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
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 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
Vanadium is a strategic metal in many countries,and it is mainly extracted from vanadium slag produced in titanomagnetite metallurgy.The traditional sodium roasting process for vanadium extraction poses environmental ...Vanadium is a strategic metal in many countries,and it is mainly extracted from vanadium slag produced in titanomagnetite metallurgy.The traditional sodium roasting process for vanadium extraction poses environmental threats,and a green calcification pro-cess has been proposed.However,the vanadium extraction rate in the calcification process is much lower than in the sodium roasting pro-cess,which is related to vanadium solid solubility in Fe_(2)TiO_(5).Previous studies about vanadium behavior in Fe_(2)TiO_(5) were conducted in air,with a vanadium oxidation state of V5+.Vanadium with lower oxidation states has been detected in the tailings in the calcification process.The present paper studied the effects of vanadium oxidation states on the solid solubility in Fe_(2)TiO_(5) through solid-state reaction,X-ray diffraction characterization,transmission electron microscopy characterization,X-ray photoelectron spectroscopy analysis,and solid solu-tion modeling.The relative interaction values between vanadium oxides and Fe_(2)TiO_(5) are obtained as|L_(V_(2)O_(3))|>|L_(V_(2)O_(4))|>|L_(V_(2)O_(5)),indicating that vanadium with lower valence is preferable to be solid dissolved in Fe_(2)TiO_(5).The results imply that insufficiently oxidized vanadium increases the vanadium content in the Fe_(2)TiO_(5) phase during vanadium slag’s calcification roasting.Besides,experimental conditions op-timization shows that higher experimental temperature,vanadium introduction as V2O3,and a high-purity argon atmosphere would lead to higher vanadium solubility in Fe_(2)TiO_(5),and high temperature is beneficial for the release of vanadium from vanadium-containing Fe_(2)TiO_(5) when dissociated in air.展开更多
The dominant oxidation state for lanthanide ions is+3 due to the loss of 5d and 6s electrons from their shared configuration of[Xe]4f^(0-14)5d^(0-16)s(2).There are however several exceptions because of the completely ...The dominant oxidation state for lanthanide ions is+3 due to the loss of 5d and 6s electrons from their shared configuration of[Xe]4f^(0-14)5d^(0-16)s(2).There are however several exceptions because of the completely empty(Ce(Ⅳ)),half-filled(Eu(Ⅱ)),or fully filled(Yb(Ⅱ))4f subshell.As such,stable complexes are formed primarily with Ln(Ⅲ)ions[1].展开更多
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
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
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
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
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
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
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
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
The Habo deposit is a typical porphyry Cu-Mo deposit in the Ailaoshan–Red River metallogenic belt.Ore minerals in the Habo deposit typically occur as veins in the monzonite porphyry.Zircon U-Pb dating suggests that t...The Habo deposit is a typical porphyry Cu-Mo deposit in the Ailaoshan–Red River metallogenic belt.Ore minerals in the Habo deposit typically occur as veins in the monzonite porphyry.Zircon U-Pb dating suggests that the monzonite porphyry formed at 35.07±0.38 Ma.The monzonite porphyry is characterized by high SiO_(2),Al_(2)O_(3),K_(2)O and Na_(2)O contents,with A/CNK ratios ranging from 0.97 to 1.02.All samples exhibit fractionated REE patterns,characterized by high(La/Yb)N ratios(9.4–13.6,average of 11.2).They show adakite-like geochemical features,high Sr concentrations(627–751 ppm,average of 700 ppm),low Y concentrations(15.13–16.86 ppm,average of 15.81 ppm)and high Sr/Y values(39.5–47.4,average of 44.3).These samples have high initial^(87)Sr/^(86)Sr ratios(0.7074–0.7076)and negativeεNd(t)values(-5.1 to-3.7),whereas the zirconεHf(t)values range from-2.2 to+0.4,suggesting that the monzonite porphyry was derived from the partial melting of a thickened juvenile lower crust.The oxygen fugacity,calculated on the basis of the chemical composition of the amphiboles,shows?NNO values ranging from+1.65 to+2.16(average of 1.94)and lg(fO_(2))ranging from-12.72 to-11.99(average of-12.25),indicating that the monzonite porphyry has high oxygen fugacity.Zircons have high Ce^(4+)/Ce^(3+)ratios(29.29–164.24,average of 84.92),with high?FMQ values ranging from+0.50 to+1.51(average of 0.87)and high lg(fO_(2))values ranging from-14.72 to-12.85(average of-14.07),which also indicates that the oxygen fugacity of the magma was high.The dissolved water content of the Habo monzonite porphyry is 9.5–11.5 wt%,according to the geochemical characteristics,zircon-saturation thermometry(692–794°C)and the mineral phases(amphibole,no plagioclase)in the deep magma chamber.Combined with previous studies,we propose that the high oxygen fugacity and high water content of magma played key roles in controlling the formation of the Habo and other Cu-Mo-Au deposits in the Ailaoshan–Red River metallogenic belt.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
This report describes the oxidative cyclopalladation activation of a C≡C bond during the Pd-catalyzed hydroalkylation of alkynes and analyzes potential reaction pathways based on density functional theory calculation...This report describes the oxidative cyclopalladation activation of a C≡C bond during the Pd-catalyzed hydroalkylation of alkynes and analyzes potential reaction pathways based on density functional theory calculations. The more favorable pathway in-volves an oxidative cyclopalladation to generate a palladacyclopropene intermediate, which is rarely examined in Pd-catalyzed alkyne transformations. The reaction pathway proposed herein is kinetically favorable relative to the commonly proposed alkyne insertion mode. Furthermore, the Laplacians of the electron density, interaction region indicators, Mayer bond orders, and localized orbital bonding are evaluated to determine the reaction processes and characterize the key intermediates. Theoretical calculations indicate covalent bonding between a Pd(II) center and the two C-atoms in three-membered palladacycle species. Finally, electrostatic potential analysis reveals that the regioselectivity is governed by the charge distribution on the palladacycle moiety during the protonation step.展开更多
Mössbauer spectroscopy has been used widely to characterize the ferric(Fe^(3+))and ferrous(Fe^(2+))proportions and coordination of solid materials.To obtain these accurately,the recoilless fraction is indispensib...Mössbauer spectroscopy has been used widely to characterize the ferric(Fe^(3+))and ferrous(Fe^(2+))proportions and coordination of solid materials.To obtain these accurately,the recoilless fraction is indispensible.The recoilless fractions(f)of iron-bearing minerals,including oxides,oxyhydroxides,silicates,carbonates,phosphates and dichalcogenides,and silicate glasses were evaluated from the temperature dependence of their center shifts or absorption area with the Debye model approximation.Generally,the resolved Debye temperature(θ_(D))of ferric iron in minerals,except dichalcogenides,through their center shifts ranging from 400 to 550 K,is significantly larger than ferrous iron ranging from 300 to 400 K,which is consistent with the conclusion from previous work.The resolved f(Fe^(3+))RT with the center shift model(CSM)ranges from 0.825 to 0.925,which is larger than that obtained for f(Fe^(2+))RT,which ranges from 0.675 to 0.750.Meanwhile,the θ_(D) and f resolved from temperature-dependence of absorption are generally lower than from center shifts,especially for ferric iron.The significant difference between f(Fe^(3+))and f(Fe^(2+))indicates the necessity of recoilless fraction correction on the Fe^(3+)/(Fe^(3+)+Fe^(2+))resolved from Mössbauer spectra.展开更多
Understanding the intrinsic activity of oxygen evolution reaction(OER) is crucial for catalyst design.To date,different metal-doping strategies have been developed to achieve this,but the involving mechanisms remain u...Understanding the intrinsic activity of oxygen evolution reaction(OER) is crucial for catalyst design.To date,different metal-doping strategies have been developed to achieve this,but the involving mechanisms remain unclear.Here,the electronic structure of the transition metal-doped NiFe_(2)O_(4)(001) surface is scrutinized for OER intrinsic activity using density functional theory calculations.Five 3d-orbital filling metals(Ti,V,Cr,Mn,and Co) are introduced as dopants onto A-and B-layers of the NiFe_(2)O_(4)(001) surface,and variation of oxidation states over Fe sites is observed on B-layer.Analyzing the magnetic moment and charge transfer of surface cation sites reveals that the variation of Fe oxidation states originates from the super-exchange effect and is influenced by the t2g-electron configuration of 3d metal dopants.This trend governs the generation of highly-active Fe3+sites on the B-layer,the adsorption strength of OER intermediates,i.e.,*O and*OH,and therefore the intrinsic activity.The finding of super-exchange mechanism induced by 3d early metal doping offers insights into electronic structure tailoring strategies for improving the intrinsic activity of OER electrocatalysts.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
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
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.
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 National Key Research and Development Program of China(No.2023YFC2908304).
文摘Vanadium is a strategic metal in many countries,and it is mainly extracted from vanadium slag produced in titanomagnetite metallurgy.The traditional sodium roasting process for vanadium extraction poses environmental threats,and a green calcification pro-cess has been proposed.However,the vanadium extraction rate in the calcification process is much lower than in the sodium roasting pro-cess,which is related to vanadium solid solubility in Fe_(2)TiO_(5).Previous studies about vanadium behavior in Fe_(2)TiO_(5) were conducted in air,with a vanadium oxidation state of V5+.Vanadium with lower oxidation states has been detected in the tailings in the calcification process.The present paper studied the effects of vanadium oxidation states on the solid solubility in Fe_(2)TiO_(5) through solid-state reaction,X-ray diffraction characterization,transmission electron microscopy characterization,X-ray photoelectron spectroscopy analysis,and solid solu-tion modeling.The relative interaction values between vanadium oxides and Fe_(2)TiO_(5) are obtained as|L_(V_(2)O_(3))|>|L_(V_(2)O_(4))|>|L_(V_(2)O_(5)),indicating that vanadium with lower valence is preferable to be solid dissolved in Fe_(2)TiO_(5).The results imply that insufficiently oxidized vanadium increases the vanadium content in the Fe_(2)TiO_(5) phase during vanadium slag’s calcification roasting.Besides,experimental conditions op-timization shows that higher experimental temperature,vanadium introduction as V2O3,and a high-purity argon atmosphere would lead to higher vanadium solubility in Fe_(2)TiO_(5),and high temperature is beneficial for the release of vanadium from vanadium-containing Fe_(2)TiO_(5) when dissociated in air.
基金supported by the National Natural Science Foundation of China(22101116,92261203,21971106)Shenzhen Fundamental Research Program(JCYJ20220530115001002 and JCYJ20220818100417037).
文摘The dominant oxidation state for lanthanide ions is+3 due to the loss of 5d and 6s electrons from their shared configuration of[Xe]4f^(0-14)5d^(0-16)s(2).There are however several exceptions because of the completely empty(Ce(Ⅳ)),half-filled(Eu(Ⅱ)),or fully filled(Yb(Ⅱ))4f subshell.As such,stable complexes are formed primarily with Ln(Ⅲ)ions[1].
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 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.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 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.
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.
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.
基金supported by grants from the National Key Research and Development Program of China(Grant Nos.2016YFC0600310 and 2019YFA0708602)the National Natural Science Foundation of China(Grant Nos.41702091,41872083 and 42022014)+2 种基金the Yunnan Applied Basic Research Project(Grant No.202101AT070073)the China Fundamental Research Funds for the Central Universities(Grant No.2652018133)the Scientific Research Fund of the Yunnan Provincial Education Department(Grant No.2022Y016)。
文摘The Habo deposit is a typical porphyry Cu-Mo deposit in the Ailaoshan–Red River metallogenic belt.Ore minerals in the Habo deposit typically occur as veins in the monzonite porphyry.Zircon U-Pb dating suggests that the monzonite porphyry formed at 35.07±0.38 Ma.The monzonite porphyry is characterized by high SiO_(2),Al_(2)O_(3),K_(2)O and Na_(2)O contents,with A/CNK ratios ranging from 0.97 to 1.02.All samples exhibit fractionated REE patterns,characterized by high(La/Yb)N ratios(9.4–13.6,average of 11.2).They show adakite-like geochemical features,high Sr concentrations(627–751 ppm,average of 700 ppm),low Y concentrations(15.13–16.86 ppm,average of 15.81 ppm)and high Sr/Y values(39.5–47.4,average of 44.3).These samples have high initial^(87)Sr/^(86)Sr ratios(0.7074–0.7076)and negativeεNd(t)values(-5.1 to-3.7),whereas the zirconεHf(t)values range from-2.2 to+0.4,suggesting that the monzonite porphyry was derived from the partial melting of a thickened juvenile lower crust.The oxygen fugacity,calculated on the basis of the chemical composition of the amphiboles,shows?NNO values ranging from+1.65 to+2.16(average of 1.94)and lg(fO_(2))ranging from-12.72 to-11.99(average of-12.25),indicating that the monzonite porphyry has high oxygen fugacity.Zircons have high Ce^(4+)/Ce^(3+)ratios(29.29–164.24,average of 84.92),with high?FMQ values ranging from+0.50 to+1.51(average of 0.87)and high lg(fO_(2))values ranging from-14.72 to-12.85(average of-14.07),which also indicates that the oxygen fugacity of the magma was high.The dissolved water content of the Habo monzonite porphyry is 9.5–11.5 wt%,according to the geochemical characteristics,zircon-saturation thermometry(692–794°C)and the mineral phases(amphibole,no plagioclase)in the deep magma chamber.Combined with previous studies,we propose that the high oxygen fugacity and high water content of magma played key roles in controlling the formation of the Habo and other Cu-Mo-Au deposits in the Ailaoshan–Red River metallogenic belt.
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.
基金supported by the National Natural Science Foundation of China(Nos.22003006,21822303,22103008,22271034)Project supported by graduate research and innovation foundation of Chongqing,China(No.CYB20045)a project(No.2018CDXZ0002)supported by the Fundamental Research Funds for the Central Universities(Chongqing University)。
文摘This report describes the oxidative cyclopalladation activation of a C≡C bond during the Pd-catalyzed hydroalkylation of alkynes and analyzes potential reaction pathways based on density functional theory calculations. The more favorable pathway in-volves an oxidative cyclopalladation to generate a palladacyclopropene intermediate, which is rarely examined in Pd-catalyzed alkyne transformations. The reaction pathway proposed herein is kinetically favorable relative to the commonly proposed alkyne insertion mode. Furthermore, the Laplacians of the electron density, interaction region indicators, Mayer bond orders, and localized orbital bonding are evaluated to determine the reaction processes and characterize the key intermediates. Theoretical calculations indicate covalent bonding between a Pd(II) center and the two C-atoms in three-membered palladacycle species. Finally, electrostatic potential analysis reveals that the regioselectivity is governed by the charge distribution on the palladacycle moiety during the protonation step.
基金support from National Natural Science Foundation of China(41873067)Postdoctoral Science Foundation of China(2018M640160,2019T120120)。
文摘Mössbauer spectroscopy has been used widely to characterize the ferric(Fe^(3+))and ferrous(Fe^(2+))proportions and coordination of solid materials.To obtain these accurately,the recoilless fraction is indispensible.The recoilless fractions(f)of iron-bearing minerals,including oxides,oxyhydroxides,silicates,carbonates,phosphates and dichalcogenides,and silicate glasses were evaluated from the temperature dependence of their center shifts or absorption area with the Debye model approximation.Generally,the resolved Debye temperature(θ_(D))of ferric iron in minerals,except dichalcogenides,through their center shifts ranging from 400 to 550 K,is significantly larger than ferrous iron ranging from 300 to 400 K,which is consistent with the conclusion from previous work.The resolved f(Fe^(3+))RT with the center shift model(CSM)ranges from 0.825 to 0.925,which is larger than that obtained for f(Fe^(2+))RT,which ranges from 0.675 to 0.750.Meanwhile,the θ_(D) and f resolved from temperature-dependence of absorption are generally lower than from center shifts,especially for ferric iron.The significant difference between f(Fe^(3+))and f(Fe^(2+))indicates the necessity of recoilless fraction correction on the Fe^(3+)/(Fe^(3+)+Fe^(2+))resolved from Mössbauer spectra.
基金supported by the Australian Research Council(FT170100224,DP210103892,IC200100023)support from Tsinghua National Laboratory for Information Science and Technology for theoretical simulations。
文摘Understanding the intrinsic activity of oxygen evolution reaction(OER) is crucial for catalyst design.To date,different metal-doping strategies have been developed to achieve this,but the involving mechanisms remain unclear.Here,the electronic structure of the transition metal-doped NiFe_(2)O_(4)(001) surface is scrutinized for OER intrinsic activity using density functional theory calculations.Five 3d-orbital filling metals(Ti,V,Cr,Mn,and Co) are introduced as dopants onto A-and B-layers of the NiFe_(2)O_(4)(001) surface,and variation of oxidation states over Fe sites is observed on B-layer.Analyzing the magnetic moment and charge transfer of surface cation sites reveals that the variation of Fe oxidation states originates from the super-exchange effect and is influenced by the t2g-electron configuration of 3d metal dopants.This trend governs the generation of highly-active Fe3+sites on the B-layer,the adsorption strength of OER intermediates,i.e.,*O and*OH,and therefore the intrinsic activity.The finding of super-exchange mechanism induced by 3d early metal doping offers insights into electronic structure tailoring strategies for improving the intrinsic activity of OER electrocatalysts.
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.
