Improvement of hydrogen permeation barrier performance by iron sulphide surface films

Fe–S compounds with hexagonal crystal structure are potential hydrogen permeation barrier during H2S corrosion. Hexagonal system Fe–S films were prepared on carbon steel through corrosion and CVD deposition, and the barrier effect of different Fe–S films on hydrogen permeation was tested using electrochemical hydrogen permeation method. After that, the electrical properties of Fe–S compound during phase transformation were measured using thermoelectric measurement system. Results show that the mackinawite has no obvious barrier effect on hydrogen penetration, as a p-type semiconductor, and pyrrhotite (including troilite) has obvious barrier effect on hydrogen penetration,as an n-type semiconductor. Hydrogen permeation tests showed peak permeation performance when the surface was deposited with a continuous film of pyrrhotite (Fe_(1–x)S) and troilite. The FeS compounds suppressed hydrogen permeation by the promotion of the hydrogen evolution reaction, semiconducting inversion from p-to n-type, and the migration of ions at the interface.

Generation process of FeS and its inhibition mechanism on iron mineral reduction in selective direct reduction of laterite nickel ore

Numerous studies have demonstrated that Na2SO4 can significantly inhibit the reduction of iron oxide in the selective reduction process of laterite nickel ore. FeS generated in the process plays an important role in selective reduction, but the generation process of FeS and its inhibition mechanism on iron reduction are not clear. To figure this out, X-ray diffraction and scanning electron microscopy analyses were conducted to study the roasted ore. The results show that when Na2SO4 is added in the roasting, the FeO content in the roasted ore increases accompanied by the emergence of FeS phase. Further analysis indicates that NaeS formed by the reaction of Na2SO4 with CO reacts with SiO2 at the FeO surface to generate FeS and Na2Si2Os. As a result, a thin film forms on the surface of FeO, hindering the contact between reducing gas and FeO. Therefore, the reduction of iron is depressed, and the FeO content in the roasted ore increases.

Simultaneous removal of Cr(Ⅵ), Cd, and Pb from aqueous solution by iron sulfide nanoparticles: Influencing factors and interactions of metals

Cadmium(Cd),lead(Pb),and hexavalent chromium(Cr(Ⅵ)) are often found in soils and water affected by metal smelting,chemical manufacturing,and electroplating.In this study,synthetic iron sulfide nanoparticles(FeS NPs) were stabilized with carboxymethyl cellulose(CMC) and utilized to remove Cr(Ⅵ),Cd,and Pb from an aqueous solution.Batch experiments,a Visual MINTEQ model,scanning electron microscopy(SEM),X-ray diffraction(XRD),and X-ray photoelectron spectrometer(XPS) analysis were used to determine the removal efficiencies,influencing factors,and mechanisms.The FeS NP suspension simultaneously removed Cr(Ⅵ),Cd,and Pb from an aqueous solution.The concentrations of Cr(Ⅵ),Cd,and Pb decreased from 50,10,and 50 mg·L^(-1) to 2.5,0.1,and 0.1 mg·L^(-1),respectively.The removal capacities were up to 418,96,and 585 mg per gram of stabilized FeS NPs,respectively.The acidic conditions significantly favored the removal of aqueous Cr(Ⅵ) while the alkaline conditions favored the removal of Cd and Pb.Oxygen slightly inhibited the removal of Cr(Ⅵ),but it had no significant influence on the removal of Cd and Pb.A potential mechanism was proposed for the simultaneous removal of Cr(Ⅵ),Cd,and Pb using FeS NPs.The interactions of the three heavy metals involved a cationic bridging effect on Cr(Ⅵ) by Cd,an enhanced adsorption effect on Cd by [Cr,Fe](OH)_3,precipitation of PbCrO_4,and transformation of PbCrO_4 to PbS.Therefore,FeS NPs have a high potential for use in the simultaneous removal of Cr(Ⅵ),Cd,and Pb from contaminated aqueous solutions.

Formation of Iron Sulfide in Water-Body Sediment and Its Influence on Environment

Iron sulfide is an important reductive pollutant in aquatic sediment,so that increasing attentions have been paid to it in recent years.In this paper,the formation of iron sulfide in water-body sediment was introduced.Moreover,its adverse influences upon environment were summarized,including direct contribution to deficiency of dissolved oxygen in water,association with eutrophication in water-bodies and impact on geochemical sulfur cycle.Since conventional chemical analysis for iron sulfide has several disadvantages,new technique for rapid determination of iron sulfide on-line was prospected.

Interface Engineering of Fe_(7)S_(8)/FeS_(2) Heterostructure in situ Encapsulated into Nitrogen‑Doped Carbon Nanotubes for High Power Sodium‑Ion Batteries

Heterostructure engineering combined with carbonaceous materials shows great promise toward promoting sluggish kinetics,improving electronic conductivity,and mitigating the huge expansion of transition metal sulfide electrodes for high-performance sodium storage.Herein,the iron sulfide-based heterostructures in situ hybridized with nitrogen-doped carbon nanotubes(Fe_(7)S_(8)/FeS_(2)/NCNT)have been prepared through a successive pyrolysis and sulfidation approach.The Fe_(7)S_(8)/FeS_(2)/NCNT heterostructure delivered a high reversible capacity of 403.2 mAh g^(−1) up to 100 cycles at 1.0 A g^(−1) and superior rate capability(273.4 mAh g^(−1) at 20.0 A g^(−1))in ester-based electrolyte.Meanwhile,the electrodes also demonstrated long-term cycling stability(466.7 mAh g^(−1) after 1,000 cycles at 5.0 A g^(−1))and outstanding rate capability(536.5 mAh g^(−1) at 20.0 A g^(−1))in ether-based electrolyte.This outstanding performance could be mainly attributed to the fast sodium-ion diffusion kinetics,high capacitive contribution,and convenient interfacial dynamics in ether-based electrolyte.

The Contact Interface Engineering of All-Sulfide-Based Solid State Batteries via Infiltrating Dissoluble Sulfide Electrolyte

All-solid-state lithium batteries(ASSLBs)based on sulfide solid electrolytes(SEs)are one of the most promising strategies for next-generation energy storage systems and electronic devices.However,the poor chemical/electrochemical stability of sulfide SEs with oxide cathode materials and high interfacial impedance,particularly due to physical contact failure,are the major limiting factors to the development of sulfide SEs in ASSLBs.Herein,the composite cathode of MOF-derived Fe_(7)S_(8)@C and Li_(6)PS_(5)Br fabricated by an infiltration method(IN-Fe_(7)S_(8))with dissoluble sulfide electrolyte(dissoluble SE)is reported.Dissoluble SE can easily infiltrate the porous sheet-type Fe_(7)S_(8)@C cathode to homogeneously contact with Fe_(7)S_(8)nanoparticles that are embedded in the surrounding carbon matrixes and form a fast ionic transport network.Benefiting from applying dissoluble SE and Fe_(7)S_(8)@C,the IN-Fe_(7)S_(8)-based cells displayed a reversible capacity of 510 mAh g^(-1)after 180 cycles at 0.045 mA cm^(-2)at 30℃.This work demonstrates a novel and practical method for the development of high-performance all-sulfide-based solid state batteries.

First-principle calculations of interaction of O_2 with pyrite, marcasite and pyrrhotite surfaces

The interaction of O2 with pyrite, marcasite and pyrrhotite surfaces was studied using first-principle calculations to obtain the oxidization mechanisms of these minerals. The results show that the adsorption energy of O2 on pyrrhotite surface is the largest, followed by that on marcasite surface and then pyrite surface. O2 molecules adsorbed on pyrite, marcasite and pyrrhotite surfaces are all dissociated. The oxygen atoms and surface atoms of pyrite, marcasite and pyrrhotite surfaces have different bonding structures. Due to more atoms on pyrrhotite and marcasite surfaces interaction with oxygen atoms, the adsorption energies of O2 on pyrrhotite and marcasite surfaces are larger than that on pyrite surface. Larger values of Mulliken populations for O？Fe bond of pyrrhotite surface result in relative larger adsorption energy compared with that on marcasite surface.

Low-cost solid FeS lubricant as a possible alternative to MoS2 for producing Fe-based friction materials

Three reaction systems of MoS_2-Fe, FeS -Fe, and Fe S-Fe-Mo were designed to investigate the use of FeS as an alternative to MoS_2 for producing Fe-based friction materials. Samples were prepared by powder metallurgy, and their phase compositions, microstructures, mechanical properties, and friction performance were characterized. The results showed that MoS_2 reacts with the matrix to produce iron-sulfides and Mo when sintered at 1050°C. Iron-sulfides produced in the MoS_2-Fe system were distributed uniformly and continuously in the matrix, leading to optimal mechanical properties and the lowest coefficient of friction among the systems studied. The lubricity observed was hypothesized to originate from the iron-sulfides produced. The Fe S-Fe-Mo system showed a phase composition, porosity, and density similar to those of the MoS_2-Fe system, but an uneven distribution of iron-sulfides and Mo in this system resulted in less-optimal mechanical properties. Finally, the Fe S-Fe system showed the poorest mechanical properties among the systems studied because of the lack of Mo reinforcement. In friction tests, the formation of a sulfide layer contributed to a decrease in coefficient of friction（COF） in all of the samples.

Highly active Fe_(7)S_(8) encapsulated in N-doped hollow carbon nanofibers for high-rate sodium-ion batteries

Nanostructured iron sulfides are regarded as a potential anode material for sodium-ion batteries in virtue of the rich natural abundance and remarkable theoretical capacity.However,poor rate performance and inferior cycling stability caused by sluggish kinetics and volume swelling represent two main obstacles at present. The previous research mainly focuses on nanostructure design and/or hybridizing with conductive materials.Further boosting the property by adjusting Fe/S atomic ratio in iron sulfides is rarely reported.In this work,Fe_7 S_8 and FeS_2 encapsulated in N-doped hollow carbon fibers(NHCFs/Fe_7 S_8 and NHCFs/FeS_2) are constructed by a combined chemical bath deposition and subsequent sulfidation treatment.The well-designed NHCFs/Fe_(7) S_(8) electrode displays a remarkable capacity of 517 mAh g^(-1) at 2 A g^(-1)after 1000 cycles and a superb rate capability with a capability of 444 mAh g^(-1) even at 20 A g^(-1) in etherbased electrolyte.Additionally,the rate capability of NHCFs/Fe_(7) S_(8) is superior to that of the contrast NHCFs/FeS_(2) electrode and also much better than the values of the most previously reported iron sulfide-based anodes.The in-depth mechanism explanation is explained by further experimental analysis and theoretical calculation,revealing Fe_(7) S_(8) displays improved intrinsic electronic conductivity and faster Na^(+) diffusion coefficient as well as higher reaction reversibility.

Design of pyrite/carbon nanospheres as high-capacity cathode for lithium-ion batteries

Transition metal sulfides are emerging as promising electrode materials for energy storage and conversion.In this work,hierarchical FeS2/C nanospheres are synthesized through a controllable solvothermal method followed by the annealing process.Spherical FeS2 core is homogeneously coated by thin carbon shell.The hierarchical nanostructure and carbon coating can enhance electron transfer and accommodate the stress originated from the volume change as well as suppress the shuttle effect of polysulfide.Consequently,as the cathode material of lithium ion batteries(LIBs),the FeS2/C nanospheres exhibit high reversible capacity of 676 m Ahg^-1 and excellent cycling life with the capacity retention of 97.1%after100 cycles.In addition,even at the high current density of 1.8 C,a reversible capacity of 437 m Ahg^-1 is obtained for the FeS2/C nanospheres,demonstrating its great prospect for practical applications in highperformance LIBs.

Photocatalytic degradation of methylene blue by nanostructured Fe/FeS powder under visible light

The photocatalytic performance of mechano-thermally synthesized Fe/FeS nanostructures formed from micron-sized starting materials was compared with that of a thermally synthesized nanostructure with nano-sized precursors in this paper. The properties of as-synthesized materials were studied by X-ray diffraction（XRD）, transmission electron microscopy（TEM）, vibrating sample magnetometry（VSM）, diffuse reflectance spectroscopy（DRS）, and ultraviolet–visible（UV-Vis） spectroscopy. The effects of irradiation time, methylene blue（MB） concentration, catalyst dosage, and p H value upon the degradation of MB were studied. Magnetic properties of the samples showed that both as-synthesized Fe/FeS photocatalysts are magnetically recoverable, eliminating the need for conventional filtration steps. Degradation of 5 ppm of the MB solution by mechano-thermally synthesized Fe/FeS with a photocatalyst dosage of 1 kg/m^3 at pH 11 can reach 96% after 12 ks irradiation under visible light. The photocatalytic efficiency is higher in alkaline solution. The kinetics of photocatalytic degradation in both samples is controlled by a first-order reaction. However, the rate-constant value in the thermally synthesized Fe/FeS photocatalyst sample is only 1.5 times greater than that of the mechano-thermally synthesized one.

All-Climate Aluminum-Ion Batteries Based on Binder-Free MOF-Derived FeS_(2)@C/CNT Cathode

Aluminum-ion batteries(AIBs)are promising next-generation batteries systems because of their features of low cost and abundant aluminum resource.However,the inferior rate capacity and poor all-climate performance,especially the decayed capacity under low temperature,are still critical challenges toward high-specific-capacity AIBs.Herein,we report a binder-free and freestanding metal-organic framework-derived FeS_(2)@C/carbon nanotube(FeS_(2)@C/CNT)as a novel all-climate cathode in AIBs working under a wide temperature window between−25 and 50℃ with exceptional flexibility.The resultant cathode not only drastically suppresses the side reaction and volu-metric expansion with high capacity and long-term stability but also greatly enhances the kinetic process in AIBs with remarkable rate capacity(above 151 mAh g^(−1) at 2 A g^(−1))at room temperature.More importantly,to break the bottleneck of the inherently low capacity in graphitic material-based all-climate AIBs,the new hierarchical conductive composite FeS_(2)@C/CNT highly promotes the all-climate performance and delivers as high as 117 mAh g^(−1) capacity even under−25°C.The well-designed metal sulfide electrode with remarkable performance paves a new way toward all-climate and flexible AIBs.

Theoretical Study on the Reaction of FeS^+(~6Σ^+,~4Ф) with COS in the Gas Phase

The possible reaction mechanisms of FeS＋（6Σ＋ and 4Ф states） with COS in the gas phase have been studied by using density functional theory at the B3LYP/TZVP and B3LYP/6-311＋G＊ levels：the O/S exchange reaction（FeS＋ ＋ COS=FeO＋ ＋ CS2）,O-transfer reaction（FeS＋ ＋ COS=FeSO＋ ＋ CS） and S-transfer reaction（FeS＋ ＋ COS=FeS2＋ ＋ CO）.The calculation results show that the large barriers（205.7 and 310.1 kJ/mol） and the small probability of forming the preceding intermediate indicate a much lower efficiency of the O/S exchange and the O-transfer reactions and their corresponding products may not be observed experimentally.FeS2＋,the product of S-transfer reaction,is predicted to be the main product.But the reactivity of the 6Σ＋ ground state of FeS＋ toward COS is lower than the earlier transition metal sulfide cations MS＋（M=Sc,Ti and V）,although it has more reaction channels and different mechanisms.

A multiphase nickel iron sulfide hybrid electrode for highly active oxygen evolution

Development of highly active electrocatalysts for oxygen evolution reaction(OER)is one of the critical issues for water splitting,and most reported catalysts operate at overpotentials above 190 mV.Here we present a multiphase nickel iron sulfide(MPS)hybrid electrode with a hierarchical structure of iron doped NiS and Ni3S2,possessing a benchmark OER activity in alkaline media with a potential as low as 1.33 V(vs.reversible hydrogen electrode)to drive an OER current density of 10 mA cm^-2.The Fe doped NiS,combined with highly conductive disulfide phase on porous Ni foam,is believed to be responsible for the ultrahigh activity.Furthermore,density functional theory simulation reveals that partially oxidized sulfur sites in Fe doped NiS could dramatically lower the energy barrier for the rate-determining elementary reaction,thus contributing to the active oxygen evolution.

Solvent-free Synthesis of Hexagonal Iron Sulfide Nanoflowers

Employing green and economic solvent-free synthesis route, hexagonal iron sulfide （Fe7Ss） nanoflowers were successfully synthesized for the first time. In the experiment, ferric hexadecylxanthate was used as the precursor, and hexagonal iron sulfide （Fe7Ss） nanoflowers were obtained by thermal decomposition of the precursor at 260 ~C without any additional solvent or inert gas protection. The as-prepared iron sulfide nanoflowers were characterized by means of X-ray diffraction （XRD）, transmission electron microscopy （TEM）, scanning electron microscopy （SEM） and energy dispersive spectrometry （EDS）. The characterization results indicated that the nanoflowers had uniform size distribution with an average size of about 160 rim. The proposed strategy provides a possible general route for the synthesis of other metal chalcogenide nanostructures.

Hierarchical graphene@MXene composite foam modified with flower-shaped FeS for efficient and broadband electromagnetic absorption

Developing high-performance broadband microwave absorption material becomes an urgent concern in the field of electromagnetic protection.In this work,an ultralight magnetic composite foam was con-structed by electrostatic self-assembly of MXene on the surface of graphene skeletons,and subsequent hydrothermal anchoring of flower-shaped FeS clusters.Under the synergistic effect of MXene coating in-creasing conductive loss and FeS clusters improving magnetic loss,the rational construction of hierarchi-cal impedance structure in foam can effectively promote the entrance and consumption of more incident electromagnetic waves.The minimum reflection loss(RL min)reaches-47.17 dB at a thickness of 4.78 mm,and the corresponding effective absorption bandwidth(EAB)is up to 6.15 GHz.More importantly,the microwave absorption performance of composite foam can be further optimized by controlling the load-ing of MXene and thermal treatment at a low temperature.The maximum of EAB for GMF-300 can be extended to an unprecedented value of 11.20 GHz(covering 6.10-17.30 GHz).

Electrospinning with sulfur powder to prepare CNF@G-Fe_(9)S_(10) nanofibers with controllable particles distribution for stable potassium-ion storage

As anode materials of electrochemical energy storage system,metal sulfides with high theoretical capacities suffer from issues of materials smashing and deactivation due to huge volume change,resulting in the inferior cycle stability.In this paper,a new strategy of adding sulfur powder into the electrospinning precursor instead of employing sulfur powder during the sulfurizing treatment is proposed to prepare Fe_(9)S_(10)composites(CNF@G-Fe_(9)S_(10)-1).In those composites,most of Fe_(9)S_(10)particles are embedded in the graphene-carbon fibers with multiple protection.As anodes for potassium-ion batteries,CNF@G-Fe_(9)S_(10)-1 display higher rate capacities and more excellent stability(103.2 mAh·g^(-1)at 1000 mA·g^(-1)after 892 cycles)than Fe_(9)S_(10)composites synthesized by the traditional method.In addition,as anodes for potassiumion hybrid capacitors,they also deliver high capacities of102.8 mAh·g^(-1)at 1000 mA·g^(-1)after 100 cycles.The morphology characterization evidences indicate that the surface and integrity of CNF@G-Fe_(9)S_(10)-1 are more smooth and complete than the Fe_(9)S_(10)composites fabricated using a common method without sulfur power in electrospinning precursor.The excellent stability and high capacity of CNF@G-Fe_(9)S_(10)-1 can be attributed to nearly full-wrapped structure of Fe_(9)S_(10)in the carbon matrix arising from the new strategy.Owing to the formation of the structure,Fe_(9)S_(10)particles are protected from the pulverization,and the structure stability of hybrid carbon fibers is enhanced.This study may provide a new strategy for the controllable synthesis of metal sulfide-CNFs and their application for high stability energy storage.

Porous FeS nanofibers with numerous nanovoids obtained by Kirkendall diffusion effect for use as anode materials for sodium-ion batteries

Porous FeS nanofibers with numerous nanovoids for use as anode materials for sodium-ion batteries were prepared by electrospinning and subsequent sulfidation. The post-treatment of the as-spun Fe（acac）3-polyacrylonitrile composite nanofibers in an air atmosphere yielded hollow Fe2O3 nanofibers due to Ostwald ripening. The ultrafine Fe2O3 nanocrystals formed at the center of the fiber diffused toward the outside of the fiber via Ostwald ripening. On sulfidation, the Fe2O3 hollow nanofibers were transformed into porous FeS nanofibers, which contained numerous nanovoids. The formation of porosity in the FeS nanofibers was driven by nanoscale Kirkendall diffusion. The porous FeS nanofibers were very structurally stable and had superior sodium-ion storage properties compared with the hollow Fe2O3 nanofibers. The discharge capacities of the porous FeS nanofibers for the Ist and 150th cycles at a current density of 500 mA.g-1 were 561 and 592 mA.h-g-1, respectively. The FeS nanofibers had final discharge capacities of 456, 437, 413, 394, 380, and 353 mA-h.g-1 at current densities of 0.2, 0.5, 1.0, 2.0, 3.0, and 5.0 A.g-1, respectively.

Corrosion Behavior of X52 Anti-H_2S Pipeline Steel Exposed to High H_2S Concentration Solutions at 90℃

Initial corrosion kinetics of X52 anti-H2S pipeline steel exposed to 90 ℃/1.61 MPa H2S solutions was investigated through high temperature and high pressure immersion tests. Corrosion rates were obtained based on weight loss calculation. The corrosion products were analyzed by scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, X-ray diffraction （XRD） and electron probe micro-analysis （EPMA）. The initial corrosion kinetics was found to obey the exponential law. With increasing immersion time, the main corrosion products changed from iron-rich mackinawite to sulfur-rich pyrrhotite. The corrosion films had two layers： an inner fine-grained layer rich in iron and an outer columnar-grained layer rich in sulfur. The corrosion film formed through the combination of outward diffusion of Fe2＋ ions and inward diffusion of HS^- ions. The variation of the corrosion products and compaction of the corrosion layer resulted in a decrease in the diffusion coefficient with increasing immersion time. The double-layered corrosion film formed after long time immersion acted as an effective barrier against diffusion.

Sandwich structured graphene-wrapped FeS-graphene nanoribbons with improved cycling stability for lithium ion batteries

Sandwich structured graphene-wrapped FeS-graphene nanoribbons （G@FeS-GNIKs） were developed. In this composite, FeS nanoparticles were sandwiched between graphene and graphene nanoribbons. When used as anodes in lithium ion batteries （L1Bs）, the G@FeS-GNR composite demonstrated an outstanding electrochemical performance. This composite showed high reversible capacity, good rate performance, and enhanced cycling stability owing to the synergy between the electrically conductive graphene, graphene nanoribbons, and FeS. The design concept developed here opens up a new avenue for constructing anodes with improved electrochemical stability for LIBs.