Designing visible light photocatalysts with a metal oxide semiconductor as the starting material could expand a new horizon for the conversion and storage of solar energy.Here,the benchmark photocatalyst TiO_(2) was u...Designing visible light photocatalysts with a metal oxide semiconductor as the starting material could expand a new horizon for the conversion and storage of solar energy.Here,the benchmark photocatalyst TiO_(2) was used to pursue this goal by anchoring aromatic acids.Extending the aromatic acid was strategically deployed to design TiO_(2) complexes with violet light-induced selective aerobic oxidation of sulfide as the probe reaction.With benzoic acid(BA)as the initial molecule,horizontally extending one or two benzene rings furnishes 2-naphthoic acid(2-NA)and 2-anthracene acid(2-AA).Moreover,triethylamine(TEA),an electron transfer mediator,was introduced to maintain the integrity of the anchored aromatic acids.Notably,there was a direct correlation between theπ-conjugation of aromatic acid ligand and the selective aerobic oxidation of sulfides.Among the three aromatic acids,2-AA delivered the best result over TiO_(2) due to the most extensiveπ-conjugated system.Ultimately,violet light-induced selective aerobic oxidation of sulfides into corresponding sulfoxides was conveniently realized by cooperative photocatalysis of 2-AA-TiO_(2) with 10 mol%of TEA.This work affords an extending strategy for designing the next-generation ligands for semiconductors to expand visible light-induced selective reactions.展开更多
A novel imidazole-functionalized dioxovanadium complex [V2O2（C2O4）（aIM）4] （aIM =1-allylimidazole） was synthesized by the reaction of VO（acac）2 with 1-allylimidazole and fully characterized by single-crystal X-...A novel imidazole-functionalized dioxovanadium complex [V2O2（C2O4）（aIM）4] （aIM =1-allylimidazole） was synthesized by the reaction of VO（acac）2 with 1-allylimidazole and fully characterized by single-crystal X-ray diffraction （SCXRD）,powder X-ray diffraction （PXRD）,X-ray photoelectron spectroscopy （XPS）,Fourier transform infrared spectroscopy （FT-IR） and elemental analyses.Interestingly,the oxalate was in-situ generated from the acetylacetone anion of VO（acac）2 and further coordinated with the vanadium cation and finally complex 1 was achieved.The crystal of complex 1 belongs to the monoclinic system,space group P21/n with a =10.7922（9）,b =10.6296（8）,c =13.2936（11） （A）,μ =0.677 mm^-1,Mr =686.48,V =1516.9（2） A^3,Z =2,Dc =1.503 g/cm^3,F（000） =708,R =0.0543,and wR =0.1517 for 2459 observed reflections with Ⅰ 〉 2σ（Ⅰ）.Notably,complex 1 is further used as catalyst in the oxidation of sulfides using H2O2 as the oxidant and exhibits excellent catalytic performance （conv.up to 95.6%,sele.up to 98.9%）.展开更多
Metal-organic frameworks(MOFs)with new topologies and enhanced properties can be obtained by connecting metal-organic layers(MOLs)using multifunctional linkers.However,new topologies constructed by this method using l...Metal-organic frameworks(MOFs)with new topologies and enhanced properties can be obtained by connecting metal-organic layers(MOLs)using multifunctional linkers.However,new topologies constructed by this method using linear-shaped ligands have not yet been explored.Herein,we present the design of NUT-123 by incorporating a near-linear perylene diimide(PDI)derivate,PDI-CH_(3)-COOH,into the preselected zirconium-based MOLs.3D electron diffraction confirms the successful construction of a novel topology in NUT-123.Furthermore,the uniformly dispersed PDI groups within the structure confer enhance photocatalytic capability while effectively circumventing the self-aggregation of PDI-CH_(3)-COOH.NUT-123 exhibits enhanced efficiency and selectivity in sulfide oxidation and demonstrates excellent substrate compatibility,achieving 100%conversion of various organic sulfides.Mechanistic studies indicate that the formation of sulfoxides is facilitated by concurrent electron and energy transfer.This work fills the gap in constructing a new topology by connecting MOLs with linear-shaped linkers and provides a photocatalyst for selective sulfide oxidation.展开更多
Zirconium-based metal-organic cages(Zr-MOCs)typically exhibit high stability,but their structural and application reports are scarce due to stringent crystallization conditions.We have successfully fluorinated the cla...Zirconium-based metal-organic cages(Zr-MOCs)typically exhibit high stability,but their structural and application reports are scarce due to stringent crystallization conditions.We have successfully fluorinated the classical Zr-MOCs(ZrT-3)for the first time,obtaining the fluorinated MOCs(ZrT-3-F).Notably,ZrT-3-F not only inherits the high stability of its parent structure,but also acts as a catalyst for the effective oxidation of benzyl thioether for the first time.The reaction can reach a conversion rate of 99%in 6 h,and the selectivity reaches 95%,which far exceeds the non-fluorinated ZrT-3.This work proves that the specific functionalization of the classical Zr-MOCs can further expand their application potential,such as catalysis.展开更多
The environmental threat posed by stibnite is an important geoenvironmental issue of current concern.To better understand stibnite oxidation pathways,aerobic abiotic batch experiments were conducted in aqueous solutio...The environmental threat posed by stibnite is an important geoenvironmental issue of current concern.To better understand stibnite oxidation pathways,aerobic abiotic batch experiments were conducted in aqueous solution with varyingδ^(18)O_(H_(2)O) value at initial neutral pH for different lengths of time(15-300 days).The sulfate oxygen and sulfur isotope compositions as well as concentrations of sulfur and antimony species were determined.The sulfur isotope fractionation factor(△^(34)S_(SO4-stibnite))values decreased from 0.8‰to-2.1‰during the first 90 days,and increased to 2.6‰at the 180 days,indicating the dominated intermediate sulfur species such as S_(2)O_(3)^(2-),S0,and H_(2)S(g)involved in Sb2S3 oxidation processes.The incorporation of O into sulfate derived from O_(2)(~100%)indicated that the dissociated O_(2)was only directly adsorbed on the stibnite-S sites in the initial stage(0-90 days).The proportion of O incorporation into sulfate from water(27%-52%)increased in the late stage(90-300 days),which suggested the oxidation mechanism changed to hydroxyl attack on stibnite-S sites promoted by nearby adsorbed O_(2)on stibnite-Sb sites.The exchange of oxygen between sulfite and water may also contributed to the increase of water derived O into SO42-.The new insight of stibnite oxidation pathway contributes to the understanding of sulfide oxidation mechanism and helps to interpret field data.展开更多
The recovery of heterogeneous catalysts can save costs and avoid secondary pollution,but its separation efficiency and recovery cost are limited by conventional separation methods such as precipitation–flocculation,c...The recovery of heterogeneous catalysts can save costs and avoid secondary pollution,but its separation efficiency and recovery cost are limited by conventional separation methods such as precipitation–flocculation,centrifugation and filtration.In this paper,we found that surface-defective metal sulfides/oxides(WS2,CuS,ZnS,MoS2,CdS,TiO2,MoO2 and ZnO)commonly used in advanced oxidation processes(AOPs)could be magnetically recovered at room temperature and atmospheric pressure by mechanically mixing with Fe3O4.Zeta potential,Raman,X-ray photoelectron spectroscopy(XPS)and electro-spin resonance(ESR)spectra were measured to explore the mechanism of the magnetic separation phenomenon.The exposed active metal sites on the surface of defective metal sulfides/oxides are beneficial for the formation of chemical bonds,which are combined with electrostatic force to be responsible for the magnetic separation.Moreover,other factors affecting the magnetic separation were also investigated,such as the addition of amount of Fe3O4,different solvents and particle sizes.Finally,WS2 was chosen to be applied as a co-catalyst in Fenton reaction,which could be well separated by the magnetic Fe3O4 to achieve the recycle of catalyst in Fenton reaction.Our research provides a general strategy for the recycle of metal sulfides/oxides in the catalytic applications.展开更多
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 press...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.展开更多
The sulfur-containing odor emitted from sludge composting could be controlled by sulfide oxidizing bacteria, yet mesophilic strains show inactivation during the thermophilic stage of composting. Aimed to investigate a...The sulfur-containing odor emitted from sludge composting could be controlled by sulfide oxidizing bacteria, yet mesophilic strains show inactivation during the thermophilic stage of composting. Aimed to investigate and characterize the thermotolerant bacterium that could oxidize sulfide into sulfate, a heterotrophic strain was isolated from sewage sludge composting and identified as Paenibacillus naphthalenovorans LYH-3. The effects of various environmental factors on sulfide oxidation capacities were studied to optimize the sulfate production, and the highest production rate (27.35%±0.86%) was obtained at pH 7.34, the rotation speed of 161.14 r/min, and the inoculation amount of 5.83%by employing BoxBehnken design. The results of serial sulfide substrates experiments indicated that strain LYH-3 could survive up to 400 mg/L of sulfide with the highest sulfide removal rate (88.79%±0.35%) obtained at 50 mg/L of sulfide. Growth kinetic analysis presented the maximum specific growth rateμm(0.5274 hr-1) after 22 hr cultivation at 50℃. The highest enzyme activities of sulfide quinone oxidoreductase (0.369±0.052 U/mg) and sulfur dioxygenase (0.255±0.014 U/mg) were both obtained at 40℃, and the highest enzyme activity of sulfite acceptor oxidoreductase (1.302±0.035 U/mg) was assessed at 50℃. The results indicated that P. naphthalenovorans possessed a rapid growth rate and efficient sulfide oxidation capacities under thermophilic conditions, promising a potential application in controlling sulfur-containing odors during the thermophilic stage of sludge composting.展开更多
A continuous fluidized bed bioreactor （FBBR） with nylon support particles was used to treat synthetic sulfide wastewater at different hydraulic retention time of 25, 50 and 75 min and upflow velocity of 14, 17 and 2...A continuous fluidized bed bioreactor （FBBR） with nylon support particles was used to treat synthetic sulfide wastewater at different hydraulic retention time of 25, 50 and 75 min and upflow velocity of 14, 17 and 20 m/hr. The effects of upflow velocity, hydraulic retention time and reactor operation time on sulfide oxidation rate were studied using statistical model. Mixed culture obtained from the activated sludge, taken from tannery effluent treatment plant, was used as a source for microorganisms. The diameter and density of the nylon particles were 2-3 mm and 1140 kg/m3, respectively. Experiments were carried out in the reactor at a temperature of （30 ± 2）°C, at a fixed bed height of 16 cm after the formation of biofilm on the surface of support particles. Biofilm thickness reached （42 ± 3） μm after 15 days from reactor start-up. The sulfide oxidation, sulfate and sulfur formation is examined at all hydraulic retention times and upflow velocities. The results indicated that almost 90%-92% sulfide oxidation was achieved at all hydraulic retention times. Statistical model could explain 94% of the variability and analysis of variance showed that upflow velocity and hydraulic retention time slightly affected the sulfide oxidation rate. The highest sulfide oxidation of 92% with 70% sulfur was obtained at hydraulic retention time of 75 min and upflow velocity of 14 m/hr.展开更多
The influence of the textural and acidic properties ofγ‐Al2O3,(γ+χ)‐Al2O3,and?‐Al2O3on the catalytic activity,selectivity,and stability of direct H2S oxidation has been studied.A comparison of the H2S‐to‐S con...The influence of the textural and acidic properties ofγ‐Al2O3,(γ+χ)‐Al2O3,and?‐Al2O3on the catalytic activity,selectivity,and stability of direct H2S oxidation has been studied.A comparison of the H2S‐to‐S conversion effectiveness of aluminas with their acidic properties(identified by Fourier transform infrared spectroscopy and temperature programmed desorption of NH3)shows that H2S adsorption occurs predominantly on weak Lewis acid sites(LAS).γ‐Alumina samples containing aχ‐phase and/or modified Mg2+ions have a greater concentration of weak LAS and exhibit greater catalytic activity.When alumina is treated with a sulfuric acid solution,strong LAS appear and the number of LAS decreases significantly.Modification of alumina with hydrochloric acid has a limited effect on LAS strength.Weak LAS are retained and double in number compared to that present in the unmodified alumina,but the treated sample has Al?Cl bonds.Alumina samples modified by sulfate and chloride anions exhibit poor catalytic activity in H2S oxidation.展开更多
Covalent organic frameworks(COFs)based photocatalysts utilizing infrared light remains unexplored due to the limitation of electronic absorption.Herein,two novel two-dimensional(2D)polyimide-linked phthalocyanine COFs...Covalent organic frameworks(COFs)based photocatalysts utilizing infrared light remains unexplored due to the limitation of electronic absorption.Herein,two novel two-dimensional(2D)polyimide-linked phthalocyanine COFs,namely MPc-DPA-COFs(M=Zn/Cu),were prepared from the imidization reaction of metal tetraanhydrides of 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato(M(TAPc))with 9,10-diphenyl anthracene(DPA).Both COFs possess highly crystalline eclipsed AA stacking structure with neighboring layer distance of 0.33 nm on the basis of powder X-ray diffraction analysis and high-resolution transmission electron microscopy.Effective π–π interaction between phthalocyanine chromophores in neighboring layers of 2D COFs leads to significant bathochromic-shift of narrow Q band from 697 nm for M(TAPc)to the infrared light absorption range of 760–1000 nm for MPc-DPA-COFs according to solid UV-vis diffuse reflectance spectra.This endows them in particular ZnPc-DPA-COF with excellent reactive oxygen species of•O_(2)^(–)and 1O_(2) generation activity under infrared light radiation(λ>760 nm)based on the electron spin resonance spectroscopy measurement,in turn resulting in the excellent photocatalytic capacity towards oxidation of sulfides under infrared light radiation.Corresponding quenching experiments reveal the contribution of both•O_(2)^(–)and 1O_(2) to the oxidation of sulfides,but the former•O_(2)^(–)species plays a leading role in this photocatalytic process.The present result not only provides a new efficient infrared light photocatalyst but also unveils the good potentials of phthalocyanine-based COFs in photocatalysis.展开更多
Cytochrome P450 enzyme-copper phosphate hybrid materials with flower-like shape were prepared with a simple but efficient coprecipitation method.The growth process of the hybrid flowers can be divided into three succe...Cytochrome P450 enzyme-copper phosphate hybrid materials with flower-like shape were prepared with a simple but efficient coprecipitation method.The growth process of the hybrid flowers can be divided into three successive steps：coordination/nucleation,growth,and further ripen.The concentration of enzymes in the mother liquor exerted great influence on the morphology and surface enzyme content of the nano-composites.The catalytic performance in the reaction of selective oxidation of sulfide to sulfoxide was also investigated.The hybrid flowers exhibited superior catalytic performance：satisfied thioanisole conversion and selectivity to methyl phenyl sulfoxide （both above 97%） with H2O2 as oxidant under mild reaction conditions,excellent stability and recyclability,and wide scope of substrates.Such results indicate that the hybrid materials are potentially good candidates in the industrial enzyme catalysis.展开更多
A technology of polymerase chain reaction-denaturing gradient gel electrophoresis(PCR-DGGE)was used to profile the structure and dynamic changes of microbial communities in a bioreactor for treating hydrocarbon-sulfid...A technology of polymerase chain reaction-denaturing gradient gel electrophoresis(PCR-DGGE)was used to profile the structure and dynamic changes of microbial communities in a bioreactor for treating hydrocarbon-sulfide-containing(HSC)wastewater.The results showed that the heterotrophic genus of Acinetobacter and the autotrophic genera of Thiobacillus and Thiomonas could survive well in all of three operating conditions.Some special genera were also observed with changes of micro-ecoenvironment in the reacto...展开更多
Low cost and green fabrication of high-performance electrocatalysts with earth-abundant resources for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are crucial for the large-scale application of rech...Low cost and green fabrication of high-performance electrocatalysts with earth-abundant resources for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are crucial for the large-scale application of rechargeable Zn-air batteries(ZABs).In this work,our density functional theory calculations on the electrocatalyst suggest that the rational construction of interfacial structure can induce local charge redistribution,improve the electronic conductivity and enhance the catalyst stability.In order to realize such a structure,we spatially immobilize heterogeneous CoS/CoO nanocrystals onto N-doped graphene to synthesize a bifunctional electrocatalyst(CoS/CoO@NGNs).The optimization of the composition,interfacial structure and conductivity of the electrocatalyst is conducted to achieve bifunctional catalytic activity and deliver outstanding efficiency and stability for both ORR and OER.The aqueous ZAB with the as-prepared CoS/CoO@NGNs cathode displays a high maximum power density of 137.8 mW cm^−2,a specific capacity of 723.9 mAh g^−1 and excellent cycling stability(continuous operating for 100 h)with a high round-trip efficiency.In addition,the assembled quasi-solid-state ZAB also exhibits outstanding mechanical flexibility besides high battery performances,showing great potential for applications in flexible and wearable electronic devices.展开更多
Developing sustainable and powerful heterogeneous catalytic systems to convert sulfides into high-value sulfoxide products has become a particularly appealing field and an arduous challenge.In this work,two porous pol...Developing sustainable and powerful heterogeneous catalytic systems to convert sulfides into high-value sulfoxide products has become a particularly appealing field and an arduous challenge.In this work,two porous polyoxometalate-pillared metal-organic frameworks,formulated as H_(3n)[Cu_(3)(pidc)_(2)(H_(2)O)_(2.5)]_(2)[PW_(12)O_(40)]_n·x H_(2)O (n=1.5,x=6 for 1,n=1,x=12 for 2;and H_(3)pidc=2-(3-pyridinyl)-1H-imidazole-4,5-dicarboxylic acid),were consciously manufacture and employed for heterogeneously catalyzed sulfide-sulfoxide transformation.Structural analysis shows that 1 and 2 exhibit similar porous frameworks with nearly identical two-dimensional metal-organic layers further pillared by tetradentate POM ligands with different coordination modes,which also result in the porosity of 1 being almost twice that of 2.In catalyzing the conversion of methyl phenyl sulfide (MPS) to methyl phenyl sulfoxide (MPSO),1 can convert nearly 100%of MPS into MPSO within 30 min,while 2 achieved the similar results requires 50 min.The higher activity of 1 may be attributed to its larger channel that can provide more active sites and more efficient mass transfer process.Systematic structure-activity analyses and mechanistic studies revealed dual-reaction pathways driven by POM sites and metal sites assisted by the structural microenvironment.展开更多
Chemical fixation of carbon dioxide(CO_(2))is an energy-saving method for alleviating the greenhouse gas emissions,whereas it persists a challenge posed by the demand for efficient catalysts.Herein,four unprecedented ...Chemical fixation of carbon dioxide(CO_(2))is an energy-saving method for alleviating the greenhouse gas emissions,whereas it persists a challenge posed by the demand for efficient catalysts.Herein,four unprecedented examples of tetradecanuclear vanadium clusters,namely,[(C_(2)H_(8)N_(2))6(CH_(3)O)8(CH_(3)OH)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(26)](V_(14)-1),[(C_(3)H_(10)N_(2))_(6)(CH_(3)O)_(8)(CH_(3)OH)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(26)](V14^(-2)),[(C_(6)H_(14)N_(2))6(CH_(3)O)8(CH_(3)OH)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(26)]·5H_(2)O(V14^(-3))and[(C_(4)H_(12)N_(2)O)_(4)(C_(4)H_(11)N_(2)O)_(2)(CH_(3)O)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(28)]·6H_(2)O(V_(14)-4),have been triumphantly designed and constructed under solvothermal conditions.Among them,compounds V_(14)-1–4 are the first cases of tetradecanuclear vanadium clusters without the introduction of inorganic acid radical ions.Two main units[V_(10)^(Ⅳ)V_(4)ⅤO_(26)]8+and[V10ⅣV4ⅤO28]4+represent brand-new configurations of tetradecanuclear vanadium clusters.Given the fact that the presence of V^(Ⅳ)/V^(Ⅴ)can potentially facilitate electron transfer and consequently expedite catalytic reactions,we explored the catalytic activities of these compounds.Remarkably,V_(14)-1 was further used as a heterogeneous catalyst in the CO_(2)fixation into cyclic carbonates under milder conditions(60℃,0.5 MPa)and exhibited higher catalytic activity.Also,the experimental results indicated that V_(14)-1 could efficiently catalyze the sulfoxidation,which could fully convert most sulfides within 40 min at room temperature.Moreover,as a stable heterogeneous catalyst employed in CO_(2)fixation with epoxides and oxidation of sulfides,V_(14)-1 could be consecutively used multiple cycles without losing its catalytic activity.展开更多
Metal sulfides as a feasible candidate with high specific capacitance for supercapacitors suffer from sluggish ion/electron transport kinetics and rapid capacitance fading. Herein, we demonstrate a method to fabricate...Metal sulfides as a feasible candidate with high specific capacitance for supercapacitors suffer from sluggish ion/electron transport kinetics and rapid capacitance fading. Herein, we demonstrate a method to fabricate a composite of reduced graphene oxide（rGO） with hollow Co9S8 derived from metal organic framework（MOF）. Due to the combined highly conductive rGO substrates and hollow shell, the prepared r GO/Co9S8 composite exhibits a high specific capacitance of 575.9 F/g at 2 A/g and 92.0% capacitance retention after 9000 cycles. Its excellent electrochemical performance provides great promise for application, and this versatile method can be extended to prepare other similar nanocomposite.展开更多
We measured sulfide-based ATP production by isolated mitochondria from four tissues of Urechis unicinctus and the effects of inhibitors of respiratory complexes on ATP production were evaluated. The results show that ...We measured sulfide-based ATP production by isolated mitochondria from four tissues of Urechis unicinctus and the effects of inhibitors of respiratory complexes on ATP production were evaluated. The results show that these mitochondria could oxidize sulfide to produce ATP. The yield of sulfide-stimulated ATP varied from 5 nmol ATP/min/mg to 90 nmol ATP/min/mg according to the sulfide concentration and the source of the mitochondria. The maximum ATP synthesis occurred in hindgut mitochondria using 5 μmol/L sulfide as a substrate. The effects of inhibitors (Rotenone, Antimycin A, Cyanide, and Salicylhydroxamic acid) on mitochondrial ATP production varied with the source of the mitochondria. Our results indicate that sulfide-based ATP production and the associated electron transport pathway are tissue-specific in U. unicinctus.展开更多
Lithium-sulfur(Li-S) batteries are promising for high energy-storage applications but suffer from sluggish conversion reaction kinetics and substantial lithium sulfide(Li_(2)S) oxidation barrier,especially under high ...Lithium-sulfur(Li-S) batteries are promising for high energy-storage applications but suffer from sluggish conversion reaction kinetics and substantial lithium sulfide(Li_(2)S) oxidation barrier,especially under high sulfur loadings.Here,we report a Li cation-doped tungsten oxide(Li_(x)WO_(x)) electrocatalyst that efficiently accelerates the S■HLi_(2)S interconversion kinetics.The incorporation of Li dopants into WO_(x) cationic vacancies enables bidirectional electrocatalytic activity for both polysulfide reduction and Li_(2)S oxidation,along with enhanced Li^(+) diffusion.In conjunction with theoretical calculations,it is discovered that the improved electrocatalytic activity originates from the Li dopant-induced geometric and electronic structural optimization of the Li_(x)WO_(x),which promotes the anchoring of sulfur species at favourable adsorption sites while facilitating the charge transfer kinetics.Consequently,Li-S cells with the Li_(x)WO_(x) bidirectional electrocatalyst show stable cycling performance and high sulfur utilization under high sulfur loadings.Our approach provides insights into cation engineering as an effective electrocatalyst design strategy for advancing high-performance Li-S batteries.展开更多
Electrocatalytic hydrogen evolution and sulfion(S^(2-))recycling are promising strategies for boosting H_(2)production and removing environmental pollutants.Here,a nano-Ni-functionalized molybdenum disulfide(MoS_(2))n...Electrocatalytic hydrogen evolution and sulfion(S^(2-))recycling are promising strategies for boosting H_(2)production and removing environmental pollutants.Here,a nano-Ni-functionalized molybdenum disulfide(MoS_(2))nanosheet was assembled on steel mesh(Ni-MoS_(2)/SM)for use in sulfide oxidation reaction-assisted,energy-saving H_(2)production.Experimental and theoretical calculation results revealed that anchoring nano-Ni on high-surface-area slack MoS_(2)nanosheets not only optimized catalyst adsorption of polysulfides but also played an important role in promoting hydrogen evolution reaction kinetics by absorbing OH_(ad),thereby greatly enhancing the catalytic performance toward sulfide oxidation reaction and hydrogen evolution reaction.Meanwhile,the Ni/MoS^(2-)based hydrogen evolution reaction+sulfide oxidation reaction system achieved nearly 100%hydrogen production efficiency and only consumed 61%less power per kWh than the oxygen evolution reaction+hydrogen evolution reaction system,which suggested our proposed Ni-MoS_(2)and novel hydrogen production system are promising for sustainable energy production.展开更多
基金funded by the National Natural Science Foundation of China(Nos.22072108 and 21773173)。
文摘Designing visible light photocatalysts with a metal oxide semiconductor as the starting material could expand a new horizon for the conversion and storage of solar energy.Here,the benchmark photocatalyst TiO_(2) was used to pursue this goal by anchoring aromatic acids.Extending the aromatic acid was strategically deployed to design TiO_(2) complexes with violet light-induced selective aerobic oxidation of sulfide as the probe reaction.With benzoic acid(BA)as the initial molecule,horizontally extending one or two benzene rings furnishes 2-naphthoic acid(2-NA)and 2-anthracene acid(2-AA).Moreover,triethylamine(TEA),an electron transfer mediator,was introduced to maintain the integrity of the anchored aromatic acids.Notably,there was a direct correlation between theπ-conjugation of aromatic acid ligand and the selective aerobic oxidation of sulfides.Among the three aromatic acids,2-AA delivered the best result over TiO_(2) due to the most extensiveπ-conjugated system.Ultimately,violet light-induced selective aerobic oxidation of sulfides into corresponding sulfoxides was conveniently realized by cooperative photocatalysis of 2-AA-TiO_(2) with 10 mol%of TEA.This work affords an extending strategy for designing the next-generation ligands for semiconductors to expand visible light-induced selective reactions.
基金supported by the NNSFC(No.21401094)Project of Shandong Province Higher Educational Science and Technology Program(No.J16LC53)+1 种基金Science and the Technology Development Plans of Liaocheng(No.2014GJH01)the National College Students'Science and Technology Innovation Fund(No.1420800)
文摘A novel imidazole-functionalized dioxovanadium complex [V2O2（C2O4）（aIM）4] （aIM =1-allylimidazole） was synthesized by the reaction of VO（acac）2 with 1-allylimidazole and fully characterized by single-crystal X-ray diffraction （SCXRD）,powder X-ray diffraction （PXRD）,X-ray photoelectron spectroscopy （XPS）,Fourier transform infrared spectroscopy （FT-IR） and elemental analyses.Interestingly,the oxalate was in-situ generated from the acetylacetone anion of VO（acac）2 and further coordinated with the vanadium cation and finally complex 1 was achieved.The crystal of complex 1 belongs to the monoclinic system,space group P21/n with a =10.7922（9）,b =10.6296（8）,c =13.2936（11） （A）,μ =0.677 mm^-1,Mr =686.48,V =1516.9（2） A^3,Z =2,Dc =1.503 g/cm^3,F（000） =708,R =0.0543,and wR =0.1517 for 2459 observed reflections with Ⅰ 〉 2σ（Ⅰ）.Notably,complex 1 is further used as catalyst in the oxidation of sulfides using H2O2 as the oxidant and exhibits excellent catalytic performance （conv.up to 95.6%,sele.up to 98.9%）.
基金supported by the Natural Science Foundation of Jiangsu Province(BK20231270)the National Science Fund for Distinguished Young Scholars(22125804).
文摘Metal-organic frameworks(MOFs)with new topologies and enhanced properties can be obtained by connecting metal-organic layers(MOLs)using multifunctional linkers.However,new topologies constructed by this method using linear-shaped ligands have not yet been explored.Herein,we present the design of NUT-123 by incorporating a near-linear perylene diimide(PDI)derivate,PDI-CH_(3)-COOH,into the preselected zirconium-based MOLs.3D electron diffraction confirms the successful construction of a novel topology in NUT-123.Furthermore,the uniformly dispersed PDI groups within the structure confer enhance photocatalytic capability while effectively circumventing the self-aggregation of PDI-CH_(3)-COOH.NUT-123 exhibits enhanced efficiency and selectivity in sulfide oxidation and demonstrates excellent substrate compatibility,achieving 100%conversion of various organic sulfides.Mechanistic studies indicate that the formation of sulfoxides is facilitated by concurrent electron and energy transfer.This work fills the gap in constructing a new topology by connecting MOLs with linear-shaped linkers and provides a photocatalyst for selective sulfide oxidation.
基金supported by National Natural Science Foundation of China(Nos.22201046,22371054)Local Innovation Research Team Project of Guangdong Pearl River Talent Plan(No.2017BT01Z032)。
文摘Zirconium-based metal-organic cages(Zr-MOCs)typically exhibit high stability,but their structural and application reports are scarce due to stringent crystallization conditions.We have successfully fluorinated the classical Zr-MOCs(ZrT-3)for the first time,obtaining the fluorinated MOCs(ZrT-3-F).Notably,ZrT-3-F not only inherits the high stability of its parent structure,but also acts as a catalyst for the effective oxidation of benzyl thioether for the first time.The reaction can reach a conversion rate of 99%in 6 h,and the selectivity reaches 95%,which far exceeds the non-fluorinated ZrT-3.This work proves that the specific functionalization of the classical Zr-MOCs can further expand their application potential,such as catalysis.
基金supported by the National Natural Science Foundation of China(No.41672245)the National Key Research and Development Program of China(No.2022YFC3702201).
文摘The environmental threat posed by stibnite is an important geoenvironmental issue of current concern.To better understand stibnite oxidation pathways,aerobic abiotic batch experiments were conducted in aqueous solution with varyingδ^(18)O_(H_(2)O) value at initial neutral pH for different lengths of time(15-300 days).The sulfate oxygen and sulfur isotope compositions as well as concentrations of sulfur and antimony species were determined.The sulfur isotope fractionation factor(△^(34)S_(SO4-stibnite))values decreased from 0.8‰to-2.1‰during the first 90 days,and increased to 2.6‰at the 180 days,indicating the dominated intermediate sulfur species such as S_(2)O_(3)^(2-),S0,and H_(2)S(g)involved in Sb2S3 oxidation processes.The incorporation of O into sulfate derived from O_(2)(~100%)indicated that the dissociated O_(2)was only directly adsorbed on the stibnite-S sites in the initial stage(0-90 days).The proportion of O incorporation into sulfate from water(27%-52%)increased in the late stage(90-300 days),which suggested the oxidation mechanism changed to hydroxyl attack on stibnite-S sites promoted by nearby adsorbed O_(2)on stibnite-Sb sites.The exchange of oxygen between sulfite and water may also contributed to the increase of water derived O into SO42-.The new insight of stibnite oxidation pathway contributes to the understanding of sulfide oxidation mechanism and helps to interpret field data.
基金financially supported by the State Key Research Development Program of China (No. 2016YFA0204200the National Natural Science Foundation of China (Nos. 21822603, 21773062, 21577036, 21377038 and 21237003)+1 种基金Shanghai Pujiang Program (No. 17PJD011)the Fundamental Research Funds for the Central Universities (No. 22A201514021)
文摘The recovery of heterogeneous catalysts can save costs and avoid secondary pollution,but its separation efficiency and recovery cost are limited by conventional separation methods such as precipitation–flocculation,centrifugation and filtration.In this paper,we found that surface-defective metal sulfides/oxides(WS2,CuS,ZnS,MoS2,CdS,TiO2,MoO2 and ZnO)commonly used in advanced oxidation processes(AOPs)could be magnetically recovered at room temperature and atmospheric pressure by mechanically mixing with Fe3O4.Zeta potential,Raman,X-ray photoelectron spectroscopy(XPS)and electro-spin resonance(ESR)spectra were measured to explore the mechanism of the magnetic separation phenomenon.The exposed active metal sites on the surface of defective metal sulfides/oxides are beneficial for the formation of chemical bonds,which are combined with electrostatic force to be responsible for the magnetic separation.Moreover,other factors affecting the magnetic separation were also investigated,such as the addition of amount of Fe3O4,different solvents and particle sizes.Finally,WS2 was chosen to be applied as a co-catalyst in Fenton reaction,which could be well separated by the magnetic Fe3O4 to achieve the recycle of catalyst in Fenton reaction.Our research provides a general strategy for the recycle of metal sulfides/oxides in the catalytic applications.
文摘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.
基金supported by the National Natural Science Foundation of China(No. 51878216)。
文摘The sulfur-containing odor emitted from sludge composting could be controlled by sulfide oxidizing bacteria, yet mesophilic strains show inactivation during the thermophilic stage of composting. Aimed to investigate and characterize the thermotolerant bacterium that could oxidize sulfide into sulfate, a heterotrophic strain was isolated from sewage sludge composting and identified as Paenibacillus naphthalenovorans LYH-3. The effects of various environmental factors on sulfide oxidation capacities were studied to optimize the sulfate production, and the highest production rate (27.35%±0.86%) was obtained at pH 7.34, the rotation speed of 161.14 r/min, and the inoculation amount of 5.83%by employing BoxBehnken design. The results of serial sulfide substrates experiments indicated that strain LYH-3 could survive up to 400 mg/L of sulfide with the highest sulfide removal rate (88.79%±0.35%) obtained at 50 mg/L of sulfide. Growth kinetic analysis presented the maximum specific growth rateμm(0.5274 hr-1) after 22 hr cultivation at 50℃. The highest enzyme activities of sulfide quinone oxidoreductase (0.369±0.052 U/mg) and sulfur dioxygenase (0.255±0.014 U/mg) were both obtained at 40℃, and the highest enzyme activity of sulfite acceptor oxidoreductase (1.302±0.035 U/mg) was assessed at 50℃. The results indicated that P. naphthalenovorans possessed a rapid growth rate and efficient sulfide oxidation capacities under thermophilic conditions, promising a potential application in controlling sulfur-containing odors during the thermophilic stage of sludge composting.
文摘A continuous fluidized bed bioreactor （FBBR） with nylon support particles was used to treat synthetic sulfide wastewater at different hydraulic retention time of 25, 50 and 75 min and upflow velocity of 14, 17 and 20 m/hr. The effects of upflow velocity, hydraulic retention time and reactor operation time on sulfide oxidation rate were studied using statistical model. Mixed culture obtained from the activated sludge, taken from tannery effluent treatment plant, was used as a source for microorganisms. The diameter and density of the nylon particles were 2-3 mm and 1140 kg/m3, respectively. Experiments were carried out in the reactor at a temperature of （30 ± 2）°C, at a fixed bed height of 16 cm after the formation of biofilm on the surface of support particles. Biofilm thickness reached （42 ± 3） μm after 15 days from reactor start-up. The sulfide oxidation, sulfate and sulfur formation is examined at all hydraulic retention times and upflow velocities. The results indicated that almost 90%-92% sulfide oxidation was achieved at all hydraulic retention times. Statistical model could explain 94% of the variability and analysis of variance showed that upflow velocity and hydraulic retention time slightly affected the sulfide oxidation rate. The highest sulfide oxidation of 92% with 70% sulfur was obtained at hydraulic retention time of 75 min and upflow velocity of 14 m/hr.
基金This work was conducted within the framework of Program of the Russian Academy of Sciences and the Federal Agency for Scientific Organizations (state‐guaranteed order for BIC, Project АААА‐А17‐117041710086‐6).
文摘The influence of the textural and acidic properties ofγ‐Al2O3,(γ+χ)‐Al2O3,and?‐Al2O3on the catalytic activity,selectivity,and stability of direct H2S oxidation has been studied.A comparison of the H2S‐to‐S conversion effectiveness of aluminas with their acidic properties(identified by Fourier transform infrared spectroscopy and temperature programmed desorption of NH3)shows that H2S adsorption occurs predominantly on weak Lewis acid sites(LAS).γ‐Alumina samples containing aχ‐phase and/or modified Mg2+ions have a greater concentration of weak LAS and exhibit greater catalytic activity.When alumina is treated with a sulfuric acid solution,strong LAS appear and the number of LAS decreases significantly.Modification of alumina with hydrochloric acid has a limited effect on LAS strength.Weak LAS are retained and double in number compared to that present in the unmodified alumina,but the treated sample has Al?Cl bonds.Alumina samples modified by sulfate and chloride anions exhibit poor catalytic activity in H2S oxidation.
文摘Covalent organic frameworks(COFs)based photocatalysts utilizing infrared light remains unexplored due to the limitation of electronic absorption.Herein,two novel two-dimensional(2D)polyimide-linked phthalocyanine COFs,namely MPc-DPA-COFs(M=Zn/Cu),were prepared from the imidization reaction of metal tetraanhydrides of 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato(M(TAPc))with 9,10-diphenyl anthracene(DPA).Both COFs possess highly crystalline eclipsed AA stacking structure with neighboring layer distance of 0.33 nm on the basis of powder X-ray diffraction analysis and high-resolution transmission electron microscopy.Effective π–π interaction between phthalocyanine chromophores in neighboring layers of 2D COFs leads to significant bathochromic-shift of narrow Q band from 697 nm for M(TAPc)to the infrared light absorption range of 760–1000 nm for MPc-DPA-COFs according to solid UV-vis diffuse reflectance spectra.This endows them in particular ZnPc-DPA-COF with excellent reactive oxygen species of•O_(2)^(–)and 1O_(2) generation activity under infrared light radiation(λ>760 nm)based on the electron spin resonance spectroscopy measurement,in turn resulting in the excellent photocatalytic capacity towards oxidation of sulfides under infrared light radiation.Corresponding quenching experiments reveal the contribution of both•O_(2)^(–)and 1O_(2) to the oxidation of sulfides,but the former•O_(2)^(–)species plays a leading role in this photocatalytic process.The present result not only provides a new efficient infrared light photocatalyst but also unveils the good potentials of phthalocyanine-based COFs in photocatalysis.
文摘Cytochrome P450 enzyme-copper phosphate hybrid materials with flower-like shape were prepared with a simple but efficient coprecipitation method.The growth process of the hybrid flowers can be divided into three successive steps：coordination/nucleation,growth,and further ripen.The concentration of enzymes in the mother liquor exerted great influence on the morphology and surface enzyme content of the nano-composites.The catalytic performance in the reaction of selective oxidation of sulfide to sulfoxide was also investigated.The hybrid flowers exhibited superior catalytic performance：satisfied thioanisole conversion and selectivity to methyl phenyl sulfoxide （both above 97%） with H2O2 as oxidant under mild reaction conditions,excellent stability and recyclability,and wide scope of substrates.Such results indicate that the hybrid materials are potentially good candidates in the industrial enzyme catalysis.
文摘A technology of polymerase chain reaction-denaturing gradient gel electrophoresis(PCR-DGGE)was used to profile the structure and dynamic changes of microbial communities in a bioreactor for treating hydrocarbon-sulfide-containing(HSC)wastewater.The results showed that the heterotrophic genus of Acinetobacter and the autotrophic genera of Thiobacillus and Thiomonas could survive well in all of three operating conditions.Some special genera were also observed with changes of micro-ecoenvironment in the reacto...
基金the National Natural Science Foundation of China(Grant Numbers 21506081)the Provincial Natural Science Foundation of Jiangsu(Grant Numbers BK20191430)+2 种基金Six Talent Peaks Project of Jiangsu Province[Grant Numbers XNY-009]High-tech research key laboratory of Zhenjiang(Grant Numbers SS2018002)a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions and the Research Foundation of Jiangsu University(Grant Numbers 17JDG007).
文摘Low cost and green fabrication of high-performance electrocatalysts with earth-abundant resources for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are crucial for the large-scale application of rechargeable Zn-air batteries(ZABs).In this work,our density functional theory calculations on the electrocatalyst suggest that the rational construction of interfacial structure can induce local charge redistribution,improve the electronic conductivity and enhance the catalyst stability.In order to realize such a structure,we spatially immobilize heterogeneous CoS/CoO nanocrystals onto N-doped graphene to synthesize a bifunctional electrocatalyst(CoS/CoO@NGNs).The optimization of the composition,interfacial structure and conductivity of the electrocatalyst is conducted to achieve bifunctional catalytic activity and deliver outstanding efficiency and stability for both ORR and OER.The aqueous ZAB with the as-prepared CoS/CoO@NGNs cathode displays a high maximum power density of 137.8 mW cm^−2,a specific capacity of 723.9 mAh g^−1 and excellent cycling stability(continuous operating for 100 h)with a high round-trip efficiency.In addition,the assembled quasi-solid-state ZAB also exhibits outstanding mechanical flexibility besides high battery performances,showing great potential for applications in flexible and wearable electronic devices.
基金financially supported by the National Natural Science Foundation of China (Nos. 21371027, 20901013)Natural Science Foundation of Liaoning Province (No. 2015020232)Fundamental Research Funds for the Central Universities (Nos. DUT19LK01, DUT15LN18)。
文摘Developing sustainable and powerful heterogeneous catalytic systems to convert sulfides into high-value sulfoxide products has become a particularly appealing field and an arduous challenge.In this work,two porous polyoxometalate-pillared metal-organic frameworks,formulated as H_(3n)[Cu_(3)(pidc)_(2)(H_(2)O)_(2.5)]_(2)[PW_(12)O_(40)]_n·x H_(2)O (n=1.5,x=6 for 1,n=1,x=12 for 2;and H_(3)pidc=2-(3-pyridinyl)-1H-imidazole-4,5-dicarboxylic acid),were consciously manufacture and employed for heterogeneously catalyzed sulfide-sulfoxide transformation.Structural analysis shows that 1 and 2 exhibit similar porous frameworks with nearly identical two-dimensional metal-organic layers further pillared by tetradentate POM ligands with different coordination modes,which also result in the porosity of 1 being almost twice that of 2.In catalyzing the conversion of methyl phenyl sulfide (MPS) to methyl phenyl sulfoxide (MPSO),1 can convert nearly 100%of MPS into MPSO within 30 min,while 2 achieved the similar results requires 50 min.The higher activity of 1 may be attributed to its larger channel that can provide more active sites and more efficient mass transfer process.Systematic structure-activity analyses and mechanistic studies revealed dual-reaction pathways driven by POM sites and metal sites assisted by the structural microenvironment.
基金supported by the Natural Science Foundation of Jiangsu(BK20191359)the National Natural Science Foundation of China(92161109)+1 种基金the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX22_1343)the Social Science Foundation of Jiangsu(19TQB002)。
文摘Chemical fixation of carbon dioxide(CO_(2))is an energy-saving method for alleviating the greenhouse gas emissions,whereas it persists a challenge posed by the demand for efficient catalysts.Herein,four unprecedented examples of tetradecanuclear vanadium clusters,namely,[(C_(2)H_(8)N_(2))6(CH_(3)O)8(CH_(3)OH)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(26)](V_(14)-1),[(C_(3)H_(10)N_(2))_(6)(CH_(3)O)_(8)(CH_(3)OH)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(26)](V14^(-2)),[(C_(6)H_(14)N_(2))6(CH_(3)O)8(CH_(3)OH)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(26)]·5H_(2)O(V14^(-3))and[(C_(4)H_(12)N_(2)O)_(4)(C_(4)H_(11)N_(2)O)_(2)(CH_(3)O)_(2)V_(10)^(Ⅳ)V_(4)ⅤO_(28)]·6H_(2)O(V_(14)-4),have been triumphantly designed and constructed under solvothermal conditions.Among them,compounds V_(14)-1–4 are the first cases of tetradecanuclear vanadium clusters without the introduction of inorganic acid radical ions.Two main units[V_(10)^(Ⅳ)V_(4)ⅤO_(26)]8+and[V10ⅣV4ⅤO28]4+represent brand-new configurations of tetradecanuclear vanadium clusters.Given the fact that the presence of V^(Ⅳ)/V^(Ⅴ)can potentially facilitate electron transfer and consequently expedite catalytic reactions,we explored the catalytic activities of these compounds.Remarkably,V_(14)-1 was further used as a heterogeneous catalyst in the CO_(2)fixation into cyclic carbonates under milder conditions(60℃,0.5 MPa)and exhibited higher catalytic activity.Also,the experimental results indicated that V_(14)-1 could efficiently catalyze the sulfoxidation,which could fully convert most sulfides within 40 min at room temperature.Moreover,as a stable heterogeneous catalyst employed in CO_(2)fixation with epoxides and oxidation of sulfides,V_(14)-1 could be consecutively used multiple cycles without losing its catalytic activity.
基金Financial support from National Key Project (No. 2017YFF0210703)Distinguished Young Scientists Program of the National Natural Science Foundation of China (Nos. 51425301, 21374021, 51673096 and U1601214)
文摘Metal sulfides as a feasible candidate with high specific capacitance for supercapacitors suffer from sluggish ion/electron transport kinetics and rapid capacitance fading. Herein, we demonstrate a method to fabricate a composite of reduced graphene oxide（rGO） with hollow Co9S8 derived from metal organic framework（MOF）. Due to the combined highly conductive rGO substrates and hollow shell, the prepared r GO/Co9S8 composite exhibits a high specific capacitance of 575.9 F/g at 2 A/g and 92.0% capacitance retention after 9000 cycles. Its excellent electrochemical performance provides great promise for application, and this versatile method can be extended to prepare other similar nanocomposite.
基金Supported by the National Natural Science Foundation of China (No. 40776074)
文摘We measured sulfide-based ATP production by isolated mitochondria from four tissues of Urechis unicinctus and the effects of inhibitors of respiratory complexes on ATP production were evaluated. The results show that these mitochondria could oxidize sulfide to produce ATP. The yield of sulfide-stimulated ATP varied from 5 nmol ATP/min/mg to 90 nmol ATP/min/mg according to the sulfide concentration and the source of the mitochondria. The maximum ATP synthesis occurred in hindgut mitochondria using 5 μmol/L sulfide as a substrate. The effects of inhibitors (Rotenone, Antimycin A, Cyanide, and Salicylhydroxamic acid) on mitochondrial ATP production varied with the source of the mitochondria. Our results indicate that sulfide-based ATP production and the associated electron transport pathway are tissue-specific in U. unicinctus.
基金financially Australian Research Council (DE210101157 and FT190100058)。
文摘Lithium-sulfur(Li-S) batteries are promising for high energy-storage applications but suffer from sluggish conversion reaction kinetics and substantial lithium sulfide(Li_(2)S) oxidation barrier,especially under high sulfur loadings.Here,we report a Li cation-doped tungsten oxide(Li_(x)WO_(x)) electrocatalyst that efficiently accelerates the S■HLi_(2)S interconversion kinetics.The incorporation of Li dopants into WO_(x) cationic vacancies enables bidirectional electrocatalytic activity for both polysulfide reduction and Li_(2)S oxidation,along with enhanced Li^(+) diffusion.In conjunction with theoretical calculations,it is discovered that the improved electrocatalytic activity originates from the Li dopant-induced geometric and electronic structural optimization of the Li_(x)WO_(x),which promotes the anchoring of sulfur species at favourable adsorption sites while facilitating the charge transfer kinetics.Consequently,Li-S cells with the Li_(x)WO_(x) bidirectional electrocatalyst show stable cycling performance and high sulfur utilization under high sulfur loadings.Our approach provides insights into cation engineering as an effective electrocatalyst design strategy for advancing high-performance Li-S batteries.
基金financially supported by the National Natural Science Foundation of China(22272131,2221154071221972111)+4 种基金the Natural Science Foundation of Chongqing(CSTB2022NSCQ-MSX1411)the Venture&Innovation Support Program for Chongqing Overseas Returnees(cx2019073)Chongqing Doctoral Research and Innovation Project(CYB21106)Chongqing Engineering Research Center for Micro-Nano Biomedical Materials and DevicesChongqing Key Laboratory for Advanced Materials and Technologies
文摘Electrocatalytic hydrogen evolution and sulfion(S^(2-))recycling are promising strategies for boosting H_(2)production and removing environmental pollutants.Here,a nano-Ni-functionalized molybdenum disulfide(MoS_(2))nanosheet was assembled on steel mesh(Ni-MoS_(2)/SM)for use in sulfide oxidation reaction-assisted,energy-saving H_(2)production.Experimental and theoretical calculation results revealed that anchoring nano-Ni on high-surface-area slack MoS_(2)nanosheets not only optimized catalyst adsorption of polysulfides but also played an important role in promoting hydrogen evolution reaction kinetics by absorbing OH_(ad),thereby greatly enhancing the catalytic performance toward sulfide oxidation reaction and hydrogen evolution reaction.Meanwhile,the Ni/MoS^(2-)based hydrogen evolution reaction+sulfide oxidation reaction system achieved nearly 100%hydrogen production efficiency and only consumed 61%less power per kWh than the oxygen evolution reaction+hydrogen evolution reaction system,which suggested our proposed Ni-MoS_(2)and novel hydrogen production system are promising for sustainable energy production.
