The exploitation of high performance redox-active substances is critically important for the development of non-aqueous redoxflow batteries.Herein,three tetrathiofulvalene(TTF)derivatives with different substitution gr...The exploitation of high performance redox-active substances is critically important for the development of non-aqueous redoxflow batteries.Herein,three tetrathiofulvalene(TTF)derivatives with different substitution groups,namely TTF diethyl ester(TTFDE),TTF tetramethyl ester(TTFTM),and TTF tetraethyl ester(TTFTE),are prepared and their energy storage properties are evaluated.It has been found that the redox potential and solubility of these TTF derivatives in conventional carbonate electrolytes increases with the number of ester groups.The battery with a catholyte of 0.2 mol L^(-1) of TTFTE delivers a specific capacity of more than 10 Ah L^(-1) at the current density of 0.5 C with two discharge voltage platforms locating at as high as 3.85 and 3.60 V vs.Li/Liþ.Its capacity retention can be improved from 2.34 Ah L^(-1) to 3.60 Ah L^(-1) after 100 cycles by the use of an anion exchange membrane to block the crossover of TTF species.The excellent cycling stability of the TIF esters is supported by their well-delocalized electrons,as revealed by the density function theory calculations.Therefore,the introduction of more and larger electron-withdrawing groups is a promising strategy to simultaneously increase the redox-potential and solubility of redox-active ma-terials for non-aqueous redoxflow batteries.展开更多
Sodium-ion batteries (SIBs) with organic electrodes are an emerging research direction due to the sustainability of organic materials based on elements like C,H,O,and sodium ions.Currently,organic electrode materials ...Sodium-ion batteries (SIBs) with organic electrodes are an emerging research direction due to the sustainability of organic materials based on elements like C,H,O,and sodium ions.Currently,organic electrode materials for SIBs are mainly used as cathodes because of their relatively high redox potentials(>1 V).Organic electrodes with low redox potential that can be used as anode are rare.Herein,a novel organic anode material (tetrasodium 1,4,5,8-naphthalenetetracarboxylate,Na_(4)TDC) has been developed with low redox potential (<0.7 V) and excellent cyclic stability.Its three-sodium storage mechanism was demonstrated with various in-situ/ex-situ spectroscopy and theoretical calculations,showing a high capacity of 208 mAh/g and an average decay rate of merely 0.022%per cycle.Moreover,the Na_(4)TDC-hard carbon composite can further acquire improved capacity and cycling stability for 1200 cycles even with a high mass loading of up to 20 mg cm^(-2).By pairing with a thick Na_(3)V_(2)(PO_(4))_(3)cathode (20.6 mg cm^(-2)),the as-fabricated full cell exhibited high operating voltage (2.8 V),excellent rate performance and cycling stability with a high capacity retention of 88.7% after 200 cycles,well highlighting the Na_(4)TDC anode material for SIBs.展开更多
To provide optimization strategies for chalcopyrite ammonia heap leaching processes,the key factors influencing chalcopyrite ammonia leaching kinetics were investigated under sealed reactor and controlled redox potent...To provide optimization strategies for chalcopyrite ammonia heap leaching processes,the key factors influencing chalcopyrite ammonia leaching kinetics were investigated under sealed reactor and controlled redox potential at ambient temperature.The results indicated that redox potential,particle size,and pH significantly affected chalcopyrite dissolution rates.The reaction orders with respect to particle size and hydroxyl ion concentration c(OH−)were determined to be−2.39 and 0.55,respectively.Temperature exhibited a marginal effect on chalcopyrite dissolution within the range of 25−45℃.The ammonium carbonate medium proved more favorable for chalcopyrite leaching than ammonium chloride and ammonium sulfate systems.Surface deposits on the residues were identified as porous iron oxides,predominantly hematite and ferrihydrite,which produced diffusion barriers during leaching.Shrinking core model analysis revealed that the second stage of reaction was controlled by product-layer diffusion,which was further confirmed by the low activation energy(10.18 kJ/mol).展开更多
Trifluoromethylation reactions are important transformations in the research and development of drugs, agrochemicals and functional materials. An oxidation/reduction process of trifluoromethyl-containing compounds is ...Trifluoromethylation reactions are important transformations in the research and development of drugs, agrochemicals and functional materials. An oxidation/reduction process of trifluoromethyl-containing compounds is thought to be involved in many recently tested catalytic trifluoromethylation reactions. To provide helpful physical chemical data for mechanistic studies on trifluoromethylation reactions, the redox potentials of a variety of trifluoromethyl-containing compounds and trifluoro- methylated radicals were studied by quantum-chemical methods. First, eoB97X-D was found to be a reliable method in predicting the ionization potentials, electron affinities, bond dissociation enthalpies and redox potentials of trifluoromethylcontaining compounds. One-electron absolute redox potentials of 79 trifluoromethyl substrates and 107 trifluoromethylated radicals in acetonitrile were then calculated with this method. The theoretical results were found to be helpful for interpreting experimental observations such as the relative reaction efficiency of different trifluoromethylation reagents. Finally, the bond dissociation free energies （BDFE） of various compounds were found to have a good linear relationship with the related bond dissociation enthalpies （BDE）. Based on this observation, a convenient method was proposed to predict one-electron redox potentials of neutral molecules.展开更多
Soil redox potential(Eh)plays an important role in the biogeochemical cycling of soil nutrients.Whereas its effect soil process and nutrients'availability under elevated atmospheric CO_(2) concentration and warmin...Soil redox potential(Eh)plays an important role in the biogeochemical cycling of soil nutrients.Whereas its effect soil process and nutrients'availability under elevated atmospheric CO_(2) concentration and warming has seldom been investigated.Thus,in this study,a field experiment was used to elucidate the effect of elevated CO_(2) concentration and warming on soil Eh,redox-sensitive elements and root radial oxygen loss(ROL).We hypothesized elevated CO_(2) and warming could alter soil Eh by promoting or inhibiting ROL.We found that soil Eh in the rhizosphere was significantly higher than that of non-rhizosphere.Elevated CO_(2) enhanced soil Eh by 11.5%,which corresponded to a significant decrease in soil Fe^(2+)and Mn^(2+)concentration.Under elevated CO_(2),the concentration of Fe^(2+)and Mn^(2+)decreased by 14.7%and 13.7%,respectively.We also found that elevated CO_(2) altered rice root aerenchyma structure and promoted rice root ROL.Under elevated CO_(2),rice root ROL increased by 79.5%and 112.2%for Yangdao 6 and Changyou 5,respectively.Warming had no effect on soil Eh and rice root ROL.While warming increased the concentration of Mn^(2+)and SO_(4)^(2-)by 4.9%and 19.3%,respectively.There was a significant interaction between elevated CO_(2) and warming on Fe^(2+)and Mn^(2+).Under elevated CO_(2),warming had no effect on the concentration of Fe^(2+)but decreased Mn^(2+)concentration significantly.Our study demonstrated that elevated atmospheric CO_(2) in the future could increase soil Eh by promoting rice root ROL,which will alter some soil nutrients'availability,such as Fe^(2+)and Mn^(2+).展开更多
Paddy fields are considered a major source of methane(CH_4)emissions.Aerobic irrigation methods have proven to be efficacious in mitigating CH_4 emissions in paddy cultivation.The promising role of compound microbial ...Paddy fields are considered a major source of methane(CH_4)emissions.Aerobic irrigation methods have proven to be efficacious in mitigating CH_4 emissions in paddy cultivation.The promising role of compound microbial agents in refining the rhizospheric ecosystem suggests their potential as novel agents in reducing CH_4 emissions from paddy fields.To explore a new method of using compound microbial agents to reduce CH_4 emissions,we conducted pot and field experiments over the period of 2022-2023.We measured CH_4 flux,the redox potential(Eh)of the soil,the concentration of dissolved oxygen(DO)in the floodwater,and the gene abundance of both methanogens(mcr A)and methanotrophs(pmo A).The results showed that the application of the compound microbial agent led to a significant increase in the DO levels within the floodwater and an increase of 9.26%to 35.01%in the Eh of the tillage soil.Furthermore,the abundance of pmo A increased by 31.20%,while the mcr A/pmo A ratio decreased by 25.96%at the maximum tillering stage.Applying 45-75 kg/hm^(2) of the compound microbial agent before transplanting resulted in a reduction of cumulative CH_4 emissions from paddy fields by 17.49%in single-cropped rice and 43.54%to 50.27%in double-cropped late rice during the tillering stage.Correlation analysis indicated that CH_4 flux was significantly negatively correlated with pmo A gene abundance and soil Eh,and positively related to the mcr A/pmo A ratio.Additionally,soil Eh was significantly positively correlated with pmo A gene abundance,suggesting that paddy soil Eh indirectly affected CH_4 flux by influencing the pmo A gene abundance.In conclusion,the pre-planting application of the compound microbial agent at a rate of 45-75 kg/hm^(2) can enhance the Eh in the rhizosphere and increase the abundance of the pmo A gene,thereby reducing CH_4 emissions from paddy fields during the tillering stage of rice growth.展开更多
The changes of pH,redox potential,concentrations of soluble iron ions and Cu^2＋ with the time of bioleaching chalcopyrite concentrates by acidithiobacillus ferrooxidans were investigated under the different condition...The changes of pH,redox potential,concentrations of soluble iron ions and Cu^2＋ with the time of bioleaching chalcopyrite concentrates by acidithiobacillus ferrooxidans were investigated under the different conditions of initial total-iron amount as well as mole ratio of Fe（III） to Fe（II） in the solutions containing synthetic extracellular polymeric substances （EPS）.When the solution potential is lower than 650 mV （vs SHE）,the inhibition of jarosites to bioleaching chalcopyrite is not vital as EPS produced by bacteria can retard the contamination through flocculating jarosites even if concentration of Fe（III） ions is up to 20 g/L but increases with increasing the concentration of Fe（III） ions;jarosites formed by bio-oxidized Fe3＋ ions are more easy to adhere to outside surface of EPS space on chalcopyrite;the EPS layer with jarosites acts as a weak diffusion barrier to further rapidly create a high redox potential of more than 650 mV by bio-oxidizing Fe^2＋ ions inside and outside EPS space into Fe^3＋ ions,resulting in a rapid deterioration of ion diffusion performance of the EPS layer to inhibit bioleaching chalcopyrite severely and irreversibly.展开更多
The alloying process of Mg-La in NaCl-KCl-MgCl_(2)-LaCl_(3)(NKML)melts during electroreduction was elucidated using electrochemical techniques and deep potential molecular dynamics(DPMD)simulations.In the NKML system,...The alloying process of Mg-La in NaCl-KCl-MgCl_(2)-LaCl_(3)(NKML)melts during electroreduction was elucidated using electrochemical techniques and deep potential molecular dynamics(DPMD)simulations.In the NKML system,the Mg^(2+)/La^(3+)electrodeposition on the tungsten(W)electrode at 973 K was found to be a one-step process.The nucleation of metal ions on the electrode surface followed an instantaneous nucleation mode and was not influenced by the alloying process.The redox potential and underpotential deposition behavior of the metal ions in the NKML system were accurately predicted by the DPMD simulations,confirming the alloying process of the Mg-La.Additionally,scanning electron microscopy with energy dispersive spectroscopy(SEM-EDS)analysis results confirmed that the cathodic deposits consisted of a bright phase and a dark phase,corresponding to the Mg-La alloys and Mg,respectively.The distribution of electrolytic products suggests that the cathodic deposit initially favors the Mg phase,with the Mg-La alloy forming more easily when the Mg source in the melt is depleted.展开更多
The sediment redox potential was raised in the laboratory to estimate reduction of internal available phosphorus loads,such as soluble reactive phosphorus(SRP)and total phosphorus(TP),as well as the main elements of s...The sediment redox potential was raised in the laboratory to estimate reduction of internal available phosphorus loads,such as soluble reactive phosphorus(SRP)and total phosphorus(TP),as well as the main elements of sediment extracts in Dianchi Lake.Several strongly reducing substances in sediments,which mainly originated from anaerobic decomposition of primary producer residues,were responsible for the lower redox potential.In a range of -400 to 200 mV raising the redox potential of sediments decreased TP and SRP in interstitial water.Redox potentials exceeding 320 mV caused increases in TP,whereas SRP maintained a relatively constant minimum level.The concentrations of Al,Fe, Ca^(2+),Mg^(2+),K^+,Na^+ and S in interstitial water were also related to the redox potential of sediments,suggesting that the mechanism for redox potential to regulate the concentration of phosphorus in interstitial water was complex.展开更多
Based on the bioleaching mechanism and electrochemical studies of metal sulfides, the dissolution rates of chalcocite and pyrite are controlled by redox potentials. Experiment on the bioleaching of chalcocite and pyri...Based on the bioleaching mechanism and electrochemical studies of metal sulfides, the dissolution rates of chalcocite and pyrite are controlled by redox potentials. Experiment on the bioleaching of chalcocite and pyrite under constant redox potential by sparging with nitrogen gas was demonstrated. By leaching at low and constant redox potential（〈760 mV, vs SHE）, copper recoveries of 90 %–98 % are achieved, which are 10 times more than iron recoveries. The iron-oxidizing bacterial populations are observed to continue to reduce under oxygen limitation conditions, but the Acidithiobacillus that have only sulfur-oxidizing capabilities are an attractive alternative for redox-controlled bioleaching of chalcocite.Thus, the described redox control technique might be one of the effective approaches to balance acid and iron in Zijinshan copper bio-heap leaching practice.展开更多
This work presents a study for chemical leaching of sphalerite concentrate under various constant Fe3+ concentrations and redox potential conditions. The effects of Fe3+ concentration and redox potential on chemical l...This work presents a study for chemical leaching of sphalerite concentrate under various constant Fe3+ concentrations and redox potential conditions. The effects of Fe3+ concentration and redox potential on chemical leaching of sphalerite were investigated. The shrinking core model was applied to analyze the experimental results. It was found that both the Fe3+ concentration and the redox potential controlled the chemical leaching rate of sphalerite. A new kinetic model was developed, in which the chemical leaching rate of sphalerite was proportional to Fe3+ concentration and Fe3+ /Fe2+ ratio. All the model parameters were evaluated from the experimental data. The model predictions fit well with the experimental observed values.展开更多
The experiments were carried out in continuous flow acidogenic reactors with molasses used as substrate to study the effects of pH and redox potential on fermentation types. The conditions for each fermentation type w...The experiments were carried out in continuous flow acidogenic reactors with molasses used as substrate to study the effects of pH and redox potential on fermentation types. The conditions for each fermentation type were investigated at different experimental stages of start up, pH regulating and redox potential regulating. The experiments confirmed that butyric acid type fermentation would occur at pH > 6, the propionic acid type fermentation at pH about 5.5 with E h> -278 mV, and the ethanol type fermentation at pH < 4.5. A higher redox potential will lead to propionic acid type fermentation because propionogens are facultative anaerobic bacteria.展开更多
Comparisons on the bioleaching and sterile oxidation of pyrite were performed at controlled redox potential of 900 mV(vs.SHE) and different temperatures of 30 and 60℃.For sterile experiments,the redox potential of ir...Comparisons on the bioleaching and sterile oxidation of pyrite were performed at controlled redox potential of 900 mV(vs.SHE) and different temperatures of 30 and 60℃.For sterile experiments,the redox potential of irrigation solution was controlled by adding hydrogen peroxide solution(15 wt%),while the redox potential of irrigation solution for bioleaching was elevated by flowing through the packed bed in which bacteria were activated and colonized.The rate of pyrite bioleaching is faster than that of sterile oxidation at temperature of 30℃.The reason is that the potential gradient of leaching solution in bioleaching column is much smaller than that in sterile column.The redox potentials of irrigation solution and leaching solution are similar for bioleaching;however,the redox potential difference of irrigation solution and leaching solution for sterile oxidation is about 150 mV.When temperature increases to 60℃ for sterile oxidation,the rate of pyrite leaching is faster than that of bioleaching at temperature of 30℃,even though the redox potential gradient of leaching solution is great.The mineralogy analyses of pyrite residue were performed by scanning electron microscopy-energy-dispersive spectroscopy(SEM-EDS),X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS) analyses.The results confirm that pyrite oxidation might only occur at specific sites with high surface energy on surface and obeys the "indirect mechanism" whether there are bacteria or not.The pyrite oxidation rate is not inhibited by inert sulfur on residue surface at elevated redox potential.According to the conclusions,the way to accelerate pyrite oxidation is proposed.展开更多
The relation between EH [Se(VI)/Se(IV)] and pH of soil aqueous extract in Kaschin-Beck disease region and the effects of natural redox agents, namely humic substances, MnO2 and Fe2+, on the redox property of the syste...The relation between EH [Se(VI)/Se(IV)] and pH of soil aqueous extract in Kaschin-Beck disease region and the effects of natural redox agents, namely humic substances, MnO2 and Fe2+, on the redox property of the system were studied. The results indicated that both humic acid and Fe2+ could enhance the reducibility of Se(VI) and MnO2, a limited oxidizability for Se(IV). Fe2+ showed a weak reducibility only at low pH value. The reducibilities of three sulfur-containing compounds for Se(VI) were in following order:thioglycollic acid > L-cysteine > sulfide展开更多
Benefitting from the tunable heterogeneous interface and electronic interaction, metal-polymer-based hybrid composites have attracted wide attention. It is highly desired to develop advanced synthesis methodology and ...Benefitting from the tunable heterogeneous interface and electronic interaction, metal-polymer-based hybrid composites have attracted wide attention. It is highly desired to develop advanced synthesis methodology and understand the structure-performance relationship. Herein, with the aniline oligomer as the key enabler, we resolve the inferior dynamics issue in the Ag+-aniline reaction system, and successfully fabricate a sub-micron anisotropic eccentric Ag@polyaniline(PANI) particle(an average size up to 340 nm) at room temperature. We demonstrate the synergy mechanism of polyvinyl pyrrolidone and insitu generated PANI for modifying the dynamic reaction interface. We further clarify the H+concentration and the surfactant types serve as main descriptors to tune the reaction dynamics. Besides, by applying other aniline oligomers, a series of similar eccentric structures can also be obtained, indicative of the good applicability of our strategy. Such a sub-micron eccentric structure furnishes the Ag@PANI composites with sound performance for microwave absorption, as demonstrated by a minimum reflection loss(RL) value of-35 d B with an effective absorption bandwidth of 3.7 GHz. This study provides an inspiring scope/concept of eccentric microstructure engineering for better meeting the demands in the high-tech military, energy, environment fields, and beyond.展开更多
By using 1-methyl-2-formyl-5-substituted pyrroles (1-Y), 1-methyl-2-formyl-5-substituted pyrrole phenylhydrazones (2-Y) and 1-methyl-2-formyl-5-substituted pyrrole (4-nitrophenyl)-hydrazones (3-Y) as model structures ...By using 1-methyl-2-formyl-5-substituted pyrroles (1-Y), 1-methyl-2-formyl-5-substituted pyrrole phenylhydrazones (2-Y) and 1-methyl-2-formyl-5-substituted pyrrole (4-nitrophenyl)-hydrazones (3-Y) as model structures for nitrogen-containing heterocyclic aromatic compounds, correlation analysis of their redox potential data show that the transition states (TS) of the polarographic process are mainly affected by the polar effects, but spin-delocalizatin effects also exist.展开更多
Aqueous zinc metal batteries feature intrinsic safety,but suffer from severe dendrite growth and water-derived side reactions.Many metal coatings have been explored for stabilizing Zn metal anode via a trialand-error ...Aqueous zinc metal batteries feature intrinsic safety,but suffer from severe dendrite growth and water-derived side reactions.Many metal coatings have been explored for stabilizing Zn metal anode via a trialand-error approach.Here,we propose an exercisable way to screen the potential metal coating on Zn anodes in view of de-polarization effect and dendrite-suppressing ability theoretically.As an output of this screening,cadmium(Cd) metal is checked experimentally.Therefore,symmetric ZnllZn cells using Cd coated Zn(Zn@Cd) exhibit an ultra-long cycle life of 3500 h(nearly 5 months) at a high current density of 10 mA cm^(-2),achieving a record-high cumulative capacity(35 A h cm^(-2)) compared to the previous reports.The full cells of Zn@Cd‖MnO_(2) display a markedly improved cycling performance under harsh conditions including a limited Zn supply(N/P ratio=1.7) and a high areal capacity(3.5 mA h cm^(-2)).The significance of this work lies in not only the first report of Cd coating for stabilizing Zn metal anode,but also a feasible way to screen the promising metal materials for other metal anodes.展开更多
A three-year experiment was conducted in the middle-lower reaches of the Yangtze River in China to study the influence of continuous wheat straw return during the rice season and continuous rice straw return in wheat ...A three-year experiment was conducted in the middle-lower reaches of the Yangtze River in China to study the influence of continuous wheat straw return during the rice season and continuous rice straw return in wheat on methane （CH 4 ） emissions from rice fields in which, the rice-wheat rotation system is the most dominant planting pattern. The field experiment was initiated in October 2009 and has continued since the wheat-growing season of that year. The analyses for the present study were conducted in the second （2011） and third （2012） rice growing seasons. Four treatments, namely, the continuous return of wheat straw and rice straw in every season （WR）, of rice straw but no wheat straw return （R）, of wheat straw but no rice straw return （W） and a control with no straw return （CK）, were laid out in a randomized split-plot design. The total seasonal CH 4 emissions ranged from 107.4 to 491.7 kg/ha （2011） and 160.3 to 909.6 kg/ha （2012）. The increase in CH 4 emissions for treatments WR and W were 289% and 230% in the second year and 185% and 225% in the third year, respectively, in relation to CK. We observed less methane emissions in the treatment R than in CK by 14%-43%, but not statistically significant. Treatment R could increase rice productivity while no more CH 4 emission occurs. The difference in the total CH 4 emissions mainly related to a difference in the methane flux rate during the first 30-35 days after transplant in the rice growing season, which was caused by the amount of dissolved oxygen in paddy water and the amount of reducible soil materials.展开更多
Most studies on dissimilatory nitrate reduction to ammonium （DNRA） in paddy soils were conducted in the laboratory and in situ studies are in need for better understanding of the DNRA process. In this study, in situ...Most studies on dissimilatory nitrate reduction to ammonium （DNRA） in paddy soils were conducted in the laboratory and in situ studies are in need for better understanding of the DNRA process. In this study, in situ incubations of soil DNRA using ^15N tracer were carried out in paddy fields under conventional water （CW） and low water （LW） managements to explore the potential of soil DNRA after liquid cattle waste （LCW） application and to investigate the impacts of soil redox potential （Eh） and labile carbon on DNRA. DNRA rates ranged from 3.06 to 10.40 mg N kg 1 dry soil d-1, which accounted for 8.55%-12.36% and 3.88% 25.44% of consumption of added NO3-^15N when Eh at 5 cm soil depth ranged from 230 to 414 mV and -225 to -65 mV, respectively. DNRA rates showed no significant difference in paddy soils under two water managements although soil Eh and/or dissolved organic carbon （DOC） were more favorable for DNRA in the paddy soil under CW management 1 d before, or 5 and 7 d after LCW application. Soil DNRA rates were negatively correlated with soil Eh （P 〈 0.05, n = 5） but positively correlated with soil DOC （P 〈 0.05, n - 5） in the paddy soil under LW management, while no significant correlations were shown in the paddy soil under CW management. The potential of DNRA measured in situ was consistent with previous laboratory studies; and the controlling factors of DNRA in paddy soils might be different under different water managements, probably due to the presence of different microfioras of DNRA.展开更多
Many researchers found that the Fe2+together with less amount of Cu2+can accelerate the leaching of chalcopyrite.In this work,the leaching of chalcopyrite with Cu2+was investigated.The leaching residuals were examined...Many researchers found that the Fe2+together with less amount of Cu2+can accelerate the leaching of chalcopyrite.In this work,the leaching of chalcopyrite with Cu2+was investigated.The leaching residuals were examined by Raman spectroscopy.Based on the leaching experiments,the chemical equilibrium in solution was calculated using Visual MINTEQ.The results showed that the Fe in chalcopyrite lattice was replaced by Cu2+;therefore,the chalcopyrite transformed into covellite.Furthermore,the formation of chalcocite occurred when Fe2+and Fe3+were added to the solution containing Cu2+.The copper extraction increased with a decrease of the initial redox potential(or the ratio of Fe3+/Fe2+).展开更多
基金supported by the National Natural Science Foundation of China(Nos:51503038 and 51873037).
文摘The exploitation of high performance redox-active substances is critically important for the development of non-aqueous redoxflow batteries.Herein,three tetrathiofulvalene(TTF)derivatives with different substitution groups,namely TTF diethyl ester(TTFDE),TTF tetramethyl ester(TTFTM),and TTF tetraethyl ester(TTFTE),are prepared and their energy storage properties are evaluated.It has been found that the redox potential and solubility of these TTF derivatives in conventional carbonate electrolytes increases with the number of ester groups.The battery with a catholyte of 0.2 mol L^(-1) of TTFTE delivers a specific capacity of more than 10 Ah L^(-1) at the current density of 0.5 C with two discharge voltage platforms locating at as high as 3.85 and 3.60 V vs.Li/Liþ.Its capacity retention can be improved from 2.34 Ah L^(-1) to 3.60 Ah L^(-1) after 100 cycles by the use of an anion exchange membrane to block the crossover of TTF species.The excellent cycling stability of the TIF esters is supported by their well-delocalized electrons,as revealed by the density function theory calculations.Therefore,the introduction of more and larger electron-withdrawing groups is a promising strategy to simultaneously increase the redox-potential and solubility of redox-active ma-terials for non-aqueous redoxflow batteries.
基金National Key Research and Development Program of China (2022YFB2402200)National Natural Science Foundation of China (22225201,22379028)+2 种基金Fundamental Research Funds for the Central Universities (20720220010)Shanghai Pilot Program for Basic Research–Fudan University 21TQ1400100 (21TQ009)Key Basic Research Program of Science and Technology Commission of Shanghai Municipality (23520750400)。
文摘Sodium-ion batteries (SIBs) with organic electrodes are an emerging research direction due to the sustainability of organic materials based on elements like C,H,O,and sodium ions.Currently,organic electrode materials for SIBs are mainly used as cathodes because of their relatively high redox potentials(>1 V).Organic electrodes with low redox potential that can be used as anode are rare.Herein,a novel organic anode material (tetrasodium 1,4,5,8-naphthalenetetracarboxylate,Na_(4)TDC) has been developed with low redox potential (<0.7 V) and excellent cyclic stability.Its three-sodium storage mechanism was demonstrated with various in-situ/ex-situ spectroscopy and theoretical calculations,showing a high capacity of 208 mAh/g and an average decay rate of merely 0.022%per cycle.Moreover,the Na_(4)TDC-hard carbon composite can further acquire improved capacity and cycling stability for 1200 cycles even with a high mass loading of up to 20 mg cm^(-2).By pairing with a thick Na_(3)V_(2)(PO_(4))_(3)cathode (20.6 mg cm^(-2)),the as-fabricated full cell exhibited high operating voltage (2.8 V),excellent rate performance and cycling stability with a high capacity retention of 88.7% after 200 cycles,well highlighting the Na_(4)TDC anode material for SIBs.
基金the financial supports from the Strategic Priority Research Program of Chinese Academy of Sciences(No.XDA0430304).
文摘To provide optimization strategies for chalcopyrite ammonia heap leaching processes,the key factors influencing chalcopyrite ammonia leaching kinetics were investigated under sealed reactor and controlled redox potential at ambient temperature.The results indicated that redox potential,particle size,and pH significantly affected chalcopyrite dissolution rates.The reaction orders with respect to particle size and hydroxyl ion concentration c(OH−)were determined to be−2.39 and 0.55,respectively.Temperature exhibited a marginal effect on chalcopyrite dissolution within the range of 25−45℃.The ammonium carbonate medium proved more favorable for chalcopyrite leaching than ammonium chloride and ammonium sulfate systems.Surface deposits on the residues were identified as porous iron oxides,predominantly hematite and ferrihydrite,which produced diffusion barriers during leaching.Shrinking core model analysis revealed that the second stage of reaction was controlled by product-layer diffusion,which was further confirmed by the low activation energy(10.18 kJ/mol).
基金supported by the National Natural Science Foundation of China(21325208,21172209,21361140372,21202006)Specialized Research Fund for the Doctoral Program(20123402110051)+5 种基金Fundamental Research Funds for the Central Universities(WK2060190025)Chinese Academy of Sciences(KJCX2-EW-J02)Fok Ying Tung Education FoundationAnhui Provincial Natural Science Foundation(1308085QB38)China Grid project funded by Ministry of Education of Chinathe supercomputer center of Shanghai and University of Science and Technology of China
文摘Trifluoromethylation reactions are important transformations in the research and development of drugs, agrochemicals and functional materials. An oxidation/reduction process of trifluoromethyl-containing compounds is thought to be involved in many recently tested catalytic trifluoromethylation reactions. To provide helpful physical chemical data for mechanistic studies on trifluoromethylation reactions, the redox potentials of a variety of trifluoromethyl-containing compounds and trifluoro- methylated radicals were studied by quantum-chemical methods. First, eoB97X-D was found to be a reliable method in predicting the ionization potentials, electron affinities, bond dissociation enthalpies and redox potentials of trifluoromethylcontaining compounds. One-electron absolute redox potentials of 79 trifluoromethyl substrates and 107 trifluoromethylated radicals in acetonitrile were then calculated with this method. The theoretical results were found to be helpful for interpreting experimental observations such as the relative reaction efficiency of different trifluoromethylation reagents. Finally, the bond dissociation free energies （BDFE） of various compounds were found to have a good linear relationship with the related bond dissociation enthalpies （BDE）. Based on this observation, a convenient method was proposed to predict one-electron redox potentials of neutral molecules.
基金supported by the National Natural Science Foundation of China (No.42277328)the Sino-German Mobility Program (No.M-0105)。
文摘Soil redox potential(Eh)plays an important role in the biogeochemical cycling of soil nutrients.Whereas its effect soil process and nutrients'availability under elevated atmospheric CO_(2) concentration and warming has seldom been investigated.Thus,in this study,a field experiment was used to elucidate the effect of elevated CO_(2) concentration and warming on soil Eh,redox-sensitive elements and root radial oxygen loss(ROL).We hypothesized elevated CO_(2) and warming could alter soil Eh by promoting or inhibiting ROL.We found that soil Eh in the rhizosphere was significantly higher than that of non-rhizosphere.Elevated CO_(2) enhanced soil Eh by 11.5%,which corresponded to a significant decrease in soil Fe^(2+)and Mn^(2+)concentration.Under elevated CO_(2),the concentration of Fe^(2+)and Mn^(2+)decreased by 14.7%and 13.7%,respectively.We also found that elevated CO_(2) altered rice root aerenchyma structure and promoted rice root ROL.Under elevated CO_(2),rice root ROL increased by 79.5%and 112.2%for Yangdao 6 and Changyou 5,respectively.Warming had no effect on soil Eh and rice root ROL.While warming increased the concentration of Mn^(2+)and SO_(4)^(2-)by 4.9%and 19.3%,respectively.There was a significant interaction between elevated CO_(2) and warming on Fe^(2+)and Mn^(2+).Under elevated CO_(2),warming had no effect on the concentration of Fe^(2+)but decreased Mn^(2+)concentration significantly.Our study demonstrated that elevated atmospheric CO_(2) in the future could increase soil Eh by promoting rice root ROL,which will alter some soil nutrients'availability,such as Fe^(2+)and Mn^(2+).
基金supported by the Zhejiang‘Ten Thousand Talents’Plan Science and Technology Innovation Leading Talent Project,China (Grant No.2020R52035)the National Rice Industry Technology System of China (Grant No.CARS-01-31)the Agricultural Science and Technology Innovation Program,China (Grant No.CAAS-ZDRW202001)。
文摘Paddy fields are considered a major source of methane(CH_4)emissions.Aerobic irrigation methods have proven to be efficacious in mitigating CH_4 emissions in paddy cultivation.The promising role of compound microbial agents in refining the rhizospheric ecosystem suggests their potential as novel agents in reducing CH_4 emissions from paddy fields.To explore a new method of using compound microbial agents to reduce CH_4 emissions,we conducted pot and field experiments over the period of 2022-2023.We measured CH_4 flux,the redox potential(Eh)of the soil,the concentration of dissolved oxygen(DO)in the floodwater,and the gene abundance of both methanogens(mcr A)and methanotrophs(pmo A).The results showed that the application of the compound microbial agent led to a significant increase in the DO levels within the floodwater and an increase of 9.26%to 35.01%in the Eh of the tillage soil.Furthermore,the abundance of pmo A increased by 31.20%,while the mcr A/pmo A ratio decreased by 25.96%at the maximum tillering stage.Applying 45-75 kg/hm^(2) of the compound microbial agent before transplanting resulted in a reduction of cumulative CH_4 emissions from paddy fields by 17.49%in single-cropped rice and 43.54%to 50.27%in double-cropped late rice during the tillering stage.Correlation analysis indicated that CH_4 flux was significantly negatively correlated with pmo A gene abundance and soil Eh,and positively related to the mcr A/pmo A ratio.Additionally,soil Eh was significantly positively correlated with pmo A gene abundance,suggesting that paddy soil Eh indirectly affected CH_4 flux by influencing the pmo A gene abundance.In conclusion,the pre-planting application of the compound microbial agent at a rate of 45-75 kg/hm^(2) can enhance the Eh in the rhizosphere and increase the abundance of the pmo A gene,thereby reducing CH_4 emissions from paddy fields during the tillering stage of rice growth.
基金Project(2010CB630904) supported by the National Basic Research Program of ChinaProject(50621063) supported by the Chinese Science Foundation for Distinguished Group
文摘The changes of pH,redox potential,concentrations of soluble iron ions and Cu^2＋ with the time of bioleaching chalcopyrite concentrates by acidithiobacillus ferrooxidans were investigated under the different conditions of initial total-iron amount as well as mole ratio of Fe（III） to Fe（II） in the solutions containing synthetic extracellular polymeric substances （EPS）.When the solution potential is lower than 650 mV （vs SHE）,the inhibition of jarosites to bioleaching chalcopyrite is not vital as EPS produced by bacteria can retard the contamination through flocculating jarosites even if concentration of Fe（III） ions is up to 20 g/L but increases with increasing the concentration of Fe（III） ions;jarosites formed by bio-oxidized Fe3＋ ions are more easy to adhere to outside surface of EPS space on chalcopyrite;the EPS layer with jarosites acts as a weak diffusion barrier to further rapidly create a high redox potential of more than 650 mV by bio-oxidizing Fe^2＋ ions inside and outside EPS space into Fe^3＋ ions,resulting in a rapid deterioration of ion diffusion performance of the EPS layer to inhibit bioleaching chalcopyrite severely and irreversibly.
基金support from the National Natural Science Foundation of China(No.U20A20147).
文摘The alloying process of Mg-La in NaCl-KCl-MgCl_(2)-LaCl_(3)(NKML)melts during electroreduction was elucidated using electrochemical techniques and deep potential molecular dynamics(DPMD)simulations.In the NKML system,the Mg^(2+)/La^(3+)electrodeposition on the tungsten(W)electrode at 973 K was found to be a one-step process.The nucleation of metal ions on the electrode surface followed an instantaneous nucleation mode and was not influenced by the alloying process.The redox potential and underpotential deposition behavior of the metal ions in the NKML system were accurately predicted by the DPMD simulations,confirming the alloying process of the Mg-La.Additionally,scanning electron microscopy with energy dispersive spectroscopy(SEM-EDS)analysis results confirmed that the cathodic deposits consisted of a bright phase and a dark phase,corresponding to the Mg-La alloys and Mg,respectively.The distribution of electrolytic products suggests that the cathodic deposit initially favors the Mg phase,with the Mg-La alloy forming more easily when the Mg source in the melt is depleted.
基金Project supported by the National Natural Science Foundation of China(No.40401029).
文摘The sediment redox potential was raised in the laboratory to estimate reduction of internal available phosphorus loads,such as soluble reactive phosphorus(SRP)and total phosphorus(TP),as well as the main elements of sediment extracts in Dianchi Lake.Several strongly reducing substances in sediments,which mainly originated from anaerobic decomposition of primary producer residues,were responsible for the lower redox potential.In a range of -400 to 200 mV raising the redox potential of sediments decreased TP and SRP in interstitial water.Redox potentials exceeding 320 mV caused increases in TP,whereas SRP maintained a relatively constant minimum level.The concentrations of Al,Fe, Ca^(2+),Mg^(2+),K^+,Na^+ and S in interstitial water were also related to the redox potential of sediments,suggesting that the mechanism for redox potential to regulate the concentration of phosphorus in interstitial water was complex.
基金financially supported by the National Natural Science Foundation of China (No.50934002)the National Basic Research Program of China (No.2010CB630905)the National High Technology Research and Development Program of China (No.2012AA060502)
文摘Based on the bioleaching mechanism and electrochemical studies of metal sulfides, the dissolution rates of chalcocite and pyrite are controlled by redox potentials. Experiment on the bioleaching of chalcocite and pyrite under constant redox potential by sparging with nitrogen gas was demonstrated. By leaching at low and constant redox potential（〈760 mV, vs SHE）, copper recoveries of 90 %–98 % are achieved, which are 10 times more than iron recoveries. The iron-oxidizing bacterial populations are observed to continue to reduce under oxygen limitation conditions, but the Acidithiobacillus that have only sulfur-oxidizing capabilities are an attractive alternative for redox-controlled bioleaching of chalcocite.Thus, the described redox control technique might be one of the effective approaches to balance acid and iron in Zijinshan copper bio-heap leaching practice.
基金Supported by the National Basic Research Program （2010CB630902, 2004CB619202） the National Natural Science Foundation of China （31070034, 30800011, 31260396）+1 种基金 the Knowledge Innovation Program of CAS （2AKSCX2-YW-JS401） the Reward Fund for Young Scientists of Shandong Province （2007BS08002） of China
文摘This work presents a study for chemical leaching of sphalerite concentrate under various constant Fe3+ concentrations and redox potential conditions. The effects of Fe3+ concentration and redox potential on chemical leaching of sphalerite were investigated. The shrinking core model was applied to analyze the experimental results. It was found that both the Fe3+ concentration and the redox potential controlled the chemical leaching rate of sphalerite. A new kinetic model was developed, in which the chemical leaching rate of sphalerite was proportional to Fe3+ concentration and Fe3+ /Fe2+ ratio. All the model parameters were evaluated from the experimental data. The model predictions fit well with the experimental observed values.
文摘The experiments were carried out in continuous flow acidogenic reactors with molasses used as substrate to study the effects of pH and redox potential on fermentation types. The conditions for each fermentation type were investigated at different experimental stages of start up, pH regulating and redox potential regulating. The experiments confirmed that butyric acid type fermentation would occur at pH > 6, the propionic acid type fermentation at pH about 5.5 with E h> -278 mV, and the ethanol type fermentation at pH < 4.5. A higher redox potential will lead to propionic acid type fermentation because propionogens are facultative anaerobic bacteria.
基金financially supported by the Research Fund for Program of Efficient Gold Extraction from Refractory Gold Ore of Sichuan Province,China (No.12120113088100)the National Natural Science Foundation of China (Nos.41401541 and 51474075)the Bureau of International Co-operation,Chinese Academy of Sciences (No.122111KYSB20150013)
文摘Comparisons on the bioleaching and sterile oxidation of pyrite were performed at controlled redox potential of 900 mV(vs.SHE) and different temperatures of 30 and 60℃.For sterile experiments,the redox potential of irrigation solution was controlled by adding hydrogen peroxide solution(15 wt%),while the redox potential of irrigation solution for bioleaching was elevated by flowing through the packed bed in which bacteria were activated and colonized.The rate of pyrite bioleaching is faster than that of sterile oxidation at temperature of 30℃.The reason is that the potential gradient of leaching solution in bioleaching column is much smaller than that in sterile column.The redox potentials of irrigation solution and leaching solution are similar for bioleaching;however,the redox potential difference of irrigation solution and leaching solution for sterile oxidation is about 150 mV.When temperature increases to 60℃ for sterile oxidation,the rate of pyrite leaching is faster than that of bioleaching at temperature of 30℃,even though the redox potential gradient of leaching solution is great.The mineralogy analyses of pyrite residue were performed by scanning electron microscopy-energy-dispersive spectroscopy(SEM-EDS),X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS) analyses.The results confirm that pyrite oxidation might only occur at specific sites with high surface energy on surface and obeys the "indirect mechanism" whether there are bacteria or not.The pyrite oxidation rate is not inhibited by inert sulfur on residue surface at elevated redox potential.According to the conclusions,the way to accelerate pyrite oxidation is proposed.
文摘The relation between EH [Se(VI)/Se(IV)] and pH of soil aqueous extract in Kaschin-Beck disease region and the effects of natural redox agents, namely humic substances, MnO2 and Fe2+, on the redox property of the system were studied. The results indicated that both humic acid and Fe2+ could enhance the reducibility of Se(VI) and MnO2, a limited oxidizability for Se(IV). Fe2+ showed a weak reducibility only at low pH value. The reducibilities of three sulfur-containing compounds for Se(VI) were in following order:thioglycollic acid > L-cysteine > sulfide
基金the support and funding from the National Natural Science Foundation of China(Nos.51673156,52202301)the Natural Science Basic Research Plan in Shaanxi Province of China(No.2022JQ-143)+1 种基金China Postdoctoral Science Foundation(No.2022TQ0256)the Fundamental Research Funds for the Central Universities(No.D5000210607)。
文摘Benefitting from the tunable heterogeneous interface and electronic interaction, metal-polymer-based hybrid composites have attracted wide attention. It is highly desired to develop advanced synthesis methodology and understand the structure-performance relationship. Herein, with the aniline oligomer as the key enabler, we resolve the inferior dynamics issue in the Ag+-aniline reaction system, and successfully fabricate a sub-micron anisotropic eccentric Ag@polyaniline(PANI) particle(an average size up to 340 nm) at room temperature. We demonstrate the synergy mechanism of polyvinyl pyrrolidone and insitu generated PANI for modifying the dynamic reaction interface. We further clarify the H+concentration and the surfactant types serve as main descriptors to tune the reaction dynamics. Besides, by applying other aniline oligomers, a series of similar eccentric structures can also be obtained, indicative of the good applicability of our strategy. Such a sub-micron eccentric structure furnishes the Ag@PANI composites with sound performance for microwave absorption, as demonstrated by a minimum reflection loss(RL) value of-35 d B with an effective absorption bandwidth of 3.7 GHz. This study provides an inspiring scope/concept of eccentric microstructure engineering for better meeting the demands in the high-tech military, energy, environment fields, and beyond.
基金the National Natural Science Foundation of China and the China Postdoctoral Science Foundation for financial support.
文摘By using 1-methyl-2-formyl-5-substituted pyrroles (1-Y), 1-methyl-2-formyl-5-substituted pyrrole phenylhydrazones (2-Y) and 1-methyl-2-formyl-5-substituted pyrrole (4-nitrophenyl)-hydrazones (3-Y) as model structures for nitrogen-containing heterocyclic aromatic compounds, correlation analysis of their redox potential data show that the transition states (TS) of the polarographic process are mainly affected by the polar effects, but spin-delocalizatin effects also exist.
基金supported by the National Nature Science Foundation of China (22105118)the Nature Science Foundation of Shandong Provinces (ZR2021QB095)the China Postdoctoral Science Foundation (2020TQ0183 and 2021M701979)。
文摘Aqueous zinc metal batteries feature intrinsic safety,but suffer from severe dendrite growth and water-derived side reactions.Many metal coatings have been explored for stabilizing Zn metal anode via a trialand-error approach.Here,we propose an exercisable way to screen the potential metal coating on Zn anodes in view of de-polarization effect and dendrite-suppressing ability theoretically.As an output of this screening,cadmium(Cd) metal is checked experimentally.Therefore,symmetric ZnllZn cells using Cd coated Zn(Zn@Cd) exhibit an ultra-long cycle life of 3500 h(nearly 5 months) at a high current density of 10 mA cm^(-2),achieving a record-high cumulative capacity(35 A h cm^(-2)) compared to the previous reports.The full cells of Zn@Cd‖MnO_(2) display a markedly improved cycling performance under harsh conditions including a limited Zn supply(N/P ratio=1.7) and a high areal capacity(3.5 mA h cm^(-2)).The significance of this work lies in not only the first report of Cd coating for stabilizing Zn metal anode,but also a feasible way to screen the promising metal materials for other metal anodes.
基金supported by the National Science and Technology Support Plan Project in China (No. 2012BAD04B08, 2011BAD16B14)
文摘A three-year experiment was conducted in the middle-lower reaches of the Yangtze River in China to study the influence of continuous wheat straw return during the rice season and continuous rice straw return in wheat on methane （CH 4 ） emissions from rice fields in which, the rice-wheat rotation system is the most dominant planting pattern. The field experiment was initiated in October 2009 and has continued since the wheat-growing season of that year. The analyses for the present study were conducted in the second （2011） and third （2012） rice growing seasons. Four treatments, namely, the continuous return of wheat straw and rice straw in every season （WR）, of rice straw but no wheat straw return （R）, of wheat straw but no rice straw return （W） and a control with no straw return （CK）, were laid out in a randomized split-plot design. The total seasonal CH 4 emissions ranged from 107.4 to 491.7 kg/ha （2011） and 160.3 to 909.6 kg/ha （2012）. The increase in CH 4 emissions for treatments WR and W were 289% and 230% in the second year and 185% and 225% in the third year, respectively, in relation to CK. We observed less methane emissions in the treatment R than in CK by 14%-43%, but not statistically significant. Treatment R could increase rice productivity while no more CH 4 emission occurs. The difference in the total CH 4 emissions mainly related to a difference in the methane flux rate during the first 30-35 days after transplant in the rice growing season, which was caused by the amount of dissolved oxygen in paddy water and the amount of reducible soil materials.
基金Supported by the National Natural Science Foundation of China (No. 30821140542)the Japan Science and Technology Agency (No. 09000075)
文摘Most studies on dissimilatory nitrate reduction to ammonium （DNRA） in paddy soils were conducted in the laboratory and in situ studies are in need for better understanding of the DNRA process. In this study, in situ incubations of soil DNRA using ^15N tracer were carried out in paddy fields under conventional water （CW） and low water （LW） managements to explore the potential of soil DNRA after liquid cattle waste （LCW） application and to investigate the impacts of soil redox potential （Eh） and labile carbon on DNRA. DNRA rates ranged from 3.06 to 10.40 mg N kg 1 dry soil d-1, which accounted for 8.55%-12.36% and 3.88% 25.44% of consumption of added NO3-^15N when Eh at 5 cm soil depth ranged from 230 to 414 mV and -225 to -65 mV, respectively. DNRA rates showed no significant difference in paddy soils under two water managements although soil Eh and/or dissolved organic carbon （DOC） were more favorable for DNRA in the paddy soil under CW management 1 d before, or 5 and 7 d after LCW application. Soil DNRA rates were negatively correlated with soil Eh （P 〈 0.05, n = 5） but positively correlated with soil DOC （P 〈 0.05, n - 5） in the paddy soil under LW management, while no significant correlations were shown in the paddy soil under CW management. The potential of DNRA measured in situ was consistent with previous laboratory studies; and the controlling factors of DNRA in paddy soils might be different under different water managements, probably due to the presence of different microfioras of DNRA.
基金Project(2016RS2016)supported by the Hunan Provincial Science and Technology Leader(Innovation Team of Interface Chemistry of Efficient and Clean Utilization of Complex Mineral Resources),ChinaProject supported by the Co-Innovation Centre for Clean and Efficient Utilization of Strategic Metal Mineral Resources,ChinaProject(2015CX005)supported by the Innovation Driven Plan of Central South University,China
文摘Many researchers found that the Fe2+together with less amount of Cu2+can accelerate the leaching of chalcopyrite.In this work,the leaching of chalcopyrite with Cu2+was investigated.The leaching residuals were examined by Raman spectroscopy.Based on the leaching experiments,the chemical equilibrium in solution was calculated using Visual MINTEQ.The results showed that the Fe in chalcopyrite lattice was replaced by Cu2+;therefore,the chalcopyrite transformed into covellite.Furthermore,the formation of chalcocite occurred when Fe2+and Fe3+were added to the solution containing Cu2+.The copper extraction increased with a decrease of the initial redox potential(or the ratio of Fe3+/Fe2+).
