The harsh corrosive environment and sluggish oxygen evolution reaction(OER)kinetics at the anode of proton exchange membrane water electrolysis(PEMWE)cells warrant the use of excess Ir,thereby hindering large-scale in...The harsh corrosive environment and sluggish oxygen evolution reaction(OER)kinetics at the anode of proton exchange membrane water electrolysis(PEMWE)cells warrant the use of excess Ir,thereby hindering large-scale industrialization.To mitigate these issues,the present study aimed at fabricating a robust low-Ir-loading electrode via one-pot synthesis for efficient PEMWE.The pre-electrode was first prepared by alloying through the co-electrodeposition of Ir and Co,followed by the fabrication of Ir–Co oxide(Co-incorporated Ir oxide)electrodes via electrochemical dealloying.Two distinct dealloying techniques resulted in a modified valence state of Ir,and the effects of Co incorporation on the activity and stability of the OER catalysts were clarified using density functional theory(DFT)calculations,which offered theoretical insights into the reaction mechanism.While direct experimental validation of the oxygen evolution mechanism remains challenging under the current conditions,DFT-based theoretical modeling provided valuable perspectives on how Co incorporation could influence key steps in oxygen evolution catalysis.The Ir–Co oxide electrode with a selectively modulated valence state showed impressive performance with an overpotential of 258 mV at 10 mA cm^(−2),a low Tafel slope of 29.4 mV dec^(−1),and stability for 100 h at 100 mA cm^(−2)in the OER,in addition to a low overpotential of 16 mV at−10 mA cm^(−2)and high stability for 24 h in the hydrogen evolution reaction.The PEMWE cell equipped with the bifunctional Ir–Co oxide electrode as the anode and cathode exhibited outstanding performance(11.4 A cm^(−2)at 2.3 Vcell)despite having a low noble-metal content of 0.4 mgNM cm^(−2).展开更多
Different reactive flame retardants have been extensively developed for vinyl ester resins(VERs),but very few of them can yield a flame-retardant resin that meets defined standards(e.g.UL-94 V-0 rating).In this work,p...Different reactive flame retardants have been extensively developed for vinyl ester resins(VERs),but very few of them can yield a flame-retardant resin that meets defined standards(e.g.UL-94 V-0 rating).In this work,phosphorous-containing 1-vinylimidazole salts(called VIDHP and VIDPP)were synthesized through the facile neutralization of the acid and 1-vinylimidazole.VIDHP and VIDPP were then applied as flame-retardant crosslinking agents of VERs,by which phosphorus-containing groups could be incorporated into the resin chain via ionic bonds.VIDHP/VER and VIDPP/VER showed a high curing activity and can be well cured in moderate temperatures.With 20 wt.%additions of VIDHP and VIDPP,VIDHP20/VER,and VIDPP20/VER presented a limiting oxygen index value of 29.7%and 28.4%,respectively,with the latter achieving a UL 94 V0 rating.In the cone calorimetric test,compared to the unmodified VERs,VIDPP20/VER exhibited large reductions in the peak heat release rate,total heat release rate,and total smoke release rate while VIDHP20/VER demonstrated comparatively inferior performance in terms of the heat release.VIDHP20/VER and VIDPP20/VER showed good thermal stability and presented a little lower glass transition temperature than the control sample.VIDPP with a low phosphorus oxidation state(+1)demonstrated high flame-retardant activities in the gaseous phase,whereas VIDHP with a high phosphorus oxidation state(+5)primarily exhibited efficacy in the condensed phase.展开更多
The highly selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dihydroxymethylfuran is an important reaction in the field of biomass hydrogenation,because it is a bridge between biomass resources and chemical in...The highly selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dihydroxymethylfuran is an important reaction in the field of biomass hydrogenation,because it is a bridge between biomass resources and chemical industry.Here,we precisely constructed carbon nitride supported Pd-based catalysts by a simple impregnation-reduction method.By changing the reduction temperature,catalysts with different oxidation state could be precisely constructed.Moreover,the important correlation between the ratio of Pd^(0)/Pd^(2+)and catalytic activity is revealed during the selective hydrogenation of HMF.The Pd/g—C_(3)N_(4)—300 catalyst with a Pd^(0)/Pd^(2+)ratio of 3/2 showed the highest catalytic activity,which could get 96.9%5-hydroxymethylfurfural conversion and 90.3%2,5-dihydroxymethylfuran selectivity.Further density functional theory calculation revealed that the synergistic effect between Pd0and Pd2+in Pd/g—C_(3)N_(4)—300 system could boost the adsorption of the substrate and the dissociation of hydrogen.In this work,we highlight the important correlation between metal oxidation state and catalytic activity,which provides valuable insights for the rational design of precious metal catalysts for hydrogenation reactions.展开更多
The oxidation state of sulfur is detected in Na20-CaO-SiO2 float glass by synchrotron radiation X-ray absorption near edge structure （XANES） spectra at the sulfur K edge. The measured spectra show the only presence ...The oxidation state of sulfur is detected in Na20-CaO-SiO2 float glass by synchrotron radiation X-ray absorption near edge structure （XANES） spectra at the sulfur K edge. The measured spectra show the only presence of S^6＋ in the Na20-CaO-SiO2 float glass and the oxidation state of sulfur do not change with the increase of glass depth. It is also found that, after the melt has gone through the molten tin bath, the S^6＋ is the dominant species, but S^2- is also present on both surfaces. It is not certain whether cation bonds to S^2- or not, because there are many cations dissolved in the melted tin which makes the spectrum complicated.展开更多
Arsenic methyltransferase（As3mt） catalyzes the conversion of inorganic arsenic（i As） to its methylated metabolites, including toxic methylarsonite（MAs~Ⅲ） and dimethylarsinite（DMAs~Ⅲ）. Knockout（KO） of As3 m...Arsenic methyltransferase（As3mt） catalyzes the conversion of inorganic arsenic（i As） to its methylated metabolites, including toxic methylarsonite（MAs~Ⅲ） and dimethylarsinite（DMAs~Ⅲ）. Knockout（KO） of As3 mt was shown to reduce the capacity to methylate i As in mice. However, no data are available on the oxidation states of As species in tissues of these mice. Here, we compare the oxidation states of As species in tissues of male C57BL/6 As3mt-KO and wild-type（WT） mice exposed to arsenite（iA s~Ⅲ） in drinking water. WT mice were exposed to50 mg/L As and As3mt-KO mice that cannot tolerate 50 mg/L As were exposed to 0, 15, 20, 25 or30 mg/L As. iA s~Ⅲaccounted for 53% to 74% of total As in liver, pancreas, adipose, lung, heart, and kidney of As3mt-KO mice; tri- and pentavalent methylated arsenicals did not exceed 10% of total As. Tissues of WT mice retained iA s and methylated arsenicals： iA s~Ⅲ, MAs~Ⅲand DMAs~Ⅲ represented 55%‐68% of the total As in the liver, pancreas, and brain. High levels of methylated species, particularly MAs~Ⅲ, were found in the intestine of WT, but not As3mt-KO mice,suggesting that intestinal bacteria are not a major source of methylated As. Blood of WT mice contained significantly higher levels of As than blood of As3mt-KO mice. This study is the first to determine oxidation states of As species in tissues of As3mt-KO mice. Results will help to design studies using WT and As3mt-KO mice to examine the role of iA s methylation in adverse effects of iA s exposure.展开更多
A method determining di-and tri-valeht cobalt extracted from soils with EDTA·2HOAc·NH4OAc solution (pH 4.65) was developed based on the difference of the stability constants of Co(II)EDTA and Co(III)EDTA. An...A method determining di-and tri-valeht cobalt extracted from soils with EDTA·2HOAc·NH4OAc solution (pH 4.65) was developed based on the difference of the stability constants of Co(II)EDTA and Co(III)EDTA. Analytical results indicated that soil cobalt existed in both two oxidation states, i. e. , di-and tri-valent cobalt. Extractable di-valent cobalt in 60 soil samples collected from various soils in China ranged from 0.02 ppm to 3.54 ppm, with the mean of 0.62 ppm, and extractable tri-valent cobalt from 0.04 ppm to 27.65 ppm, with the mean of 2.93 ppm.展开更多
Electrocatalytic CO_(2) reduction(ECR)is a promising approach for achieving carbon neutrality due to its ability to convert CO_(2) to valuable chemicals.Recent advances have significantly enhanced the ECR performance ...Electrocatalytic CO_(2) reduction(ECR)is a promising approach for achieving carbon neutrality due to its ability to convert CO_(2) to valuable chemicals.Recent advances have significantly enhanced the ECR performance of various catalysts by tuning their oxidation states,particularly for Cu-based catalysts that can reduce CO_(2) to multiple products.However,the oxidation state of copper(OSCu),especially Cu+,changes during the reaction process,posing significant challenges for both catalyst characterization and performance.In this review,the current understanding of the effect of oxidation states on product selectivity was first discussed.A comprehensive overview of in situ/operando characterization techniques,used to monitor the dynamic evolution of oxidation states during ECR,was then provided.Various strategies for stabilizing oxidation states through modification of catalysts and manipulation of external conditions were discussed.This review aimed to deepen the understanding of oxidation states in ECR and enlighten the development of more efficient electrocatalysts.展开更多
Photoresponsive materials are considered as promising systems for intelligent technology applications owing to the contactless spatial and temporal control.Herein,controllable multi-photoresponsive behaviors are reali...Photoresponsive materials are considered as promising systems for intelligent technology applications owing to the contactless spatial and temporal control.Herein,controllable multi-photoresponsive behaviors are realized in benzo[b]thiophene derivatives(o-DMP-S,o-DMP-SO,and o-DMP-SO_(2))by modulating the sulfur oxidation state.Among them,o-DMP-S is photo-unreactive but possesses denser molecular packing upon ultraviolet(UV)light irradiation,exhibiting photoenhanced room-temperature phosphorescence properties.Through stoichiometric oxidation of the sulfur atom in o-DMP-S,the resulting sulfoxide compound o-DMP-SO undergoes a radical photolysis reaction involving photodeoxygenation and photochemical rearrangement,thereby leading to the photomechanical effect.The sulfone compound o-DMP-SO_(2)displays prominent reversible photochromism,resulting from the radical photocyclization under 365 nm UV light irradiation.Based on comprehensive experimental and computational investigations,the diverse photoresponsive behaviors of these benzo[b]thiophene derivatives are demonstrated to depend on the intersystem crossing efficiency and radical-mediated photochemical reaction activity in excited states due to the different sulfur oxidation states.This work provides an insightful understanding of the relationship between molecular structure and photoresponsive behavior and opens up the opportunity for the development of photoresponsive materials with potential applications.展开更多
One of the crucial issues in the chemical looping technology lies in its bed material:the oxygen carrier.Particle size analysis of an oxygen carrier is important since in a fluidized bed the material can only work wel...One of the crucial issues in the chemical looping technology lies in its bed material:the oxygen carrier.Particle size analysis of an oxygen carrier is important since in a fluidized bed the material can only work well within a specific size range.While the favorable size ranges for oxygen carrier materials have already been reported,none of the published studies has analyzed the particle size and shape of oxygen carriers in detail.Furthermore,the effect of oxygen carriers'oxidation degree on such properties has not been considered either.This study aimed to report the particle size and shape analysis of five iron-based oxygen carriers,one natural ore,one synthetic material,and three residue products,at different oxidation degrees using dynamic image analysis(DIA).The oxygen carriers were prepared at different mass conversion degrees in a fluidized bed batch reactor.The size distribution,sphericity,and aspect ratio of the oxygen carrier particles were examined experimentally using a Camsizer instrument.Our results show that the DIA method was successfully able to analyze the particle size and shape of our oxygen carriers with satisfying accuracy for comparison.The oxidation state of the investigated materials seems to only affect the particle size and shape of oxygen carriers to a minor extent.However,exposures to redox cycles in a fluidized bed reactor may alter the particle size and shape of most oxygen carriers.展开更多
Co_(3)O_(4) is considered as one of promising cathode catalysts for lithium oxygen(Li-O_(2))batteries,which contains both tetrahedral Co^(2+)sites(Co^(2+)Td)and octahedral Co^(3+)sites(Co^(3+)Oh).It is important to re...Co_(3)O_(4) is considered as one of promising cathode catalysts for lithium oxygen(Li-O_(2))batteries,which contains both tetrahedral Co^(2+)sites(Co^(2+)Td)and octahedral Co^(3+)sites(Co^(3+)Oh).It is important to reveal the effect of optimal geometric configuration and oxidation state of cobalt ion in Co_(3)O_(4) to improve the performance of Li-O_(2) batteries.Herein,through regulating the synthesis process,Co^(2+)and Co^(3+)sites in Co_(3)O_(4) were replaced with Zn and Al atoms to form materials with a unique Co site.The Li-O_(2) batteries based on ZnCo_(2)O_(4) showed longer cycle life than that of CoAl_(2)O_(4),suggesting that in Co_(3)O_(4),the Co^(3+)Oh site is a relatively better geometric configuration than Co^(2+)Td site for Li-O_(2) batteries.Theoretical calculations revealed that Co^(3+)Oh sites provide higher catalysis activity,regulating the adsorption energy of the intermediate LiO_(2) and accelerating the kinetics of the reaction in batteries,which further leads to the change of the morphology of the discharge product and ultimately improves the electrochemical performance of the batteries.展开更多
Relativistic quantum chemistry investigations are carried out to tackle the puzzling oxidation state problem in a series of MO3 trioxide anions of all d- and f-block elements with five valence electrons. We have shown...Relativistic quantum chemistry investigations are carried out to tackle the puzzling oxidation state problem in a series of MO3 trioxide anions of all d- and f-block elements with five valence electrons. We have shown here that while the oxidation states of V, Nb, Ta, Db, Pa are, as usual, all ＋V with divalent oxygen O（-II） in MO3- anions, the lanthanide elements Pr and Gd cannot adopt such high ＋V oxidation state in similar trioxide anions. Instead, lanthanide element Gd retains its usual ＋III oxi- dation state, while Pr retains a ＋IV oxidation state, thus forcing oxygen into a non-innocent ligand with an uncommon mono- valent radical （O＇） of oxidation state -I. A unique Pr＂- ＂（0）3 biradical with highly delocalized unpairing electron density on Pr（IV） and three O atoms is found to be responsible for stabilizing the monovalent-oxygen species in PRO3- ion, while GdO3 ion is in fact an OGd＋（O22-） complex with Gd（III）. These results show that a naive assignment of oxidation state of a chemical element without electronic structure analysis can lead to erroneous conclusions.展开更多
The high price of state-of-the-art Pt electrocatalysts has plagued the acidic water electrolysis technique for decades. As a cheaper alternative to Pt, ruthenium is considered an inferior hydrogen evolution reaction (...The high price of state-of-the-art Pt electrocatalysts has plagued the acidic water electrolysis technique for decades. As a cheaper alternative to Pt, ruthenium is considered an inferior hydrogen evolution reaction (HER) catalyst than Pt due to its high susceptibility to oxidation and loss of activity. Herein, we reveal that the HER activity on Ru based catalysts could surpass Pt via tuning Ru oxidation state. Specifically, RuP clusters encapsulated in few layers of N, P-doped carbon (RuP@NPC) display a minimum over potential of 15.6 mV to deliver 10 mA·cm^(−2). Moreover, we for the first time show that a Ru based catalyst could afford current density up to 4 A·cm^(−2) in a practical water electrolysis cell, with voltage even lower than the Pt/C-based cell, as well as high robustness during 200 h operation. Using a combination of experiment probing and calculation, we postulate that the suitably charged Ru (∼ +2.4) catalytic center is the origin for its superior catalytic behavior. While the moderately charged Ru is empowered with optimized H adsorption behavior, the carbon encapsulation layers protect RuP clusters from over oxidation, thereby conferring the catalyst with high robustness.展开更多
Electrocatalysts for the oxygen reduction reaction(ORR)are critically important in the development of fuel cells and metal-air batteries.Intensive research interests have been devoted to improving the electrocatalytic...Electrocatalysts for the oxygen reduction reaction(ORR)are critically important in the development of fuel cells and metal-air batteries.Intensive research interests have been devoted to improving the electrocatalytic performance by tuning the morphology and defect-active sites.Herein,we demonstrate that the oxidation state can also serve as an effective strategy for designingORR electrocatalysts.Valencemodels of silver with gradient chemical valence from zero valence to trivalence were successfully built.Their oxidation states were evaluated by cryo-X-ray photoelectron spectroscopy,X-ray absorptionfinestructure,and electron paramagnetic resonance spectroscopy.For the first time,our results demonstrated that the electrocatalytic activities of silver species can be improved by increasing their valence,conforming the orderofAg<Ag_(2)O<Ag_(2)O_(2)<Ag_(3)O_(4)<Ag_(2)O_(3).Computational studies reveal that higher valence Ag species possess a higher proportion of d band holes andmore electrons closer to the Fermi level.Therefore,the oxygen adsorption and activation energy on the Ag sites can be regulated to a near-optimal level and the ORR catalytic efficiency increases.This work clearly presents that oxidation state is another degree of freedom in designing efficient ORR electrocatalysts.展开更多
Electrocatalytic nitrate reduction reaction (NO_(3)-RR) to ammonia under ambient conditions is expected to be a green process for ammonia synthesis and alleviate water pollution issues.We report a CuO nanoparticles in...Electrocatalytic nitrate reduction reaction (NO_(3)-RR) to ammonia under ambient conditions is expected to be a green process for ammonia synthesis and alleviate water pollution issues.We report a CuO nanoparticles incorporated on nitrogen-doped porous carbon (CuO@NC) catalyst for NO_(3)-RR.Part of Cu(Ⅱ) is reduced to Cu(Ⅰ) during the NO_(3)-RR process to construct Cu(Ⅰ)-Cu(Ⅱ) pairs,confirmed by in situ X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy.Density functional theory (DFT) calculations indicated that the formation of Cu(Ⅰ) could provide a reaction path with smaller energy barrier for NO_(3)-RR,while Cu(Ⅱ) effectively suppressed the competition of hydrogen evolution reaction (HER).As a result,CuO@NC catalyst achieved a Faradaic efficiency of 84.2% at -0.49 V versus reversible hydrogen electrode (RHE),and a NH_(3)yield rate of 17.2 mg h^(-1)mg^(-1)cat.at -0.79 V vs.RHE,higher than the HaberBosch process (<3.4 g h^(-1)g^(-1)cat.).This work may open a new avenue for effective NO_(3)-RR by modulating oxidation states.展开更多
Cobalt pentlandite(Co9S8)is a promising non-precious catalyst due to its superior oxygen reduction reaction activity and excellent stability.However,its oxygen reduction reaction catalytic activity has traditionally b...Cobalt pentlandite(Co9S8)is a promising non-precious catalyst due to its superior oxygen reduction reaction activity and excellent stability.However,its oxygen reduction reaction catalytic activity has traditionally been limited to the four-electron pathway because of strong*OOH intermediate adsorption.In this study,we synthesized electron-deficient Co9S8 nanocrystals with an increased number of Co^(3+)states compared to conventional Co9S8.This was achieved by incorporating a high density of surface ligands in small-sized Co9S8nanocrystals,which enabled the transition of the electrochemical reduction pathway from four-electron oxygen reduction reaction to two-electron oxygen reduction reaction by decreasing*OOH adsorption strength.As a result,the Co^(3+)-enriched Co9S8 nanocrystals exhibited a high onset potential of 0.64 V(vs RHE)for two-electron oxygen reduction reaction,achieving H_(2)O_(2) selectivity of 70-80%over the potential range from 0.05 to 0.6 V.Additionally,these nanocrystals demonstrated a stable H_(2)O_(2) electrosynthesis at a rate of459.12 mmol g^(-1) h^(-1) with a H_(2)O_(2) Faradaic efficiency over 90%under alkaline conditions.This study provides insights into nanoscale catalyst design for modulating electrochemical reactions.展开更多
Biogenic manganese oxides （BioMnOx） were synthesized by the oxidation of Mn（II） with Mn- oxidizing bacteria Pseudomonas sp. G7 under different initial pH values and Mn（II） dosages, and were characterized by X-ra...Biogenic manganese oxides （BioMnOx） were synthesized by the oxidation of Mn（II） with Mn- oxidizing bacteria Pseudomonas sp. G7 under different initial pH values and Mn（II） dosages, and were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and UV-Vis absorption spectroscopy. The crystal structure and Mn oxidation states of BioMnOx depended on the initial pH and Mn（lI） dosages of the medium. The superoxide radical （O2） was observed in Mn-containing （III/IV） BioMnOx suspensions by electron spin resonance measurements. BioMnOx（0.4）-7, with mixed valence of Mn（II/III/IV） and the strongest O^- signals, was prepared in the initial pH 7 and Mn（II） dosage of 0.4 mmol/L condition, and exhibited the highest activity for ciproftoxacin degradation and no Mn（II） release. During the degradation of ciprofloxacin, the oxidation of the Mn（II） formed came from biotic and abiotic reactions in BioMnOx suspensions on the basis of the Mn（II） release and O2- formation from different BioMnOx. The degradation process of ciprofloxacin was shown to involve the cleavage of the hexatomic ring having a secondary amine and carbon-carbon double bond connected to a carboxyl group, producing several compounds containing amine groups as well as small organic acids.展开更多
Manganese-based perovskite is popular for research on ferromagnetic materials,and its spectroscopic studies are essential for understanding its electronic structure,dielectric,electrical,and magnetic properties.In thi...Manganese-based perovskite is popular for research on ferromagnetic materials,and its spectroscopic studies are essential for understanding its electronic structure,dielectric,electrical,and magnetic properties.In this paper,the M-edge spectra of La ions and the M-edge,L-edge,and K-edge spectra of Mn ions in LaMnO3 are calculated by considering both the free-ion multiplet calculation and the crystal field effects.We analyze spectral shapes,identify peak origins,and estimate the oxidation states of La and Mn ions in LaMnO3 theoretically.It is concluded that La ions in LaMnO3 predominantly exist in the trivalent state,while Mn ions exist primarily in the trivalent state with a minor presence of tetravalent ions.Furthermore,the calculated spectra are in better conformity with the experimental spectra when the proportion of Mn3+is 90%and Mn4+is 10%.This article enhances our comprehension of the oxidation states of La and Mn within the crystal and also provides a valuable guidance for spectroscopic investigations of other manganates.展开更多
Sulfate adsorption by poly（m-phenylenediamine）s（PmPDs） with various oxidation states synthesized through chemically oxidative polymerization was investigated.Series of sorption experiments were conducted,and the a...Sulfate adsorption by poly（m-phenylenediamine）s（PmPDs） with various oxidation states synthesized through chemically oxidative polymerization was investigated.Series of sorption experiments were conducted,and the adsorption mechanism and the relationship between oxidation state and adsorption performance were studied with the characterization of Fourier transform infrared spectroscopy（FTIR）,X-ray photoelectron spectroscopy（XPS）,pH tracking and energy calculation.The results show that the adsorption performance in acidic solution is improved with the decrease of oxidation state of poly（m-phenylenediamine）（PmPD）.The rate constant is as high as 425.5 mg/（g·min） in the short equilibrium time of 30 min.The estimated highest adsorptivity of sulfate ions is 95.1%.According to the Langmuir equation,the adsorbance is 108.5 mg/g.The sulfate desorption efficiency is about 95% and the accumulative adsorbance is up to 487.95 mg/g in 5 cycles.展开更多
The mantle xenoliths in the Quaternary ChangbaishanVolcano in southern Jilin Province contain spinel-facies lherzolites. The equilibration temperatures for these samples range from 902℃ to 1064℃ based on the two-pyr...The mantle xenoliths in the Quaternary ChangbaishanVolcano in southern Jilin Province contain spinel-facies lherzolites. The equilibration temperatures for these samples range from 902℃ to 1064℃ based on the two-pyroxene thermometer of Brey and Kohler （1990）, and using the oxybarometry of Nell and Wood （1991）, the oxidation state was estimated from FMQ-1.32 to -0.38 with an average value of FMQ-0.81 （n = 8）, which is comparable to that of abyssal peridotites and the asthenospheric mantle. ThefO2 values of peridotites, together with their bulk rock compositions （e.g., Mg#, Al2O3, CaO, Ni, Co, Cr） and mineral compositions （e.g., Mg# of olivine and pyroxene, Cr# [=Cr/ [Cr＋Al]] and Mg# [=Mg/[Mg＋Fe2~] of spinel）, suggest that the present-day subcontinental lithospheric mantle （SCLM） beneath the Changbaishan Volcano most likely formed from an upwelling asthenosphere at some time after the late Mesozoic and has undergone a low degree of partial melting. The studied lherzolite xenoliths show low concentrations of S, Cu, and platinum group elements （PGE）, which plot a flat pattern on primitive-mantle normalized diagram. Very low concentrations in our samples suggest that PGEs occur as alloys or hosted by silicate and oxide minerals. The compositions of the studied samples are similar to those of peridotite xenoliths in the Longgang volcanic field （LVF） in their mineralogy and bulk rock compositions including the abundance of chalcophile and siderophile elements. However, they are distinctly different from those of peridotite xenoliths in other areas of the North China Craton （NCC） in terms of Cu, S and PGE. Our data suggest that the SCLM underlying the northeastern part of the NCC may represent a distinct unit of the newly formed lithospberic mantle.展开更多
Rhenium is one of important components for heterogeneous catalysts,which has been recently used for the catalytic reactions related to the production of biomass-derived chemicals such as deoxydehydration of vicinal OH...Rhenium is one of important components for heterogeneous catalysts,which has been recently used for the catalytic reactions related to the production of biomass-derived chemicals such as deoxydehydration of vicinal OH groups,C-O hydrogenolysis,and hydrogenation of carboxylic acids,and so on.Suitable oxidation state of Re as a catalytic active species is strongly dependent on the catalytic reactions.The control of the oxidation state of Re species on the catalysts is crucial on the catalyst development.展开更多
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(RS-2024-00340074,RS-2024-00409901,2022M3I3A1081901,and RS-2024-00413272)。
文摘The harsh corrosive environment and sluggish oxygen evolution reaction(OER)kinetics at the anode of proton exchange membrane water electrolysis(PEMWE)cells warrant the use of excess Ir,thereby hindering large-scale industrialization.To mitigate these issues,the present study aimed at fabricating a robust low-Ir-loading electrode via one-pot synthesis for efficient PEMWE.The pre-electrode was first prepared by alloying through the co-electrodeposition of Ir and Co,followed by the fabrication of Ir–Co oxide(Co-incorporated Ir oxide)electrodes via electrochemical dealloying.Two distinct dealloying techniques resulted in a modified valence state of Ir,and the effects of Co incorporation on the activity and stability of the OER catalysts were clarified using density functional theory(DFT)calculations,which offered theoretical insights into the reaction mechanism.While direct experimental validation of the oxygen evolution mechanism remains challenging under the current conditions,DFT-based theoretical modeling provided valuable perspectives on how Co incorporation could influence key steps in oxygen evolution catalysis.The Ir–Co oxide electrode with a selectively modulated valence state showed impressive performance with an overpotential of 258 mV at 10 mA cm^(−2),a low Tafel slope of 29.4 mV dec^(−1),and stability for 100 h at 100 mA cm^(−2)in the OER,in addition to a low overpotential of 16 mV at−10 mA cm^(−2)and high stability for 24 h in the hydrogen evolution reaction.The PEMWE cell equipped with the bifunctional Ir–Co oxide electrode as the anode and cathode exhibited outstanding performance(11.4 A cm^(−2)at 2.3 Vcell)despite having a low noble-metal content of 0.4 mgNM cm^(−2).
基金supported by the National Natural Science Foundation of China(Grant Nos.51991351 and51903132)the Young Elite Scientist Sponsorship Program by CAST(No.2022QNRC001).
文摘Different reactive flame retardants have been extensively developed for vinyl ester resins(VERs),but very few of them can yield a flame-retardant resin that meets defined standards(e.g.UL-94 V-0 rating).In this work,phosphorous-containing 1-vinylimidazole salts(called VIDHP and VIDPP)were synthesized through the facile neutralization of the acid and 1-vinylimidazole.VIDHP and VIDPP were then applied as flame-retardant crosslinking agents of VERs,by which phosphorus-containing groups could be incorporated into the resin chain via ionic bonds.VIDHP/VER and VIDPP/VER showed a high curing activity and can be well cured in moderate temperatures.With 20 wt.%additions of VIDHP and VIDPP,VIDHP20/VER,and VIDPP20/VER presented a limiting oxygen index value of 29.7%and 28.4%,respectively,with the latter achieving a UL 94 V0 rating.In the cone calorimetric test,compared to the unmodified VERs,VIDPP20/VER exhibited large reductions in the peak heat release rate,total heat release rate,and total smoke release rate while VIDHP20/VER demonstrated comparatively inferior performance in terms of the heat release.VIDHP20/VER and VIDPP20/VER showed good thermal stability and presented a little lower glass transition temperature than the control sample.VIDPP with a low phosphorus oxidation state(+1)demonstrated high flame-retardant activities in the gaseous phase,whereas VIDHP with a high phosphorus oxidation state(+5)primarily exhibited efficacy in the condensed phase.
基金supported by the National Key Research and Development Program of China(2021YFA1500500)。
文摘The highly selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dihydroxymethylfuran is an important reaction in the field of biomass hydrogenation,because it is a bridge between biomass resources and chemical industry.Here,we precisely constructed carbon nitride supported Pd-based catalysts by a simple impregnation-reduction method.By changing the reduction temperature,catalysts with different oxidation state could be precisely constructed.Moreover,the important correlation between the ratio of Pd^(0)/Pd^(2+)and catalytic activity is revealed during the selective hydrogenation of HMF.The Pd/g—C_(3)N_(4)—300 catalyst with a Pd^(0)/Pd^(2+)ratio of 3/2 showed the highest catalytic activity,which could get 96.9%5-hydroxymethylfurfural conversion and 90.3%2,5-dihydroxymethylfuran selectivity.Further density functional theory calculation revealed that the synergistic effect between Pd0and Pd2+in Pd/g—C_(3)N_(4)—300 system could boost the adsorption of the substrate and the dissociation of hydrogen.In this work,we highlight the important correlation between metal oxidation state and catalytic activity,which provides valuable insights for the rational design of precious metal catalysts for hydrogenation reactions.
基金Funded by the National Natural Science Foundation of China(No.50972136)
文摘The oxidation state of sulfur is detected in Na20-CaO-SiO2 float glass by synchrotron radiation X-ray absorption near edge structure （XANES） spectra at the sulfur K edge. The measured spectra show the only presence of S^6＋ in the Na20-CaO-SiO2 float glass and the oxidation state of sulfur do not change with the increase of glass depth. It is also found that, after the melt has gone through the molten tin bath, the S^6＋ is the dominant species, but S^2- is also present on both surfaces. It is not certain whether cation bonds to S^2- or not, because there are many cations dissolved in the melted tin which makes the spectrum complicated.
基金supported by NIH grant No. 2 R01 ES010845 to M.S.the UNC Nutrition Obesity Research Center grant no. DK056350,+1 种基金NIH grant No. P30ES010126 to the UNC Center for Environmental Health and Susceptibilitysupported by a pre-doctoral traineeship (National Research Service Award T32 ES007126) from the National Institute of Environmental Health Sciences, NIH
文摘Arsenic methyltransferase（As3mt） catalyzes the conversion of inorganic arsenic（i As） to its methylated metabolites, including toxic methylarsonite（MAs~Ⅲ） and dimethylarsinite（DMAs~Ⅲ）. Knockout（KO） of As3 mt was shown to reduce the capacity to methylate i As in mice. However, no data are available on the oxidation states of As species in tissues of these mice. Here, we compare the oxidation states of As species in tissues of male C57BL/6 As3mt-KO and wild-type（WT） mice exposed to arsenite（iA s~Ⅲ） in drinking water. WT mice were exposed to50 mg/L As and As3mt-KO mice that cannot tolerate 50 mg/L As were exposed to 0, 15, 20, 25 or30 mg/L As. iA s~Ⅲaccounted for 53% to 74% of total As in liver, pancreas, adipose, lung, heart, and kidney of As3mt-KO mice; tri- and pentavalent methylated arsenicals did not exceed 10% of total As. Tissues of WT mice retained iA s and methylated arsenicals： iA s~Ⅲ, MAs~Ⅲand DMAs~Ⅲ represented 55%‐68% of the total As in the liver, pancreas, and brain. High levels of methylated species, particularly MAs~Ⅲ, were found in the intestine of WT, but not As3mt-KO mice,suggesting that intestinal bacteria are not a major source of methylated As. Blood of WT mice contained significantly higher levels of As than blood of As3mt-KO mice. This study is the first to determine oxidation states of As species in tissues of As3mt-KO mice. Results will help to design studies using WT and As3mt-KO mice to examine the role of iA s methylation in adverse effects of iA s exposure.
文摘A method determining di-and tri-valeht cobalt extracted from soils with EDTA·2HOAc·NH4OAc solution (pH 4.65) was developed based on the difference of the stability constants of Co(II)EDTA and Co(III)EDTA. Analytical results indicated that soil cobalt existed in both two oxidation states, i. e. , di-and tri-valent cobalt. Extractable di-valent cobalt in 60 soil samples collected from various soils in China ranged from 0.02 ppm to 3.54 ppm, with the mean of 0.62 ppm, and extractable tri-valent cobalt from 0.04 ppm to 27.65 ppm, with the mean of 2.93 ppm.
基金supported by the National Natural Science Foundation of China(No.52221004)the Shenzhen Science and Technology Program(No.RCJC20221008092758099)+1 种基金the Shenzhen Pengrui Young Faculty Program of Shenzhen Pengrui Foundation(No.SZPR2023004)the Guangdong Higher Education Institutions Innovative Research Team of Urban Water Cycle and Ecological Safety(No.2023KCXTD053).
文摘Electrocatalytic CO_(2) reduction(ECR)is a promising approach for achieving carbon neutrality due to its ability to convert CO_(2) to valuable chemicals.Recent advances have significantly enhanced the ECR performance of various catalysts by tuning their oxidation states,particularly for Cu-based catalysts that can reduce CO_(2) to multiple products.However,the oxidation state of copper(OSCu),especially Cu+,changes during the reaction process,posing significant challenges for both catalyst characterization and performance.In this review,the current understanding of the effect of oxidation states on product selectivity was first discussed.A comprehensive overview of in situ/operando characterization techniques,used to monitor the dynamic evolution of oxidation states during ECR,was then provided.Various strategies for stabilizing oxidation states through modification of catalysts and manipulation of external conditions were discussed.This review aimed to deepen the understanding of oxidation states in ECR and enlighten the development of more efficient electrocatalysts.
基金supported by the Agency for Science,Technology and Research Singapore through its Manufacturing,Trade and Connectivity Individual Research Grant(grant no.M22K2c0077)the National Natural Science Foundation of China(grant nos.21788102,22375066,21874121,and 21974128)the Guangdong Basic and Applied Basic Research Foundation(grant nos.2023B1515040003 and 2022A1515010315).
文摘Photoresponsive materials are considered as promising systems for intelligent technology applications owing to the contactless spatial and temporal control.Herein,controllable multi-photoresponsive behaviors are realized in benzo[b]thiophene derivatives(o-DMP-S,o-DMP-SO,and o-DMP-SO_(2))by modulating the sulfur oxidation state.Among them,o-DMP-S is photo-unreactive but possesses denser molecular packing upon ultraviolet(UV)light irradiation,exhibiting photoenhanced room-temperature phosphorescence properties.Through stoichiometric oxidation of the sulfur atom in o-DMP-S,the resulting sulfoxide compound o-DMP-SO undergoes a radical photolysis reaction involving photodeoxygenation and photochemical rearrangement,thereby leading to the photomechanical effect.The sulfone compound o-DMP-SO_(2)displays prominent reversible photochromism,resulting from the radical photocyclization under 365 nm UV light irradiation.Based on comprehensive experimental and computational investigations,the diverse photoresponsive behaviors of these benzo[b]thiophene derivatives are demonstrated to depend on the intersystem crossing efficiency and radical-mediated photochemical reaction activity in excited states due to the different sulfur oxidation states.This work provides an insightful understanding of the relationship between molecular structure and photoresponsive behavior and opens up the opportunity for the development of photoresponsive materials with potential applications.
基金the project EU CLARA(Chemical Looping Gasification for Sustainable Production of Biofuels),which has received funding from the European Union's Horizon 2020 research and innovation program under grant agreement No 817841the Swedish Energy Agency(Project 51430-1)and Stiftelsen AForsk(Project 20-269).Boliden AB is acknowledged for iron sand sourcing.The authors would like to thank Bio4Energy,a Strategic Research Environment appointed by the Swedish government.
文摘One of the crucial issues in the chemical looping technology lies in its bed material:the oxygen carrier.Particle size analysis of an oxygen carrier is important since in a fluidized bed the material can only work well within a specific size range.While the favorable size ranges for oxygen carrier materials have already been reported,none of the published studies has analyzed the particle size and shape of oxygen carriers in detail.Furthermore,the effect of oxygen carriers'oxidation degree on such properties has not been considered either.This study aimed to report the particle size and shape analysis of five iron-based oxygen carriers,one natural ore,one synthetic material,and three residue products,at different oxidation degrees using dynamic image analysis(DIA).The oxygen carriers were prepared at different mass conversion degrees in a fluidized bed batch reactor.The size distribution,sphericity,and aspect ratio of the oxygen carrier particles were examined experimentally using a Camsizer instrument.Our results show that the DIA method was successfully able to analyze the particle size and shape of our oxygen carriers with satisfying accuracy for comparison.The oxidation state of the investigated materials seems to only affect the particle size and shape of oxygen carriers to a minor extent.However,exposures to redox cycles in a fluidized bed reactor may alter the particle size and shape of most oxygen carriers.
基金supported by the National Key R&D Program of China(No.2021YFF0500503)the National Natural Science Foundation of China(Nos.21925202 and U22B2071).
文摘Co_(3)O_(4) is considered as one of promising cathode catalysts for lithium oxygen(Li-O_(2))batteries,which contains both tetrahedral Co^(2+)sites(Co^(2+)Td)and octahedral Co^(3+)sites(Co^(3+)Oh).It is important to reveal the effect of optimal geometric configuration and oxidation state of cobalt ion in Co_(3)O_(4) to improve the performance of Li-O_(2) batteries.Herein,through regulating the synthesis process,Co^(2+)and Co^(3+)sites in Co_(3)O_(4) were replaced with Zn and Al atoms to form materials with a unique Co site.The Li-O_(2) batteries based on ZnCo_(2)O_(4) showed longer cycle life than that of CoAl_(2)O_(4),suggesting that in Co_(3)O_(4),the Co^(3+)Oh site is a relatively better geometric configuration than Co^(2+)Td site for Li-O_(2) batteries.Theoretical calculations revealed that Co^(3+)Oh sites provide higher catalysis activity,regulating the adsorption energy of the intermediate LiO_(2) and accelerating the kinetics of the reaction in batteries,which further leads to the change of the morphology of the discharge product and ultimately improves the electrochemical performance of the batteries.
基金supported by the National Basic Research Program of China(2013CB834603)the National Natural Science Foundation of China(21173053,21433005,91426302,21221062,21201106)
文摘Relativistic quantum chemistry investigations are carried out to tackle the puzzling oxidation state problem in a series of MO3 trioxide anions of all d- and f-block elements with five valence electrons. We have shown here that while the oxidation states of V, Nb, Ta, Db, Pa are, as usual, all ＋V with divalent oxygen O（-II） in MO3- anions, the lanthanide elements Pr and Gd cannot adopt such high ＋V oxidation state in similar trioxide anions. Instead, lanthanide element Gd retains its usual ＋III oxi- dation state, while Pr retains a ＋IV oxidation state, thus forcing oxygen into a non-innocent ligand with an uncommon mono- valent radical （O＇） of oxidation state -I. A unique Pr＂- ＂（0）3 biradical with highly delocalized unpairing electron density on Pr（IV） and three O atoms is found to be responsible for stabilizing the monovalent-oxygen species in PRO3- ion, while GdO3 ion is in fact an OGd＋（O22-） complex with Gd（III）. These results show that a naive assignment of oxidation state of a chemical element without electronic structure analysis can lead to erroneous conclusions.
基金The authors acknowledge funding from the National Key R&D Program of China (No. 2018YFB1502400)the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDA21090400)the Jilin Province Science and Technology Development Program (Nos. 20190201300JC and 20180101030JC).
文摘The high price of state-of-the-art Pt electrocatalysts has plagued the acidic water electrolysis technique for decades. As a cheaper alternative to Pt, ruthenium is considered an inferior hydrogen evolution reaction (HER) catalyst than Pt due to its high susceptibility to oxidation and loss of activity. Herein, we reveal that the HER activity on Ru based catalysts could surpass Pt via tuning Ru oxidation state. Specifically, RuP clusters encapsulated in few layers of N, P-doped carbon (RuP@NPC) display a minimum over potential of 15.6 mV to deliver 10 mA·cm^(−2). Moreover, we for the first time show that a Ru based catalyst could afford current density up to 4 A·cm^(−2) in a practical water electrolysis cell, with voltage even lower than the Pt/C-based cell, as well as high robustness during 200 h operation. Using a combination of experiment probing and calculation, we postulate that the suitably charged Ru (∼ +2.4) catalytic center is the origin for its superior catalytic behavior. While the moderately charged Ru is empowered with optimized H adsorption behavior, the carbon encapsulation layers protect RuP clusters from over oxidation, thereby conferring the catalyst with high robustness.
基金This work was financially supported by the Basic Research Project of the Science and Technology Innovation Commission of Shenzhen(no.JCYJ20200109141640095)the Shenzhen Key Laboratory of Interfacial Science and Engineering of Materials(no.ZDSYS20200421111401738)+3 种基金the Leading Talents of Guangdong Province Program(no.2016LJ06C536)the National Natural Science Foundation of China(no.21875097)Z.J.and G.L.were supported by the Introduced Innovative R&D Team of Guangdong(no.2017ZT07C062)the fund of the Guangdong Provincial Key Laboratory of Computational Science and Material Design(no.2019B030301001).
文摘Electrocatalysts for the oxygen reduction reaction(ORR)are critically important in the development of fuel cells and metal-air batteries.Intensive research interests have been devoted to improving the electrocatalytic performance by tuning the morphology and defect-active sites.Herein,we demonstrate that the oxidation state can also serve as an effective strategy for designingORR electrocatalysts.Valencemodels of silver with gradient chemical valence from zero valence to trivalence were successfully built.Their oxidation states were evaluated by cryo-X-ray photoelectron spectroscopy,X-ray absorptionfinestructure,and electron paramagnetic resonance spectroscopy.For the first time,our results demonstrated that the electrocatalytic activities of silver species can be improved by increasing their valence,conforming the orderofAg<Ag_(2)O<Ag_(2)O_(2)<Ag_(3)O_(4)<Ag_(2)O_(3).Computational studies reveal that higher valence Ag species possess a higher proportion of d band holes andmore electrons closer to the Fermi level.Therefore,the oxygen adsorption and activation energy on the Ag sites can be regulated to a near-optimal level and the ORR catalytic efficiency increases.This work clearly presents that oxidation state is another degree of freedom in designing efficient ORR electrocatalysts.
基金National Natural Science Foundation of China (52371228, 52402045)fund of Key Laboratory of Advanced Materials of Ministry of Education(Advmat-2414)。
文摘Electrocatalytic nitrate reduction reaction (NO_(3)-RR) to ammonia under ambient conditions is expected to be a green process for ammonia synthesis and alleviate water pollution issues.We report a CuO nanoparticles incorporated on nitrogen-doped porous carbon (CuO@NC) catalyst for NO_(3)-RR.Part of Cu(Ⅱ) is reduced to Cu(Ⅰ) during the NO_(3)-RR process to construct Cu(Ⅰ)-Cu(Ⅱ) pairs,confirmed by in situ X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy.Density functional theory (DFT) calculations indicated that the formation of Cu(Ⅰ) could provide a reaction path with smaller energy barrier for NO_(3)-RR,while Cu(Ⅱ) effectively suppressed the competition of hydrogen evolution reaction (HER).As a result,CuO@NC catalyst achieved a Faradaic efficiency of 84.2% at -0.49 V versus reversible hydrogen electrode (RHE),and a NH_(3)yield rate of 17.2 mg h^(-1)mg^(-1)cat.at -0.79 V vs.RHE,higher than the HaberBosch process (<3.4 g h^(-1)g^(-1)cat.).This work may open a new avenue for effective NO_(3)-RR by modulating oxidation states.
基金supported by the Korea Institute of Energy Technology Evaluation and Planning(KETEP)and the Ministry of Trade,Industry&Energy(MOTIE)of the Republic of Korea(no.20224000000020)supported by the MSIT(Ministry of Science and ICT),Korea,under the ICAN(ICT Challenge and Advanced Network of HRD)support program(IITP-2024-RS-2024-00437186)supervised by the IITP(Institute for Information&Communications Technology Planning&Evaluation)。
文摘Cobalt pentlandite(Co9S8)is a promising non-precious catalyst due to its superior oxygen reduction reaction activity and excellent stability.However,its oxygen reduction reaction catalytic activity has traditionally been limited to the four-electron pathway because of strong*OOH intermediate adsorption.In this study,we synthesized electron-deficient Co9S8 nanocrystals with an increased number of Co^(3+)states compared to conventional Co9S8.This was achieved by incorporating a high density of surface ligands in small-sized Co9S8nanocrystals,which enabled the transition of the electrochemical reduction pathway from four-electron oxygen reduction reaction to two-electron oxygen reduction reaction by decreasing*OOH adsorption strength.As a result,the Co^(3+)-enriched Co9S8 nanocrystals exhibited a high onset potential of 0.64 V(vs RHE)for two-electron oxygen reduction reaction,achieving H_(2)O_(2) selectivity of 70-80%over the potential range from 0.05 to 0.6 V.Additionally,these nanocrystals demonstrated a stable H_(2)O_(2) electrosynthesis at a rate of459.12 mmol g^(-1) h^(-1) with a H_(2)O_(2) Faradaic efficiency over 90%under alkaline conditions.This study provides insights into nanoscale catalyst design for modulating electrochemical reactions.
基金supported by the National Natural Science Foundation of China(No.51138009,21125731,51221892)the National High Technology Research and Development Program of China(No.2012AA062606)the project of the Chinese Academy of Sciences(No.KZCX2-EW-410)
文摘Biogenic manganese oxides （BioMnOx） were synthesized by the oxidation of Mn（II） with Mn- oxidizing bacteria Pseudomonas sp. G7 under different initial pH values and Mn（II） dosages, and were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and UV-Vis absorption spectroscopy. The crystal structure and Mn oxidation states of BioMnOx depended on the initial pH and Mn（lI） dosages of the medium. The superoxide radical （O2） was observed in Mn-containing （III/IV） BioMnOx suspensions by electron spin resonance measurements. BioMnOx（0.4）-7, with mixed valence of Mn（II/III/IV） and the strongest O^- signals, was prepared in the initial pH 7 and Mn（II） dosage of 0.4 mmol/L condition, and exhibited the highest activity for ciproftoxacin degradation and no Mn（II） release. During the degradation of ciprofloxacin, the oxidation of the Mn（II） formed came from biotic and abiotic reactions in BioMnOx suspensions on the basis of the Mn（II） release and O2- formation from different BioMnOx. The degradation process of ciprofloxacin was shown to involve the cleavage of the hexatomic ring having a secondary amine and carbon-carbon double bond connected to a carboxyl group, producing several compounds containing amine groups as well as small organic acids.
基金Project supported by the National Natural Science Foundation of China(Grant No.11974253).
文摘Manganese-based perovskite is popular for research on ferromagnetic materials,and its spectroscopic studies are essential for understanding its electronic structure,dielectric,electrical,and magnetic properties.In this paper,the M-edge spectra of La ions and the M-edge,L-edge,and K-edge spectra of Mn ions in LaMnO3 are calculated by considering both the free-ion multiplet calculation and the crystal field effects.We analyze spectral shapes,identify peak origins,and estimate the oxidation states of La and Mn ions in LaMnO3 theoretically.It is concluded that La ions in LaMnO3 predominantly exist in the trivalent state,while Mn ions exist primarily in the trivalent state with a minor presence of tetravalent ions.Furthermore,the calculated spectra are in better conformity with the experimental spectra when the proportion of Mn3+is 90%and Mn4+is 10%.This article enhances our comprehension of the oxidation states of La and Mn within the crystal and also provides a valuable guidance for spectroscopic investigations of other manganates.
基金Project(50925417) supported by China National Funds for Distinguished Young ScientistsProject(50830301) supported by the National Natural Science Foundation of China+1 种基金Project(2009ZX07212-001-01) supported by Major Science and Technology Program for Water Pollution Control and Treatment of ChinaProject(2011) supported by Hunan Nonferrous Fundamental Research Fund
文摘Sulfate adsorption by poly（m-phenylenediamine）s（PmPDs） with various oxidation states synthesized through chemically oxidative polymerization was investigated.Series of sorption experiments were conducted,and the adsorption mechanism and the relationship between oxidation state and adsorption performance were studied with the characterization of Fourier transform infrared spectroscopy（FTIR）,X-ray photoelectron spectroscopy（XPS）,pH tracking and energy calculation.The results show that the adsorption performance in acidic solution is improved with the decrease of oxidation state of poly（m-phenylenediamine）（PmPD）.The rate constant is as high as 425.5 mg/（g·min） in the short equilibrium time of 30 min.The estimated highest adsorptivity of sulfate ions is 95.1%.According to the Langmuir equation,the adsorbance is 108.5 mg/g.The sulfate desorption efficiency is about 95% and the accumulative adsorbance is up to 487.95 mg/g in 5 cycles.
基金supported by grants from National Natural Science Foundation of China (Nos.40873016,41173034,90814003)supportedby a grant from China Geological Survey (No.1212011121088)
文摘The mantle xenoliths in the Quaternary ChangbaishanVolcano in southern Jilin Province contain spinel-facies lherzolites. The equilibration temperatures for these samples range from 902℃ to 1064℃ based on the two-pyroxene thermometer of Brey and Kohler （1990）, and using the oxybarometry of Nell and Wood （1991）, the oxidation state was estimated from FMQ-1.32 to -0.38 with an average value of FMQ-0.81 （n = 8）, which is comparable to that of abyssal peridotites and the asthenospheric mantle. ThefO2 values of peridotites, together with their bulk rock compositions （e.g., Mg#, Al2O3, CaO, Ni, Co, Cr） and mineral compositions （e.g., Mg# of olivine and pyroxene, Cr# [=Cr/ [Cr＋Al]] and Mg# [=Mg/[Mg＋Fe2~] of spinel）, suggest that the present-day subcontinental lithospheric mantle （SCLM） beneath the Changbaishan Volcano most likely formed from an upwelling asthenosphere at some time after the late Mesozoic and has undergone a low degree of partial melting. The studied lherzolite xenoliths show low concentrations of S, Cu, and platinum group elements （PGE）, which plot a flat pattern on primitive-mantle normalized diagram. Very low concentrations in our samples suggest that PGEs occur as alloys or hosted by silicate and oxide minerals. The compositions of the studied samples are similar to those of peridotite xenoliths in the Longgang volcanic field （LVF） in their mineralogy and bulk rock compositions including the abundance of chalcophile and siderophile elements. However, they are distinctly different from those of peridotite xenoliths in other areas of the North China Craton （NCC） in terms of Cu, S and PGE. Our data suggest that the SCLM underlying the northeastern part of the NCC may represent a distinct unit of the newly formed lithospberic mantle.
文摘Rhenium is one of important components for heterogeneous catalysts,which has been recently used for the catalytic reactions related to the production of biomass-derived chemicals such as deoxydehydration of vicinal OH groups,C-O hydrogenolysis,and hydrogenation of carboxylic acids,and so on.Suitable oxidation state of Re as a catalytic active species is strongly dependent on the catalytic reactions.The control of the oxidation state of Re species on the catalysts is crucial on the catalyst development.
