter-intuitively,the partially aged SZVI(ASZVI)showed greater reactivity than SZVI when exposed to oxygenated water for a period ranging from 0.5 to 14 d.In addition,the ASZVI with 0.5 d of aging time(ASZVI-0.5)not only maintained reactivity in successive runs but also increased the Cr(VI)removal capacity from 9.1 mg/g by SZVI to 19.1 mg/g by ASZVI-0.5.Correlation analysis further revealed that the electron transfer from the Fe0 core to the shell was mediated by the conductive FeS and FeS2 in the subshell of ASZVI.Meanwhile,the lepidocrocite and magnetite on the surface of ASZVI facilitated Cr(VI)adsorption and subsequent electron transfer for Cr(VI)reduction.Moreover,the iron(hydr)oxide shell could retain the conductive FeS and FeS2 in the subshell,allowing ASZVI to reduce Cr(VI)efficiently and sustainably.In general,partial aging can enhance the reactive durability of ZVI when coupled with sulfidation and this synergistic effect will be beneficial to the application of SZVI-based technology for wastewater treatment.

Influence of modified biochar supported sulfidation of nano-zero-valent-iron(S-nZVI/BC) on nitrate removal and greenhouse gas emission in constructed wetland

In this study,the biochar (BC) produced from sawdust,sludge,reed and walnut were used to support sulfidation of nano-zero-valent-iron (S-nZVI) to enhance nitrate NO_(3)^(-) removal and investigate the impact on greenhouse gas emissions.Batch experiment results showed the S-nZVI/BC(sawdust (2:1,500)),S-n ZVI/BC(sludge (2:1,900)),S-n ZVI/BC(reed (2:1,700)),and S-n ZVI/BC(walnut (2:1,700))respectively improved NO_(3)^(-) removal efficiencies by 22%,20%,3%and0.1%,and the selectivity toward N_(2)by 22%,25%,22%and 18%.S-nZVI uniformly loaded on BC provided electrons for the conversion of NO_(3)^(-) to N_(2)through Fe0.At the same time,FeSxlayer was formed on the outer layer of ZVI in the sulfidation process to prevent iron oxidation,so as to improve the electrons utilization efficiency After adding four kinds of S-nZVI/BC into constructed wetlands (CWs),the NO_(3)^(-) removal efficiencies could reach 100%and the N_(2)O emission fluxes were reduced by 24.17%-36.63%.And the average removal efficiencies of TN,COD,TP were increased by 21.9%,-16.5%,44.3%,repectively.The increasing relative abundances of denitrifying bacteria,such as Comamonas and Simplicispira,suggested that S-nZVI/BC could also improve the process of microbial denitrification.In addition,different S-nZVI/BC had different effects on denitrification functional genes (narG,nirk,nirS and nos Z genes),methanotrophs (pmoA) and methanogenesis (mcrA).This research provided an effective method to improve NO_(3)^(-) removal and reduce N_(2)O emission in CWs.

Hydrogen sulfide-linked persulfidation of ABI4 controls ABA responses through the transactivation of MAPKKK18 in Arabidopsis

Hydrogen sulfide(H2S)is a signaling molecule that regulates plant hormone and stress responses.The phytohormone abscisic acid(ABA)plays an important role in plant adaptation to unfavorable environmental conditions and induces the persulfidation of L-CYSTEINE DESULFHYDRASE1(DES1)and the production of H2S in guard cells.However,it remains largely unclear how H2S and protein persulfidation participate in the relay of ABA signals.In this study,we discovered that ABSCISIC ACID INSENSITIVE 4(ABI4)acts downstream of DES1 in the control of ABA responses in Arabidopsis.ABI4 undergoes persulfidation at Cys250 that is triggered in a time-dependent manner by ABA,and loss of DES1 function impairs this process.Cys250 and its persulfidation are essential for ABI4 function in the regulation of plant responses to ABA and the H2S donor NaHS during germination,seedling establishment,and stomatal closure,which are abolished in the ABI4Cys250Ala mutated variant.Introduction of the ABI4Cys250Ala variant into the abi4 des1 mutant did not rescue its hyposensitivity to ABA.Cys250 is critical for the binding of ABI4 to its cognate motif in the promoter of Mitogen-Activated Protein Kinase Kinase Kinase 18(MAPKKK18),which propagates the MAPK signaling cascade induced by ABA.Furthermore,the DES1-mediated persulfidation of ABI4 enhances the transactivation activity of ABI4 toward MAPKKK18,and ABI4 can bind the DES1 promoter,forming a regulatory loop.Taken together,these findings advance our understanding of a post-translational regulatory mechanism and suggest that ABI4 functions as an integrator of ABA and MAPK signals through a process in which DES1-produced H2S persulfidates ABI4 at Cys250.