The non-aqueous solid-liquid biphasic solvent of 2-amino-2-methyl-1-propanol(AMP)/piperazine(PZ)/dipropylene glycol dimethyl ether(DME)features a high CO_(2)absorption loading,favorable phase separation behavior and h...The non-aqueous solid-liquid biphasic solvent of 2-amino-2-methyl-1-propanol(AMP)/piperazine(PZ)/dipropylene glycol dimethyl ether(DME)features a high CO_(2)absorption loading,favorable phase separation behavior and high regeneration efficiency.Different with the liquid-liquid phase change solvent,the reaction kinetics of CO_(2)capture into solid-liquid biphasic solvent was rarely studied.In the present work,the reaction kinetics of CO_(2)absorption into AMP/PZ/DME solid-liquid biphasic solvent was investigated into the double stirred kettle reactor.The absorption reaction followed a pseudo-first-order kinetic model according to the zwitterion mechanism.The overall reaction rate constant(kov)and the enhancement factor(E)of CO_(2)absorption both increased with increasing temperature.The total mass transfer resistance of the absorbent decreased with increasing temperature and increased with increasing absorption loading,so the higher reaction temperature was conducive to the absorption,and the liquid phase mass transfer resistance was the main factor affecting the absorption rate.展开更多
The actual performance of vanadium redox flow batteries (VRFBs) is still significantly constrained by the slow kinetics and major parasitic reactivity of anode issues. Herein, a B-site management strategy of SrBO3 (B ...The actual performance of vanadium redox flow batteries (VRFBs) is still significantly constrained by the slow kinetics and major parasitic reactivity of anode issues. Herein, a B-site management strategy of SrBO3 (B = Ti, Zr, Hf) perovskites was proposed to promote the anode reaction jointly explored by experiments and first-principle calculations. As the atomic number of B increases, the enhanced polarity of the B-O bond and the increased oxygen defect can boost the adsorption of vanadium ions, while the weakened orbital hybridization of the B-O bond facilitates the charge transfer of anode reaction. Compared with SrTiO3 and SrZrO3, oversized particles and deformed crystals of SrHfO3 reduce its catalysis. Of SrBO3 perovskites, SrZrO3 stands out in catalysis, owing to its outstanding combination of high hydrophilicity, large surface area, and desired crystal structure. Further, the VRFB using SrZrO3 presents a superior energy efficiency (EE) of 63.2% at 300 mA cm-2 and an increase of 15% in EE compared with the pristine cell at 200 mA cm-2. This work lays the foundation for building the connections between the structural and compositional flexibility and the tunable perovskite properties desirable for vanadium redox reactions.展开更多
Hydrogen(H_(2))is a promising renewable energy which finds wide applications as the world gears toward low-carbon economy.However,current H_(2) production via steam methane reforming of natural gas or gasification of ...Hydrogen(H_(2))is a promising renewable energy which finds wide applications as the world gears toward low-carbon economy.However,current H_(2) production via steam methane reforming of natural gas or gasification of coal are laden with high CO_(2) footprints.Recently,methane(CH_(4))pyrolysis has emerged as a potential technology to generate low-carbon H_(2) and solid carbon.In this review,the current state-of-art and recent progress of H_(2) production from CH_(4) pyrolysis are reviewed in detail.Aspects such as funda-mental mechanism and chemistry involved,effect of process parameters on the conversion efficiency and reaction kinetics for various reaction media and catalysts are elucidated and critically discussed.Temper-ature,among other factors,plays the most critical influence on the methane pyrolysis reaction.Molten metal/salt could lower the operating temperature of methane pyrolysis to<1000℃,whereas plasma technology usually operates in the regime of>1000℃.Based on the reaction kinetics,metal-based cata-lysts were more efficient in lowering the activation energy of the reaction to 29.5-88 kJ/mol from that of uncatalyzed reaction(147-420.7 kJ/mol).Besides,the current techno-economic performance of the pro-cess reveals that the levelized cost of H_(2) is directly influenced by the sales price of carbon(by-product)generated,which could offset the overall cost.Lastly,the main challenges of reactor design for efficient product separation and retrieval,as well as catalyst deactivation/poisoning need to be debottlenecked.展开更多
Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reserv...Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reservoir.Here,alloying Li metal with low-content magnesium(Mg)is proposed to mitigate the reaction kinetics between Li metal anodes and electrolytes.Mg atoms enter the lattice of Li atoms,forming solid solution due to the low amount(5 wt%)of Mg.Mg atoms mainly concentrate near the surface of Mg-alloyed Li metal anodes.The reactivity of Mg-alloyed Li metal is mitigated kinetically,which results from the electron transfer from Li to Mg atoms due to the electronegativity difference.Based on quantitative experimental analysis,the consumption rate of active Li and electrolytes is decreased by using Mgalloyed Li metal anodes,which increases the cycle life of Li metal batteries under demanding conditions.Further,a pouch cell(1.25 Ah)with Mg-alloyed Li metal anodes delivers an energy density of 340 Wh kg^(-1)and a cycle life of 100 cycles.This work inspires the strategy of modifying Li metal anodes to kinetically mitigate the side reactions with electrolytes.展开更多
The thermal decomposition behavior and nonisothermal reaction kinetics of the double-base gun propellants containing the mixed ester of triethyleneglycol dinitrate（TEGDN） and nitroglycerin（NG） were investigated by...The thermal decomposition behavior and nonisothermal reaction kinetics of the double-base gun propellants containing the mixed ester of triethyleneglycol dinitrate（TEGDN） and nitroglycerin（NG） were investigated by thermogravimetry（TG） and differential thermogravimetry（DTG）, and differential scanning calorimetry（DSC） under the high-pressure dynamic ambience. The results show that the thermal decomposition processes of the mixed nitric ester gun propellants have two mass-loss stages. Nitric ester evaporates and decomposes in the first stage, and nitrocellulose and centralite II（C2） decompose in the second stage. The mass loss, the DTG peak points, and the terminated temperatures of the two stages are changeable with the difference of the mass ratio of TEGDN to NG. There is only one obvious exothermic peak in the DSC curves under the different pressures. With the increase in the furnace pressure, the peak temperature decreases, and the decomposition heat increases. With the increase in the content of TEGDN, the decomposition heat decreases at 0.1 MPa and rises at high pressure. The variety of mass ratio of TEGDN to NG makes few effect on the exothermic peak temperatures in the DSC curves at different pressures. The kinetic equation of the main exothermal decomposition reaction of the gun propellant TG0601 was determined as： dα/dt=1021.59（1-α）3e-2.60×104/T. The reaction mechanism of the process can be classified as chemical reaction. The critical temperatures of the thermal explosion（Tbe and Tbp） obtained from the onset temperature（Te） and the peak temperature（Tp） are 456.46 and 473.40 K, respectively. ΔS≠, ΔH≠, and ΔG≠ of the decomposition reaction are 163.57 J·mol^-1·K^-1, 209.54 kJ·mol^-1, and 133.55 kJ·mol^-1, respectively.展开更多
Based on the theory of first-order reaction kinetics,a thermal reaction kinetic model in integral form has been derive.To make the model more applicable,the effects of time and the conversion degree on the reaction ra...Based on the theory of first-order reaction kinetics,a thermal reaction kinetic model in integral form has been derive.To make the model more applicable,the effects of time and the conversion degree on the reaction rate parameters were considered.Two types of undetermined functions were used to compensate for the intrinsic variation of the reaction rate,and two types of correction methods are provided.The model was explained and verified using published experimental data of different polymer thermal reaction systems,and its effectiveness and wide adaptability were confirmed.For the given kinetic model,only one parameter needs to be determined.The proposed empirical model is expected to be used in the numerical simulation of polymer thermal reaction process.展开更多
One-sixth of the currently known natural products containα,β-unsaturated carbonyl groups.Our previous studies reported a rare C-sulfonate metabolic pathway.Sulfonate groups were linked to theβ-carbon ofα,β-unsatu...One-sixth of the currently known natural products containα,β-unsaturated carbonyl groups.Our previous studies reported a rare C-sulfonate metabolic pathway.Sulfonate groups were linked to theβ-carbon ofα,β-unsaturated carbonyl-based natural compounds through this pathway.However,the mechanism of this type of metabolism is still not fully understood,especially whether it is formed through enzyme-mediated biotransformation or direct sulfite addition.In this work,the enzyme-mediated and non-enzymatic pathways were studied.First,the sulfite content in rat intestine was determined by LC-MS/MS.The results showed that the amount of sulfite in rat intestinal contents was from 41.5 to 383μg·g^(-1),whereas the amount of sulfite in rat feed was lower than the lower limit of quantitation(20μg·g^(-1)).Second,the reaction kinetics of sulfite-andrographolide reactions in phosphate buffer solutions(pH 6-8)was studied.The half-lives of andrographolide ranged from minutes to hours.This was suggested that the C-sulfonate reaction of andrographolide was very fast.Third,the C-sulfonate metabolites of andrographolide were both detected when andrographolide and L-cysteine-S-conjugate andrographolide were incubated with the rat small intestine contents or sulfite,indicating that the sulfite amount in rat intestine contents was high enough to react with andrographolide,which assisted a significant portion of andrographolide metabolism.Finally,the comparison of andrographolide metabolite profiles among liver homogenate(with NADPH),liver S9(with NADPH),small intestine contents homogenate(with no NADPH),and sulfite solution incubations showed that the C-sulfonate metabolites were predominantly generated in the intestinal tract by non-enzymatic pathway.In summary,sulfite can serve as a substrate for C-sulfonate metabolism,and these results identified non-enzymatically nucleophilic addition as the potential mechanism for C-sulfonate metabolism of compounds containingα,β-unsaturated carbonyl moiety.展开更多
Toluene-2,4-bisurea (TBU) is an important intermediate for urea route to dimethyl toluene-2,4-dicarbamate and the study on TBU synthesis via the reaction of 2,4-toluene diamine (TDA) and urea is of great significance....Toluene-2,4-bisurea (TBU) is an important intermediate for urea route to dimethyl toluene-2,4-dicarbamate and the study on TBU synthesis via the reaction of 2,4-toluene diamine (TDA) and urea is of great significance. Firstly, thermodynamic analysis shows that the reaction is exothermic and a high equilibrium conversion of TDA is expected due to its large reaction equilibrium constant. Secondly, under the suitable reaction conditions, 130 °C, 7 h, and molar ratio of TDA/zinc acetate/urea/sulfolane 1/0.05/3.5/10, TDA conversion is 54.3%, and TBU yield and selectivity are 39.8% and 73.3% respectively. Lastly, the synthesis of TBU is a 1st order reaction with respect to TDA and the reaction kinetics model is established. This work will provide useful information for commercializing the urea route to toluene-2,4-dicarbamate (TDC).展开更多
High energy density Li-CO_(2)batteries have attracted much attention owing to the"two birds with one stone"feature in fixing greenhouse gas CO_(2)and providing renewable energy.However,poor reversibility of ...High energy density Li-CO_(2)batteries have attracted much attention owing to the"two birds with one stone"feature in fixing greenhouse gas CO_(2)and providing renewable energy.However,poor reversibility of the discharge product Li_(2)CO_(3)is one of the main problems that limit its application,resulting in poor cycling stability and severe polarization.Herein,copper indium sulfide(CIS),a semiconducting non-precious metal sulfide,is fabricated as cathode catalysts for high-performance Li-CO_(2)batteries.Combined with the synergistic effect of bimetallic valence bonding and coordinated electron transfer,Li-CO_(2)batteries using CIS cathodes exhibit high full specific discharge capacity,excellent rate capability and cycle stability,namely it delivers a high specific full discharge capacity of 8878μAh cm^(-2),runs steadily from 10 to 100μA cm^(-2),and performs a stable long-term cycling behavior(>1050 h)under a high energy efficiency of 84%and a low charge voltage of approximately 3.4 V at 20μA cm^(-2)within 100μAh cm^(-2).In addition,a flexible Li-CO_(2)pouch cell is constructed to reveal the potential of employing CIS to fabricate flexible high energy storage devices in practical applications.This work shows a promising development pathway toward next-generation sustainable energy storage devices.展开更多
As one of the few renewable aromatic resources,the research of depolymerization of lignin into highvalue chemicals has attracted extensive attention in recent years.Catalytic wet aerobic oxidation(CWAO)is an effective...As one of the few renewable aromatic resources,the research of depolymerization of lignin into highvalue chemicals has attracted extensive attention in recent years.Catalytic wet aerobic oxidation(CWAO)is an effective technology to convert lignin like sodium lignosulfonate(SL),a lignin derivative,into aromatic aldehydes such as vanillin and syringaldehyde.However,how to improve the yield of aromatic aldehyde and conversion efficiency is still a challenge,and many operating conditions that significantly affect the yield of these aromatic compounds have rarely been investigated systematically.In this work,we adopted the stirred tank reactor(STR)for the CWAO process with nano-CuO as catalyst to achieve the conversion of SL into vanillin and syringaldehyde.The effect of operating conditions including reaction time,oxygen partial pressure,reaction temperature,SL concentration,rotational speed,catalyst amount,and NaOH concentration on the yield of single phenolic compound was systematically investigated.The results revealed that all these operating conditions exhibit a significant effect on the aromatic aldehyde yield.Therefore,they should be regulated in an optimal value to obtain high yield of these aldehydes.More importantly,the reaction kinetics of the lignin oxidation was explored.This work could provide basic data for the optimization and design of industrial operation of lignin oxidation.展开更多
Baotou RE concentrate was decomposed with concentrated sulfuric acid by controlling the roasting temperature below 500℃.Thermogravimetry-differential thermal analysis（TG-DTA） and chemical analytical methods were us...Baotou RE concentrate was decomposed with concentrated sulfuric acid by controlling the roasting temperature below 500℃.Thermogravimetry-differential thermal analysis（TG-DTA） and chemical analytical methods were used to study the thermal decomposition process and the thermal decomposition effect.The Freeman-Carroll method was applied to analyze the TG-DTA curves.The activation energy, reaction order, and reaction frequency factor at different stages were calculated.The Satava method was used to deduce the reaction mechanism and the relative reaction rate during the thermal decomposition process.展开更多
In this study, the kinetics of isopropyl palmitate synthesis including the reaction mechanism was studied based on the two-step noncatalytic method. The liquid-phase diffusion effect on the reaction process was elimin...In this study, the kinetics of isopropyl palmitate synthesis including the reaction mechanism was studied based on the two-step noncatalytic method. The liquid-phase diffusion effect on the reaction process was eliminated by adjusting the stirring rate. The results showed that the two-step reaction followed a tetrahedral mechanism and conformed to second-order reaction kinetics. Nucleophilic attack on the carbonyl carbon afforded an intermediate, containing a tetrahedral carbon center. The intermediate ultimately decomposed by elimination of the leaving group, affording isopropyl palmitate. The experimental data were analyzed at different temperatures by the integral method. The kinetic equations of the each step were deduced, and the activation energy and frequency factor were obtained. Experiments were performed to verify the feasibility of kinetic equations, and the result showed that the kinetic equations were reliable. This study could be very signi ficant to both industrial application and determining the continuous production of isopropyl palmitate.展开更多
The time integration method with four-order accuracy, self-starting and implicit for the diffuse chemical reaction kinetics equation or the transient instantaneous temperature filed equation was presented. The example...The time integration method with four-order accuracy, self-starting and implicit for the diffuse chemical reaction kinetics equation or the transient instantaneous temperature filed equation was presented. The examples show that both accuracy and stability are better than Runge-Kutta method with four-order. The coefficients of the equation are stored with sparse matrix pattern, so an algorithm is presented which combines a compact storage scheme with reduced computation cost. The computation of the competitive and consecutive reaction in the rotating packed bed, taken as examples, shows that the method is effective.展开更多
The reaction kinetics of the heterogeneous oxidation of toluene with Mn 3+ was studied by considering the effects of disproportionation of Mn 3+ in reaction system, a 'parallel' modulus was set up. A...The reaction kinetics of the heterogeneous oxidation of toluene with Mn 3+ was studied by considering the effects of disproportionation of Mn 3+ in reaction system, a 'parallel' modulus was set up. And then the concentration of Mn 3+ in disproportionation and the concentration of benzaldehyde in oxidation were respectively determined in turn, the rate constant, order and pseudo activation energy of the heterogeneous oxidation were obtained by mathematical deduction and the kinetic equation was concluded. In addition, the reaction mechanism was analyzed. It shows that the results are completely consistent with modulus.展开更多
The continuous rise in CO_(2)emissions from fossil fuel consumption has intensified the search for alternative clean energy sources.Hydrogen produced from renewable sources like ethanol offers a promising alternative ...The continuous rise in CO_(2)emissions from fossil fuel consumption has intensified the search for alternative clean energy sources.Hydrogen produced from renewable sources like ethanol offers a promising alternative to fossil fuels,mitigating CO_(2)emissions.This study investigates the kinetics of hydrogen production via ethanol steam reforming using a nickel-based catalyst,specifically the Ar-401 catalyst.Characterization techniques,including scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy,transmission electron microscopy,Brunauer–Emmett–Teller method,temperature-programmed reduction,and powder X-ray diffraction,were used to analyze the catalyst properties.Under optimal conditions of 973 K,atmospheric pressure,and a steam-to-ethanol ratio of 9,we achieved 100%ethanol conversion,74.8%hydrogen selectivity,and 85%hydrogen yield.Kinetic experiments were conducted under kinetically controlled conditions,examining the effects of temperature(473–673 K)and weight hourly space velocity ranging from 1 to 15(g·h/mol).A power law kinetic model was developed,yielding an activation energy of 11.17 kJ/mol and a reaction order of 0.46,with an absolute average deviation of 3.23%between predicted and experimental rates.This study provides key insights into the reaction mechanisms and highlights the effectiveness of the nickel-based catalyst,providing valuable insights for the design of efficient chemical reactors for sustainable hydrogen production.展开更多
Uncontrolled dendrite growth,sluggish reaction kinetics,and drastic side reactions on the anodeelectrolyte interface are the main obstacles that restrict the application prospect of aqueous zinc-ion batteries.Traditio...Uncontrolled dendrite growth,sluggish reaction kinetics,and drastic side reactions on the anodeelectrolyte interface are the main obstacles that restrict the application prospect of aqueous zinc-ion batteries.Traditional glass fiber(GF)separator with chemical inertness is almost ineffective in restricting these challenges.Herein,inspired by the ionic enrichment behavior of seaweed plants,a facile biomass species,anionic sodium alginate(SA),is purposely decorated on the commercial GF separator to tackle these issues towards Zn anode.Benefiting from the abundant zincophilic functional groups and superior mechanical strength properties,the as-obtained SA@GF separator could act as ion pump to boost the Zn^(2+)transference number(0.68),reduce the de-solvation energy barrier of hydrated Zn^(2+),and eliminate the undesired concentration polarization effect,which are verified by experimental tests,theoretical calculations,and finite element simulation,respectively.Based on these efficient modulation mechanisms,the SA@GF separator can synchronously achieve well-aligned Zn deposition and the suppression of parasitic side-reactions.Therefore,the Zn‖Zn coin cell integrated with SA@GF separator could yield a prolonged calendar lifespan over 1230 h(1 mA cm^(-2)and 1 mAh cm^(-2)),exhibiting favorable competitiveness with previously reported separator modification strategies.Impressively,the Zn-MnO_(2)full and pouch cell assembled with the SA@GF separator also delivered superior cycling stability and rate performance,further verifying its practical application effect.This work provides a new design philosophy to stabilize the Zn anode from the aspect of separator.展开更多
Highly active and low-cost oxygen evolution reaction(OER)catalytic electrodes are extremely essential for exploration of green hydrogen via water splitting.Herein,an advanced Fe-Ni-F electrocatalyst is fabricated by a...Highly active and low-cost oxygen evolution reaction(OER)catalytic electrodes are extremely essential for exploration of green hydrogen via water splitting.Herein,an advanced Fe-Ni-F electrocatalyst is fabricated by a facile annealing strategy using ammonium fluoride,of which the structure feature is unveiled by XRD,FESEM,TEM,EDS,BET,and XPS measurements.The as-prepared Fe-Ni-F addresses a low overpotential of 277 mV and a small Tafel slope of 49 mV dec^(-1)at a current density of 10 mA cm^(-2),significantly outperforming other control samples as well as the state-of-the-art RuO_(2).The advanced nature of our Fe-Ni-F catalyst could also be further evidenced from the robust stability in KOH alkaline solution,showing as 5.41%degradation after 24 h continuous working.Upon analysis,it suggests that the decent catalytic activity should be attributed to the formed bimetallic(oxy)hydroxides because of the introduction of fluoride and the synergistic effect of iron and nickel towards oxygen generation.This work represents the potential of Fe-and/or Ni-based fluoride as efficient catalyst for low-energy consumption oxygen generation.展开更多
Ultrafast reaction kinetics is essential for rapid detection,synthesis,and process monitoring,but the intrinsic energy barrier as a basic material property is challenging to tailor.With the involvement of nanointerfac...Ultrafast reaction kinetics is essential for rapid detection,synthesis,and process monitoring,but the intrinsic energy barrier as a basic material property is challenging to tailor.With the involvement of nanointerfacial chemistry,we propose a carbonization-based strategy for achieving ultrafast chemical reaction.In a case study,ultrafast Griess reaction within 1 min through the carbonization of N-(1-naphthalene)ethylenediamine(NETH)was realized.The carbonization-mediated ultrafast reaction is attributed to the synergic action of reduced electrostatic repulsion,enriched reactant concentration,and boosted NETH nucleophilicity.The enhanced reaction kinetics in o-phenylenediamine-Cu^(2)+and ophenylenediamine-ascorbic acid systems validate the universality of carbonization-engineered ultrafast chemical reaction strategy.The finding of this work offers a novel and simple tactic for the fabrication of multifunctional nanoparticles as ultrafast and effective nanoreactants and/or reporters in analytical,biological,and material aspects.展开更多
CO_(2)injection into geological formations has been proven to be an effective approach for carbon storage.When dissolved in formation water,CO_(2)forms carbonic acid that induces mineral dissolution at pore surfaces u...CO_(2)injection into geological formations has been proven to be an effective approach for carbon storage.When dissolved in formation water,CO_(2)forms carbonic acid that induces mineral dissolution at pore surfaces under acidic conditions.Comprehensive understanding of geochemical interaction between carbonic acid and reservoir rocks is crucial for assessing environmental impact on geological formations.This study focuses on a tight oil sandstone reservoir.After characterizing basic petrophysical properties and mineral composition of rock samples,a series of carbonic acid corrosion experiments with both core and corresponding pure mineral samples were carried out,respectively.Dissolution solutions collected during the experiments were analyzed to examine the variations of ion concentrations in both core and pure mineral solutions.The carbonic acid-pure mineral corrosion kinetics were investigated.The correlations between carbonic acid with core and pure mineral corrosion scenarios were established from the sample mass,reaction rate,and ion concentration.The results show that after corrosion,the mass of calcite and dolomite in the rock sample decreased by 66.7%and 27.3%,respectively.When the corrosion was stabilized,the concentrations of Ca^(2+)and Mg^(2+)in the core solution were 72.9 and 74.4 mg/L.respectively,which was 40.5-41.3 times higher than that of Na+.The reaction kinetics analysis of carbonic acid-rock revealed a two-stage reaction in the pure mineral corrosion process,rapid reaction stage,and slow reaction stage,with different reaction rate constants and reaction orders for each ion.With the correlation between carbonic acid reaction with core and pure minerals,an effective and rapid evaluation method with pure minerals for the carbonic water-rock reaction is established,which costs a shorter time and is easier to investigate.This study provides a simple and faster method to evaluate the carbonic acid corrosion reaction during geological carbon storage.展开更多
Aqueous Zn-I_(2)-Mn hybrid batteries demonstrate enhanced capacity,superior redox reaction kinetics,and prolonged cycle life compared to their Zn-I_(2)and Zn-Mn counterparts,making them promising candidates for grid-s...Aqueous Zn-I_(2)-Mn hybrid batteries demonstrate enhanced capacity,superior redox reaction kinetics,and prolonged cycle life compared to their Zn-I_(2)and Zn-Mn counterparts,making them promising candidates for grid-scale energy storage.Nevertheless,challenges remain in developing multifunctional positive electrode materials and elucidating the mechanistic synergy governing iodine and manganese redox reactions.Herein,we present a high-performance free-standing electrode composed of birnessite(KMnO)nanosheet arrays in situ grown on carbon cloth(CC@KMnO)for constructing a Zn-I_(2)-Mn hybrid battery.Combined theoretical studies and in situ characterizations reveal that CC@KMnO enhances iodine species adsorption,lowers the Gibbs free energy change for iodine reduction,and significantly accelerates I^(-)/I_(3)^(-)/I_(5)^(-)redox kinetics while suppressing polyiodide shuttling and corrosion effects.Synchronously,the Zn I_(2)electrolyte facilitates the dissolution of residual and exfoliated KMnO,thereby improving manganese redox reaction kinetics,reversibility,and enhancing cycling stability.Leveraging this mutually reinforcing effect,the Zn-I_(2)-Mn hybrid battery achieves an impressive areal capacity of2.02 m Ah cm^(-2)and maintains long-term durability over 3600 cycles at 2 mA cm^(-2).This work provides valuable insights into designing efficient and durable hybrid energy storage systems.展开更多
基金supported by the National Natural Science Foundation of China(No.22276064)the Youth Innovation Grant of Xiamen,Fujian Province(No.3502Z20206006)+1 种基金the MOE Key Laboratory of Resources and Environmental System Optimization(No.KLRE-KF202205)Fujian Science and Technology Project(No.2022Y3007).
文摘The non-aqueous solid-liquid biphasic solvent of 2-amino-2-methyl-1-propanol(AMP)/piperazine(PZ)/dipropylene glycol dimethyl ether(DME)features a high CO_(2)absorption loading,favorable phase separation behavior and high regeneration efficiency.Different with the liquid-liquid phase change solvent,the reaction kinetics of CO_(2)capture into solid-liquid biphasic solvent was rarely studied.In the present work,the reaction kinetics of CO_(2)absorption into AMP/PZ/DME solid-liquid biphasic solvent was investigated into the double stirred kettle reactor.The absorption reaction followed a pseudo-first-order kinetic model according to the zwitterion mechanism.The overall reaction rate constant(kov)and the enhancement factor(E)of CO_(2)absorption both increased with increasing temperature.The total mass transfer resistance of the absorbent decreased with increasing temperature and increased with increasing absorption loading,so the higher reaction temperature was conducive to the absorption,and the liquid phase mass transfer resistance was the main factor affecting the absorption rate.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.51872090 and 51772097)the Hebei Natural Science Fund for Distinguished Young Scholar(Grant No.E2019209433)+2 种基金the Youth Talent Program of Hebei Provincial Education Department(Grant No.BJ2018020)the Natural Science Foundation of Hebei Province(Grant No.E2020209151)the Natural Science Foundation of Liaoning Province(Grant No.2020-MS-012).
文摘The actual performance of vanadium redox flow batteries (VRFBs) is still significantly constrained by the slow kinetics and major parasitic reactivity of anode issues. Herein, a B-site management strategy of SrBO3 (B = Ti, Zr, Hf) perovskites was proposed to promote the anode reaction jointly explored by experiments and first-principle calculations. As the atomic number of B increases, the enhanced polarity of the B-O bond and the increased oxygen defect can boost the adsorption of vanadium ions, while the weakened orbital hybridization of the B-O bond facilitates the charge transfer of anode reaction. Compared with SrTiO3 and SrZrO3, oversized particles and deformed crystals of SrHfO3 reduce its catalysis. Of SrBO3 perovskites, SrZrO3 stands out in catalysis, owing to its outstanding combination of high hydrophilicity, large surface area, and desired crystal structure. Further, the VRFB using SrZrO3 presents a superior energy efficiency (EE) of 63.2% at 300 mA cm-2 and an increase of 15% in EE compared with the pristine cell at 200 mA cm-2. This work lays the foundation for building the connections between the structural and compositional flexibility and the tunable perovskite properties desirable for vanadium redox reactions.
基金support by the Education University of Hong Kong to perform this project under International Grant(UMT/International Grant/2020/53376).
文摘Hydrogen(H_(2))is a promising renewable energy which finds wide applications as the world gears toward low-carbon economy.However,current H_(2) production via steam methane reforming of natural gas or gasification of coal are laden with high CO_(2) footprints.Recently,methane(CH_(4))pyrolysis has emerged as a potential technology to generate low-carbon H_(2) and solid carbon.In this review,the current state-of-art and recent progress of H_(2) production from CH_(4) pyrolysis are reviewed in detail.Aspects such as funda-mental mechanism and chemistry involved,effect of process parameters on the conversion efficiency and reaction kinetics for various reaction media and catalysts are elucidated and critically discussed.Temper-ature,among other factors,plays the most critical influence on the methane pyrolysis reaction.Molten metal/salt could lower the operating temperature of methane pyrolysis to<1000℃,whereas plasma technology usually operates in the regime of>1000℃.Based on the reaction kinetics,metal-based cata-lysts were more efficient in lowering the activation energy of the reaction to 29.5-88 kJ/mol from that of uncatalyzed reaction(147-420.7 kJ/mol).Besides,the current techno-economic performance of the pro-cess reveals that the levelized cost of H_(2) is directly influenced by the sales price of carbon(by-product)generated,which could offset the overall cost.Lastly,the main challenges of reactor design for efficient product separation and retrieval,as well as catalyst deactivation/poisoning need to be debottlenecked.
基金supported by the National Key Research and Development Program(2021YFB2400300)National Natural Science Foundation of China(22379013 and 22209010)the Beijing Institute of Technology“Xiaomi Young Scholars”program。
文摘Lithium(Li)metal is regarded as a promising anode candidate for high-energy-density rechargeable batteries.Nevertheless,Li metal is highly reactive against electrolytes,leading to rapid decay of active Li metal reservoir.Here,alloying Li metal with low-content magnesium(Mg)is proposed to mitigate the reaction kinetics between Li metal anodes and electrolytes.Mg atoms enter the lattice of Li atoms,forming solid solution due to the low amount(5 wt%)of Mg.Mg atoms mainly concentrate near the surface of Mg-alloyed Li metal anodes.The reactivity of Mg-alloyed Li metal is mitigated kinetically,which results from the electron transfer from Li to Mg atoms due to the electronegativity difference.Based on quantitative experimental analysis,the consumption rate of active Li and electrolytes is decreased by using Mgalloyed Li metal anodes,which increases the cycle life of Li metal batteries under demanding conditions.Further,a pouch cell(1.25 Ah)with Mg-alloyed Li metal anodes delivers an energy density of 340 Wh kg^(-1)and a cycle life of 100 cycles.This work inspires the strategy of modifying Li metal anodes to kinetically mitigate the side reactions with electrolytes.
基金the National Natural Science Foundation of China(No.20573098)the Foundation of Key Laboratory of Science and Technology for National Defence of Propellant and Explosive of China(No.9140C3503020605).
文摘The thermal decomposition behavior and nonisothermal reaction kinetics of the double-base gun propellants containing the mixed ester of triethyleneglycol dinitrate（TEGDN） and nitroglycerin（NG） were investigated by thermogravimetry（TG） and differential thermogravimetry（DTG）, and differential scanning calorimetry（DSC） under the high-pressure dynamic ambience. The results show that the thermal decomposition processes of the mixed nitric ester gun propellants have two mass-loss stages. Nitric ester evaporates and decomposes in the first stage, and nitrocellulose and centralite II（C2） decompose in the second stage. The mass loss, the DTG peak points, and the terminated temperatures of the two stages are changeable with the difference of the mass ratio of TEGDN to NG. There is only one obvious exothermic peak in the DSC curves under the different pressures. With the increase in the furnace pressure, the peak temperature decreases, and the decomposition heat increases. With the increase in the content of TEGDN, the decomposition heat decreases at 0.1 MPa and rises at high pressure. The variety of mass ratio of TEGDN to NG makes few effect on the exothermic peak temperatures in the DSC curves at different pressures. The kinetic equation of the main exothermal decomposition reaction of the gun propellant TG0601 was determined as： dα/dt=1021.59（1-α）3e-2.60×104/T. The reaction mechanism of the process can be classified as chemical reaction. The critical temperatures of the thermal explosion（Tbe and Tbp） obtained from the onset temperature（Te） and the peak temperature（Tp） are 456.46 and 473.40 K, respectively. ΔS≠, ΔH≠, and ΔG≠ of the decomposition reaction are 163.57 J·mol^-1·K^-1, 209.54 kJ·mol^-1, and 133.55 kJ·mol^-1, respectively.
基金supported by the National Key Research and Development Program of China(Grant No.2018YFB2001002)。
文摘Based on the theory of first-order reaction kinetics,a thermal reaction kinetic model in integral form has been derive.To make the model more applicable,the effects of time and the conversion degree on the reaction rate parameters were considered.Two types of undetermined functions were used to compensate for the intrinsic variation of the reaction rate,and two types of correction methods are provided.The model was explained and verified using published experimental data of different polymer thermal reaction systems,and its effectiveness and wide adaptability were confirmed.For the given kinetic model,only one parameter needs to be determined.The proposed empirical model is expected to be used in the numerical simulation of polymer thermal reaction process.
基金supported by the National Natural Science Foundation of China(No.81873079)。
文摘One-sixth of the currently known natural products containα,β-unsaturated carbonyl groups.Our previous studies reported a rare C-sulfonate metabolic pathway.Sulfonate groups were linked to theβ-carbon ofα,β-unsaturated carbonyl-based natural compounds through this pathway.However,the mechanism of this type of metabolism is still not fully understood,especially whether it is formed through enzyme-mediated biotransformation or direct sulfite addition.In this work,the enzyme-mediated and non-enzymatic pathways were studied.First,the sulfite content in rat intestine was determined by LC-MS/MS.The results showed that the amount of sulfite in rat intestinal contents was from 41.5 to 383μg·g^(-1),whereas the amount of sulfite in rat feed was lower than the lower limit of quantitation(20μg·g^(-1)).Second,the reaction kinetics of sulfite-andrographolide reactions in phosphate buffer solutions(pH 6-8)was studied.The half-lives of andrographolide ranged from minutes to hours.This was suggested that the C-sulfonate reaction of andrographolide was very fast.Third,the C-sulfonate metabolites of andrographolide were both detected when andrographolide and L-cysteine-S-conjugate andrographolide were incubated with the rat small intestine contents or sulfite,indicating that the sulfite amount in rat intestine contents was high enough to react with andrographolide,which assisted a significant portion of andrographolide metabolism.Finally,the comparison of andrographolide metabolite profiles among liver homogenate(with NADPH),liver S9(with NADPH),small intestine contents homogenate(with no NADPH),and sulfite solution incubations showed that the C-sulfonate metabolites were predominantly generated in the intestinal tract by non-enzymatic pathway.In summary,sulfite can serve as a substrate for C-sulfonate metabolism,and these results identified non-enzymatically nucleophilic addition as the potential mechanism for C-sulfonate metabolism of compounds containingα,β-unsaturated carbonyl moiety.
基金Supported by the National Natural Science Foundation of China （20976035, 21076059） the Natural Science Foundation of Hebei Province （B2010000019）
文摘Toluene-2,4-bisurea (TBU) is an important intermediate for urea route to dimethyl toluene-2,4-dicarbamate and the study on TBU synthesis via the reaction of 2,4-toluene diamine (TDA) and urea is of great significance. Firstly, thermodynamic analysis shows that the reaction is exothermic and a high equilibrium conversion of TDA is expected due to its large reaction equilibrium constant. Secondly, under the suitable reaction conditions, 130 °C, 7 h, and molar ratio of TDA/zinc acetate/urea/sulfolane 1/0.05/3.5/10, TDA conversion is 54.3%, and TBU yield and selectivity are 39.8% and 73.3% respectively. Lastly, the synthesis of TBU is a 1st order reaction with respect to TDA and the reaction kinetics model is established. This work will provide useful information for commercializing the urea route to toluene-2,4-dicarbamate (TDC).
基金supports by the National Natural Science Foundation of China(No.52072352,21875226,U20A2072,52102320)the Foundation for the Youth S&T Innovation Team of Sichuan Province(2020JDTD0035)+1 种基金Tianfu Rencai Plan,the Science Foundation for Distinguished Young Scholars of Sichuan Province(2017JQ0036)the Chengdu Talent plan,Science and Technology Projects for Administration for Market Regulation of Sichuan Province(SCSJ2020016).
文摘High energy density Li-CO_(2)batteries have attracted much attention owing to the"two birds with one stone"feature in fixing greenhouse gas CO_(2)and providing renewable energy.However,poor reversibility of the discharge product Li_(2)CO_(3)is one of the main problems that limit its application,resulting in poor cycling stability and severe polarization.Herein,copper indium sulfide(CIS),a semiconducting non-precious metal sulfide,is fabricated as cathode catalysts for high-performance Li-CO_(2)batteries.Combined with the synergistic effect of bimetallic valence bonding and coordinated electron transfer,Li-CO_(2)batteries using CIS cathodes exhibit high full specific discharge capacity,excellent rate capability and cycle stability,namely it delivers a high specific full discharge capacity of 8878μAh cm^(-2),runs steadily from 10 to 100μA cm^(-2),and performs a stable long-term cycling behavior(>1050 h)under a high energy efficiency of 84%and a low charge voltage of approximately 3.4 V at 20μA cm^(-2)within 100μAh cm^(-2).In addition,a flexible Li-CO_(2)pouch cell is constructed to reveal the potential of employing CIS to fabricate flexible high energy storage devices in practical applications.This work shows a promising development pathway toward next-generation sustainable energy storage devices.
基金supported by the National Key Research and Development Program of China(2019YFA0210302)the National Natural Science Foundation of China(21878009).
文摘As one of the few renewable aromatic resources,the research of depolymerization of lignin into highvalue chemicals has attracted extensive attention in recent years.Catalytic wet aerobic oxidation(CWAO)is an effective technology to convert lignin like sodium lignosulfonate(SL),a lignin derivative,into aromatic aldehydes such as vanillin and syringaldehyde.However,how to improve the yield of aromatic aldehyde and conversion efficiency is still a challenge,and many operating conditions that significantly affect the yield of these aromatic compounds have rarely been investigated systematically.In this work,we adopted the stirred tank reactor(STR)for the CWAO process with nano-CuO as catalyst to achieve the conversion of SL into vanillin and syringaldehyde.The effect of operating conditions including reaction time,oxygen partial pressure,reaction temperature,SL concentration,rotational speed,catalyst amount,and NaOH concentration on the yield of single phenolic compound was systematically investigated.The results revealed that all these operating conditions exhibit a significant effect on the aromatic aldehyde yield.Therefore,they should be regulated in an optimal value to obtain high yield of these aldehydes.More importantly,the reaction kinetics of the lignin oxidation was explored.This work could provide basic data for the optimization and design of industrial operation of lignin oxidation.
基金supported by the National Natural Science Foundation of China (No. 20877008)the Program for New Century Excellent Telents in University of the Ministry of Education of China (No. 20407003)
文摘Baotou RE concentrate was decomposed with concentrated sulfuric acid by controlling the roasting temperature below 500℃.Thermogravimetry-differential thermal analysis（TG-DTA） and chemical analytical methods were used to study the thermal decomposition process and the thermal decomposition effect.The Freeman-Carroll method was applied to analyze the TG-DTA curves.The activation energy, reaction order, and reaction frequency factor at different stages were calculated.The Satava method was used to deduce the reaction mechanism and the relative reaction rate during the thermal decomposition process.
文摘In this study, the kinetics of isopropyl palmitate synthesis including the reaction mechanism was studied based on the two-step noncatalytic method. The liquid-phase diffusion effect on the reaction process was eliminated by adjusting the stirring rate. The results showed that the two-step reaction followed a tetrahedral mechanism and conformed to second-order reaction kinetics. Nucleophilic attack on the carbonyl carbon afforded an intermediate, containing a tetrahedral carbon center. The intermediate ultimately decomposed by elimination of the leaving group, affording isopropyl palmitate. The experimental data were analyzed at different temperatures by the integral method. The kinetic equations of the each step were deduced, and the activation energy and frequency factor were obtained. Experiments were performed to verify the feasibility of kinetic equations, and the result showed that the kinetic equations were reliable. This study could be very signi ficant to both industrial application and determining the continuous production of isopropyl palmitate.
文摘The time integration method with four-order accuracy, self-starting and implicit for the diffuse chemical reaction kinetics equation or the transient instantaneous temperature filed equation was presented. The examples show that both accuracy and stability are better than Runge-Kutta method with four-order. The coefficients of the equation are stored with sparse matrix pattern, so an algorithm is presented which combines a compact storage scheme with reduced computation cost. The computation of the competitive and consecutive reaction in the rotating packed bed, taken as examples, shows that the method is effective.
文摘The reaction kinetics of the heterogeneous oxidation of toluene with Mn 3+ was studied by considering the effects of disproportionation of Mn 3+ in reaction system, a 'parallel' modulus was set up. And then the concentration of Mn 3+ in disproportionation and the concentration of benzaldehyde in oxidation were respectively determined in turn, the rate constant, order and pseudo activation energy of the heterogeneous oxidation were obtained by mathematical deduction and the kinetic equation was concluded. In addition, the reaction mechanism was analyzed. It shows that the results are completely consistent with modulus.
基金supports of the Mitacs Accelerate(IT29592),Proteum Hydrogen Technology,Natural Sciences and Engineering Research Council of Canada(NSERC DG:RGPIN-2024-04760)the Canada Foundation for Innovation(CFI JELF:37758)are gratefully acknowledged。
文摘The continuous rise in CO_(2)emissions from fossil fuel consumption has intensified the search for alternative clean energy sources.Hydrogen produced from renewable sources like ethanol offers a promising alternative to fossil fuels,mitigating CO_(2)emissions.This study investigates the kinetics of hydrogen production via ethanol steam reforming using a nickel-based catalyst,specifically the Ar-401 catalyst.Characterization techniques,including scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy,transmission electron microscopy,Brunauer–Emmett–Teller method,temperature-programmed reduction,and powder X-ray diffraction,were used to analyze the catalyst properties.Under optimal conditions of 973 K,atmospheric pressure,and a steam-to-ethanol ratio of 9,we achieved 100%ethanol conversion,74.8%hydrogen selectivity,and 85%hydrogen yield.Kinetic experiments were conducted under kinetically controlled conditions,examining the effects of temperature(473–673 K)and weight hourly space velocity ranging from 1 to 15(g·h/mol).A power law kinetic model was developed,yielding an activation energy of 11.17 kJ/mol and a reaction order of 0.46,with an absolute average deviation of 3.23%between predicted and experimental rates.This study provides key insights into the reaction mechanisms and highlights the effectiveness of the nickel-based catalyst,providing valuable insights for the design of efficient chemical reactors for sustainable hydrogen production.
基金supported by research grants from the National Natural Science Foundation of China(52173235,22008193,52106110)the Key Research and Development Project of Hainan Province(ZDYF2024SHFZ038)+2 种基金Venture&Innovation Support Program for Chongqing Overseas Returnees(CX2021018)Research Foundation of Chongqing University of Science and Technology(ckrc2021071)Numerical computations were performed on Hefei Advanced Computing Center.
文摘Uncontrolled dendrite growth,sluggish reaction kinetics,and drastic side reactions on the anodeelectrolyte interface are the main obstacles that restrict the application prospect of aqueous zinc-ion batteries.Traditional glass fiber(GF)separator with chemical inertness is almost ineffective in restricting these challenges.Herein,inspired by the ionic enrichment behavior of seaweed plants,a facile biomass species,anionic sodium alginate(SA),is purposely decorated on the commercial GF separator to tackle these issues towards Zn anode.Benefiting from the abundant zincophilic functional groups and superior mechanical strength properties,the as-obtained SA@GF separator could act as ion pump to boost the Zn^(2+)transference number(0.68),reduce the de-solvation energy barrier of hydrated Zn^(2+),and eliminate the undesired concentration polarization effect,which are verified by experimental tests,theoretical calculations,and finite element simulation,respectively.Based on these efficient modulation mechanisms,the SA@GF separator can synchronously achieve well-aligned Zn deposition and the suppression of parasitic side-reactions.Therefore,the Zn‖Zn coin cell integrated with SA@GF separator could yield a prolonged calendar lifespan over 1230 h(1 mA cm^(-2)and 1 mAh cm^(-2)),exhibiting favorable competitiveness with previously reported separator modification strategies.Impressively,the Zn-MnO_(2)full and pouch cell assembled with the SA@GF separator also delivered superior cycling stability and rate performance,further verifying its practical application effect.This work provides a new design philosophy to stabilize the Zn anode from the aspect of separator.
基金supported by the National Natural Science Foundation of China(No.51804223,52272202)the Innovation Foundation of Key Laboratory of Green Chemical Process of Ministry of Education(No.GCX202113)+1 种基金Bintuan Science and Technology Program(No.2020DB002,2022DB009)the Shenzhen Science and Technology Innovation Committee(No.JCYJ20200109141412308).
文摘Highly active and low-cost oxygen evolution reaction(OER)catalytic electrodes are extremely essential for exploration of green hydrogen via water splitting.Herein,an advanced Fe-Ni-F electrocatalyst is fabricated by a facile annealing strategy using ammonium fluoride,of which the structure feature is unveiled by XRD,FESEM,TEM,EDS,BET,and XPS measurements.The as-prepared Fe-Ni-F addresses a low overpotential of 277 mV and a small Tafel slope of 49 mV dec^(-1)at a current density of 10 mA cm^(-2),significantly outperforming other control samples as well as the state-of-the-art RuO_(2).The advanced nature of our Fe-Ni-F catalyst could also be further evidenced from the robust stability in KOH alkaline solution,showing as 5.41%degradation after 24 h continuous working.Upon analysis,it suggests that the decent catalytic activity should be attributed to the formed bimetallic(oxy)hydroxides because of the introduction of fluoride and the synergistic effect of iron and nickel towards oxygen generation.This work represents the potential of Fe-and/or Ni-based fluoride as efficient catalyst for low-energy consumption oxygen generation.
基金supported by the National Natural Science Foundation of China(Nos.82160153,21505162,22074005,and 22101027)Natural Science Foundation of Hunan Province,China(No.2022SK2102)+1 种基金Hunan Provincial Department of Education Scientific Research Project(No.240994)the Natural Science Foundation of Beijing Municipality(No.2202038).
文摘Ultrafast reaction kinetics is essential for rapid detection,synthesis,and process monitoring,but the intrinsic energy barrier as a basic material property is challenging to tailor.With the involvement of nanointerfacial chemistry,we propose a carbonization-based strategy for achieving ultrafast chemical reaction.In a case study,ultrafast Griess reaction within 1 min through the carbonization of N-(1-naphthalene)ethylenediamine(NETH)was realized.The carbonization-mediated ultrafast reaction is attributed to the synergic action of reduced electrostatic repulsion,enriched reactant concentration,and boosted NETH nucleophilicity.The enhanced reaction kinetics in o-phenylenediamine-Cu^(2)+and ophenylenediamine-ascorbic acid systems validate the universality of carbonization-engineered ultrafast chemical reaction strategy.The finding of this work offers a novel and simple tactic for the fabrication of multifunctional nanoparticles as ultrafast and effective nanoreactants and/or reporters in analytical,biological,and material aspects.
基金the National Natural Science Foundation of China(52474073,52288101,52120105007,51804327)Shandong Provincial Natural Science Foundation(ZR2023ME016)Climb Taishan Scholar Program in Shandong Province(tspd20230605).
文摘CO_(2)injection into geological formations has been proven to be an effective approach for carbon storage.When dissolved in formation water,CO_(2)forms carbonic acid that induces mineral dissolution at pore surfaces under acidic conditions.Comprehensive understanding of geochemical interaction between carbonic acid and reservoir rocks is crucial for assessing environmental impact on geological formations.This study focuses on a tight oil sandstone reservoir.After characterizing basic petrophysical properties and mineral composition of rock samples,a series of carbonic acid corrosion experiments with both core and corresponding pure mineral samples were carried out,respectively.Dissolution solutions collected during the experiments were analyzed to examine the variations of ion concentrations in both core and pure mineral solutions.The carbonic acid-pure mineral corrosion kinetics were investigated.The correlations between carbonic acid with core and pure mineral corrosion scenarios were established from the sample mass,reaction rate,and ion concentration.The results show that after corrosion,the mass of calcite and dolomite in the rock sample decreased by 66.7%and 27.3%,respectively.When the corrosion was stabilized,the concentrations of Ca^(2+)and Mg^(2+)in the core solution were 72.9 and 74.4 mg/L.respectively,which was 40.5-41.3 times higher than that of Na+.The reaction kinetics analysis of carbonic acid-rock revealed a two-stage reaction in the pure mineral corrosion process,rapid reaction stage,and slow reaction stage,with different reaction rate constants and reaction orders for each ion.With the correlation between carbonic acid reaction with core and pure minerals,an effective and rapid evaluation method with pure minerals for the carbonic water-rock reaction is established,which costs a shorter time and is easier to investigate.This study provides a simple and faster method to evaluate the carbonic acid corrosion reaction during geological carbon storage.
基金financially supported by the National Natural Science Foundation of China(22302177)the Key Science and Technology Project of Jinhua City(2024-1-004)the Self Designed Scientific Research of Zhejiang Normal University(2021ZS0604)。
文摘Aqueous Zn-I_(2)-Mn hybrid batteries demonstrate enhanced capacity,superior redox reaction kinetics,and prolonged cycle life compared to their Zn-I_(2)and Zn-Mn counterparts,making them promising candidates for grid-scale energy storage.Nevertheless,challenges remain in developing multifunctional positive electrode materials and elucidating the mechanistic synergy governing iodine and manganese redox reactions.Herein,we present a high-performance free-standing electrode composed of birnessite(KMnO)nanosheet arrays in situ grown on carbon cloth(CC@KMnO)for constructing a Zn-I_(2)-Mn hybrid battery.Combined theoretical studies and in situ characterizations reveal that CC@KMnO enhances iodine species adsorption,lowers the Gibbs free energy change for iodine reduction,and significantly accelerates I^(-)/I_(3)^(-)/I_(5)^(-)redox kinetics while suppressing polyiodide shuttling and corrosion effects.Synchronously,the Zn I_(2)electrolyte facilitates the dissolution of residual and exfoliated KMnO,thereby improving manganese redox reaction kinetics,reversibility,and enhancing cycling stability.Leveraging this mutually reinforcing effect,the Zn-I_(2)-Mn hybrid battery achieves an impressive areal capacity of2.02 m Ah cm^(-2)and maintains long-term durability over 3600 cycles at 2 mA cm^(-2).This work provides valuable insights into designing efficient and durable hybrid energy storage systems.
