In the municipal solid waste incineration process,it is difficult to effectively control the gas oxygen content by setting the air flow according to artificial experience.To address this problem,this paper proposes an...In the municipal solid waste incineration process,it is difficult to effectively control the gas oxygen content by setting the air flow according to artificial experience.To address this problem,this paper proposes an optimization control method of gas oxygen content based on model predictive control.First,a stochastic configuration network is utilized to establish a prediction model of gas oxygen content.Second,an improved differential evolution algorithm that is based on parameter adaptive and t-distribution strategy is employed to address the set value of air flow.Finally,model predictive control is combined with the event triggering strategy to reduce the amount of computation and the controller's frequent actions.The experimental results show that the optimization control method proposed in this paper obtains a smaller degree of fluctuation in the air flow set value,which can ensure the tracking control performance of the gas oxygen content while reducing the amount of calculation.展开更多
Seawater splitting is a prospective approach to yield renewable and sustainable hydrogen energy.Complex preparation processes and poor repeatability are currently considered to be an insuperable impediment to the prom...Seawater splitting is a prospective approach to yield renewable and sustainable hydrogen energy.Complex preparation processes and poor repeatability are currently considered to be an insuperable impediment to the promotion of the large-scale production and application of electrocatalysts.Avoiding the use of intricate instruments,corrosion engineering is an intriguing strategy to reduce the cost and presents considerable potential for electrodes with catalytic performance.An anode comprising quinary AlCoCrFeNi layered double hydroxides uniformly decorated on an AlCoCrFeNi high-entropy alloy is proposed in this paper via a one-step corrosion engineering method,which directly serves as a remarkably active catalyst for boosting the oxygen evolution reaction(OER)in alkaline seawater.Notably,the best-performing catalyst exhibited oxygen evolution reaction activity with overpotential values of 272.3 and 332 mV to achieve the current densities of 10 and100 mA·cm^(-2),respectively.The failure mechanism of the obtained catalyst was identified for advancing the development of multicomponent catalysts.展开更多
Direct seawater electrolysis for hydrogen production has been regarded as a viable route to utilize surplus renewable energy and address the climate crisis.However,the harsh electrochemical environment of seawater,par...Direct seawater electrolysis for hydrogen production has been regarded as a viable route to utilize surplus renewable energy and address the climate crisis.However,the harsh electrochemical environment of seawater,particularly the presence of aggressive Cl^(-),has been proven to be prone to parasitic chloride ion oxidation and corrosion reactions,thus restricting seawater electrolyzer lifetime.Herein,hierarchical structure(Ni,Fe)O(OH)@NiCoS nanorod arrays(NAs)catalysts with heterointerfaces and localized oxygen vacancies were synthesized at nickel foam substrates via the combination of hydrothermal and annealing methods to boost seawater dissociation.The hiera rchical nanostructure of NiCoS NAs enhanced electrode charge transfer rate and active surface area to accelerate oxygen evolution reaction(OER)and generated sulfate gradient layers to repulsive aggressive Cl^(-).The fabricated heterostructure and vacancies of(Ni,Fe)O(OH)tuned catalyst electronic structure into an electrophilic state to enhance the binding affinity of hydroxyl intermediates and facilitate the structural transformation into amorphousγ-NiFeOOH for promoting OER.Furthermore,through operando electrochemistry techniques,we found that theγ-NiFeOOH possessing an unsaturated coordination environment and lattice-oxygen-participated OER mechanism can minimize electrode Cl^(-)corrosion enabled by stabilizing the adsorption of OH*intermediates,making it one of the best OER catalysts in the seawater medium reported to date.Consequently,these catalysts can deliver current densities of 100 and 500 mA cm-2for boosting OER at minimal overpotentials of 245and 316 mV,respectively,and thus prevent chloride ion oxidation simultaneously.Impressively,a highly stable anion exchange membrane(AEM)seawater electrolyzer based on the non-noble metal heterostructure electrodes reached a record low degradation rate under 100μV h-1at constant industrial current densities of 400 and 600 mA cm-2over 300 h,which exhibits a promising future for the nonprecious and stable AEMWE in the direct seawater electrolysis industry.展开更多
The development of efficient and robust anode materials for stable alkaline seawater electrolysis is severely limited by chlorine evolution reaction and chloride corrosion.Here,the sulfur-doped cobalt-nickel bimetalli...The development of efficient and robust anode materials for stable alkaline seawater electrolysis is severely limited by chlorine evolution reaction and chloride corrosion.Here,the sulfur-doped cobalt-nickel bimetallic phosphides(CoNiPS)are specifically designed as a pre-catalyst for navigating a surface reconstruction to fabricate the anions(PO^(3-)_(4) and SO^(2-)_(4))-decorated Co(Ni)OOH catalyst(R-CoNiPS)with exceptional durability and high activity for stable alkaline seawater oxidation(ASO).Various experiment techniques together with theoretical simulations both demonstrate that the in situ-generated PO^(3-)_(4) and SO^(2-)_(4) anions on catalyst surface can improve the oxygen evolution reaction(OER)activity,regulating and stabilizing the catalytic active species Co(Ni)OOH,as well as make a critical role in inhibiting the adsorp-tion of chloride ions and extending the service life of electrode.Therefore,this R-CoNiPS electrode exhi-bits superb OER activity toward AsO and stands out among the non-precious ASO electrocatalysts reported recently,requiring low overpotentials of 420 and 440 mV to attain large current densities of 500 and 1000 mA cm^(-2) in an alkaline natural seawater electrolyte,respectively.Particularly,the catalyst displays a negligible chloride corrosion at room temperature during ASO operation(>200 h)at 500 mA cm^(-2).This work opens up a new viewpoint for designing high-activity and durable electrocata-lystsforseawaterelectrolysis.展开更多
Isothermal oxidation behaviors of Ti-45Al-2Fe-2Mo-1Cr intermetallics with different oxygen contents were studied under the condition of 950 °C, 100 h in air, and the oxidation kinetic parameters were also evaluat...Isothermal oxidation behaviors of Ti-45Al-2Fe-2Mo-1Cr intermetallics with different oxygen contents were studied under the condition of 950 °C, 100 h in air, and the oxidation kinetic parameters were also evaluated. The results show that the oxidation resistance of the TiAl intermetallics is negatively related to the oxygen content, and both the mass gain and thickness of oxide scale increase with the oxygen content. The sub-surface microstructure of the oxide scales varies with the oxygen content. Z phase is observed in the sub-surface area of the low-oxygen-content alloy, while the τ2(Al2FeTi) phase is found in the medium-oxygen-content and the high-oxygen-content alloys. The deterioration of oxidation resistance is due to the enhanced internal oxidation with the increase of oxygen content. It is possible to improve the oxidation resistance by controlling the oxygen content.展开更多
Although Pt Ni catalyst possesses good oxygen reduction activity, its poor stability is the main obstacle for the commercialization of proton exchange membrane fuel cells(PEMFCs). In this work, we introduce the acid-r...Although Pt Ni catalyst possesses good oxygen reduction activity, its poor stability is the main obstacle for the commercialization of proton exchange membrane fuel cells(PEMFCs). In this work, we introduce the acid-resistant refractory Mo to enhance the structure stability and modify the electronic structure of Pt in the prepared PtNi catalyst, improving the catalytic activity for oxygen reduction reaction(ORR). In addition, near-surface Pt content in the nanoparticle is also optimized to balance the ORR activity and stability. The electrochemical results show that the alloy formed by Mo and Pt Ni is obviously more stable than the PtNi alloy alone, because the acid-resistant Mo and its oxides effectively prevent the dissolution of Pt. Especially, the Pt3 Ni3 MoN/C exhibits the optimal ORR catalytic performance in O2-saturated 0.1 mol L^(-1) HClO4 aqueous solutions, with mass activity(MA) of 900 m A mg^(-1) Pt at 0.90 V vs. RHE, which is 3.75 times enhancement compared with the commercial Pt/C(240 mA mg^(-1) Pt). After 30 k accelerated durability tests, its MA(690 m A mg^(-1) Pt) is still 2.88 times higher than the pristine Pt/C. This study thus provides a valuable method to design stable ORR catalysts with high efficiency and has great significance for the commercialization of PEMFCs.展开更多
The complex fluoride, KNiF3, with perovskite structure was synthesized by refluxing KF and Ni(NO3)2·6H20 in ethanediol. The samples were characterized by X-ray diffraction(XRD), transmission electron microsc...The complex fluoride, KNiF3, with perovskite structure was synthesized by refluxing KF and Ni(NO3)2·6H20 in ethanediol. The samples were characterized by X-ray diffraction(XRD), transmission electron microscopy(TEM), X-ray photoelectron spectroscopy(XPS), and ultraviolet-visible diffuse reflectance speetroseopy(UV-Vis DRS). The results indicate that the mean diameter of KNiF3 particles is about 30-60 nm and the oxygen content in the samples is ≤5%. The prepared KNiF3 shows obvious absorption peaks at 400-830 nm.展开更多
The oxidation of oxygen ions and the generation of an anode effect at a low oxygen content of 150 mg/kg were discussed in this paper.Cyclic voltammetry and square-wave voltammetry tests were conducted to explore the a...The oxidation of oxygen ions and the generation of an anode effect at a low oxygen content of 150 mg/kg were discussed in this paper.Cyclic voltammetry and square-wave voltammetry tests were conducted to explore the anodic processes of LiF-NdF_(3)melt after a lengthy period of pre-electrolysis purification at 1000℃(during which the oxygen content reduced from 413 to 150 mg/kg).The oxidation process of oxygen ions was found to have two stages:oxidation product adsorption and CO/CO_(2)gas evolution.The adsorption stage was controlled by diffusion,whereas the gas evolution was controlled by the electrochemical reaction.In comparison with oxygen content of 413 mg/kg,the decrease in the amplitude of the current at low oxygen content of 150 mg/kg was much gentler during the forward scanning process when the anode effect occurred.Fluorine-ion oxidation peaks that occurred at about 4.2 V vs.Li/Li+could be clearly observed in the reverse scanning processes,in which fluorine ions were oxidized and perfluorocarbons were produced,which resulted in an anode effect.展开更多
The oxidizing behavior of Si-containing steel was investigated in an O2 and N2 binary-component gas with oxygen contents ranging between 0.5 vol% and 4.0 vol% under anisothermal-oxidation conditions. A simultaneous th...The oxidizing behavior of Si-containing steel was investigated in an O2 and N2 binary-component gas with oxygen contents ranging between 0.5 vol% and 4.0 vol% under anisothermal-oxidation conditions. A simultaneous thermal analyzer was employed to simulate the heating process of Si-containing steel in industrial reheating furnaces. The oxidation gas mixtures were introduced from the commencement of heating. The results show that the oxidizing rate remains constant in the isothermal holding process at high temperatures; therefore, the mass change versus time presents a linear law. A linear relation also exists between the oxidizing rate and the oxygen content. Using the linear regression equation, the oxidation rate at different oxygen contents can be predicted. In addition, the relationship between the total mass gain and the oxygen content is linear; thus, the total mass gain at oxygen contents between 0.5 vol%–4.0 vol% can be determined. These results enrich the theoretical studies of the oxidation process in Si-containing steels.展开更多
By measuring the content of oxygen and nitrogen in welds of six kinds of self-shielded flux-cored wires,the effect of oxygen on nitrogen content in weld is studied and the different absorptive mechanisms of nitrogen a...By measuring the content of oxygen and nitrogen in welds of six kinds of self-shielded flux-cored wires,the effect of oxygen on nitrogen content in weld is studied and the different absorptive mechanisms of nitrogen at a low oxygen level([O] lower than 0.02%) and a high oxygen level ([O] higher than 0.03%) have been discovered.The results indicate that the content of nitrogen in weld can be made lowest by modifying the composition of flux and controlling the content of oxygen to the range of 0.02%~0.03%.展开更多
Heteroatom-doped carbon-based transition-metal single-atom catalysts(SACs) are promising electrocatalysts for oxygen reduction reaction(ORR). Herein, with the aid of hierarchically porous silica as hard template, a fa...Heteroatom-doped carbon-based transition-metal single-atom catalysts(SACs) are promising electrocatalysts for oxygen reduction reaction(ORR). Herein, with the aid of hierarchically porous silica as hard template, a facile and general melting perfusion and mesopore-confined pyrolysis method was reported to prepare single-atomic Fe/N–S-doped carbon catalyst(FeNx/NC-S) with hierarchically porous structure and well-defined morphology. The FeNx/NC-S exhibited excellent ORR activity with a half-wave potential(E_(1/2)) of 0.92 V, and a lower overpotential of 320 mV at a current density of 10 mA cm^(-2)for OER under alkaline condition. The remarkable electrocatalysis performance can be attributed to the hierarchically porous carbon nanospheres with S doping and high content of Fe-Nx sites(up to 3.7 wt% of Fe), resulting from the nano-confinement effect of the hierarchically porous silica spheres(NKM-5) during the pyrolysis process. The rechargeable Zn-air battery with FeNx/NC-S as a cathode catalyst demonstrated a superior power density of 194.5 mW cm-2charge–discharge stability. This work highlights a new avenue to design advanced SACs for efficient sustainable energy storage and conversion.展开更多
The influence of dissolved oxygen on calcareous deposits formed under galvanostatic polarization mode was studied.When the dissolved oxygen concentration was less than 7 mg L^(-1),the cathodic protection potential sho...The influence of dissolved oxygen on calcareous deposits formed under galvanostatic polarization mode was studied.When the dissolved oxygen concentration was less than 7 mg L^(-1),the cathodic protection potential showed a plateau at the initial polarization,and then quickly shifted negatively.While the dissolved oxygen was more than 9 mg L^(-1),the potential shifted negatively in a linear form.After 168 h of polarization,the final protection potential shifted negatively with the decreasing dissolved oxygen concentration.The deposition progress was monitored by electrochemical impedance spectroscopy,and only one single loop was found in Nyquist diagram,indicating deposits of ineffective protectiveness precipitation under the experimental conditions.The protection factor of deposits increased with the decreasing dissolved oxygen concentration which was detected by linear polarization resistance technique.The cathodic electrochemical reaction could change very shortly from oxygen reduction to hydrogen evolution after cathodic protection under very low dissolved oxygen concentration,such as 1 mg L^(-1),resulting in the hydrogen bubbling from the metallic surface and the decrease of deposits protection factor.Observation by scanning electron microscopy and X-ray diffraction analysis demonstrated that the deposits were mainly of calcite under the experimental conditions,and that dissolved oxygen had no effect on the crystalline types of calcium carbonate.展开更多
The influence of dissolved oxygen content on the oxidative stability of a linked polymer solution (LPS) was studied by micro-filtration, dynamic light scattering and viscosity measurements. The results showed that at ...The influence of dissolved oxygen content on the oxidative stability of a linked polymer solution (LPS) was studied by micro-filtration, dynamic light scattering and viscosity measurements. The results showed that at the same temperature, the degree of the oxidative degradation of the LPS increased and the rapidity of the oxidative degradation was accelerated with the increase of the dissolved oxygen content. Consequently, the size of linked polymer coils (LPCs) of the LPS became small, and the plugging capability of the LPS decreased. At a fixed content of dissolved oxygen, with increasing degradation temperature, almost the same results were observed, namely, an increased degree of oxidative degradation, accelerated rapidity of the oxidative degradation and decreased plugging capacity, with decreased oxidative stability of LPS. At 90 °C, in the presence of oxygen, LPS lost its plugging capability after having been degraded for a period of time. But at 40 °C, LPS with low dissolved oxygen content could be stable for a long time. The decreased plugging ability of LPS after oxidative degradation is mainly caused by the decreased size and number of the LPCs due to the breaking of hydrolyzed polyacrylamide (HPAM) molecule segments and the structural changing of HPAM molecules.展开更多
Seawater splitting into hydrogen,a promising technology,is seriously limited by the durability and tolerance of electrocatalysts for chlorine ions in seawater at large current densities due to chloride oxidation and c...Seawater splitting into hydrogen,a promising technology,is seriously limited by the durability and tolerance of electrocatalysts for chlorine ions in seawater at large current densities due to chloride oxidation and corrosion.Here,we present a robust and weak-nucleophilicity nickel-iron hydroxide electrocatalyst with excellent selectivity for oxygen evolution and an inert response for chlorine ion oxidation which are key and highly desired for efficient seawater electrolysis.Such a weak-nucleophilicity electrocatalyst can well match with strong-nucleophilicity OH-compared with the weak-nucleophilicity Cl^(-),resultantly,the oxidation of OH-in electrolyte can be more easily achieved relative to chlorine ion oxidation,confirmed by ethylenediaminetetraacetic acid disodium probing test.Further,no strongly corrosive hypochlorite is produced when the operating voltage reaches about 2.1 V vs.RHE,a potential that is far beyond the thermodynamic potential of chlorine ion oxidatio n.This concept and approach to reasonably designing weaknucleophilicity electrocatalysts that can greatly avoid chlorine ion oxidation under alkaline seawater environments can push forward the seawater electrolysis technology and also accelerate the development of green hydrogen technique.展开更多
Hydrogen generation through seawater electrolysis provides a promising,attractive pathway towards the utilization of sustainable energy.However,the catalytic activity and stability of oxygen evolution anode are severe...Hydrogen generation through seawater electrolysis provides a promising,attractive pathway towards the utilization of sustainable energy.However,the catalytic activity and stability of oxygen evolution anode are severely limited by the chloride-induced corrosion and competitive oxidation reactions.In this work,we demonstrate an anion-assisted performance improvement strategy by quick and universal screening of electrolyte additive via correlating Cl-repellency with the anionic properties.Particularly,the addition of phosphate ions is found to enable highly stable alkaline seawater splitting at industry-level current density(0.5 A cm^(-2))over 500 h using transition metal hydroxides as anodic electrocatalysts.In situ experiments and theoretical simulations further reveal that the dynamic anti-corrosion behaviors of surface-adsorbed phosphate ions are attributed to three factors including repelling Cl-ions without significantly blocking OH-diffusion,preventing transition metal dissolution and acting as a local pH buffer to compensate the fast OH-consumption under high current electrolysis.展开更多
To improve both oxygen evolution efficiency and stability at high temperatures, Mn, Mn+Mo, Mn+Mo+V, and Mn+Fe+V oxide electrodes were prepared on a Ti substrate, with an intermediate layer of IrO_2, by an anodic depos...To improve both oxygen evolution efficiency and stability at high temperatures, Mn, Mn+Mo, Mn+Mo+V, and Mn+Fe+V oxide electrodes were prepared on a Ti substrate, with an intermediate layer of IrO_2, by an anodic deposition method. The crystal structure, surface morphology, pore size distribution, specific surface area, and voltammetric charge were then characterized for each electrode. The results demonstrated that for Mn-O electrodes, the preferential orientation of the(100) crystal plane and the mesopore structure played negative roles in the oxygen evolution reaction. On the basis of the electrocatalytic properties of MnO2-based electrodes in seawater, the outer surface voltammetric charge at a scan rate of 500 mV·s-1 was shown to effectively indicate whether oxygen evolution reactions were preferred over chlorine evolution reactions. The Mn-O electrode exhibited oxygen evolution efficiency of only 47.27%, whereas the Mn+Mo, Mn+Mo+V and Mn+Fe+V oxide electrodes displayed oxygen evolution efficiency of nearly 100%. This means that adding Mo, V, and Fe elements to the electrode can improve its crystal structure and morphology as well as further enhancing its oxygen evolution efficiency.展开更多
The metallurgical properties and fatigue life of bearing steel processed by electric furnace (EAF), ladle refining (LF-VD), continous casting (CC) and electroslag remelting (ESR) have been investigated. The main resul...The metallurgical properties and fatigue life of bearing steel processed by electric furnace (EAF), ladle refining (LF-VD), continous casting (CC) and electroslag remelting (ESR) have been investigated. The main results obtained are as follows: (1) Due to low oxygen content and dispersion inclusions in steel, the fatigue Life of LF-VD-IC or CC is three times as high as that of EAF steel; (2) The oxygen content in steel produced by CC process is about 9.0x10(-6), the carbon segregation (C/C(0)) is from 0.92 to 1.10 and the fatigue life of CC steel is equal to that of ladle refining ingot casting steel; (3) Although the amount of inclusion and oxygen in ESR steel is higher than that of LF-VD-IC or CC steel, the fatigue life of ESR steel is higher than that of the latter because of its fine and well dispersed inclusions.展开更多
-During the multi-disciplinary investigations on the waters of Nansa Islands for three cruises respectively in 1985. 1986. 1987. it is found that the dissolved oxygen maximum (DOmax) in its vertical distribution usual...-During the multi-disciplinary investigations on the waters of Nansa Islands for three cruises respectively in 1985. 1986. 1987. it is found that the dissolved oxygen maximum (DOmax) in its vertical distribution usually exists between 20m and 75m deep. The deep position of O2 maximum is near the thermocline below and above the deep chlorophyll maximum, as well as above the light-beam attenuation coefficient maximum. In the parts of O2 maximum occurring, the minimum of CO2 partial pressure and the maximum of pH value are also found at the same depth. It is still difficult to explain the features exactly by using the published research results about the oxygen maximum in its vertical distribution on the waters of middle and high latitude.In the present paper, the dissolved oxygen maximum in its vertical distribution on the waters of low latitude is described. It is made by an internal wave which holds eddy mixture. The feature appears to arise from the biological photosynthesis with stratification, from the action of the thermocline preventing oxygen from escaping to the atmosphere, when the environment is suitable for organisms to grow.展开更多
Melt treatment is well known to have an important influence on the properties of metallic glasses(MGs).However,for the MGs quenched from different melt temperatures with a quartz tube,the underlying physical origin re...Melt treatment is well known to have an important influence on the properties of metallic glasses(MGs).However,for the MGs quenched from different melt temperatures with a quartz tube,the underlying physical origin responsible for the variation of properties remains poorly understood.In the present work,we systematically studied the influence of melt treatment on the thermal properties of a Zr50Cu36Al14 glass-forming alloy and unveiled the microscopic origins.Specifically,we quenched the melt at different temperatures ranging from 1.1Tl to 1.5Tl(Tl is the liquidus temperature)to obtain melt-spun MG ribbons and investigated the variation of thermal properties of the MGs upon heating.We found that glass transition temperature,Tg,increases by as much as 36 K,and the supercooled liquid region disappears in the curve of differential scanning calorimetry when the melt is quenched at a high temperature up to 1.5Tl.The careful chemical analyses indicate that the change in glass transition behavior originates from the incorporation of oxygen and silicon in the molten alloys.The incorporated oxygen and silicon can both enhance the interactions between atoms,which renders the cooperative rearrangements of atoms difficult,and thus enhances the kinetic stability of the MGs.展开更多
基金supported by the National Natural Science Foundation of China(62373017,62073006)and the Beijing Natural Science Foundation of China(4212032)。
文摘In the municipal solid waste incineration process,it is difficult to effectively control the gas oxygen content by setting the air flow according to artificial experience.To address this problem,this paper proposes an optimization control method of gas oxygen content based on model predictive control.First,a stochastic configuration network is utilized to establish a prediction model of gas oxygen content.Second,an improved differential evolution algorithm that is based on parameter adaptive and t-distribution strategy is employed to address the set value of air flow.Finally,model predictive control is combined with the event triggering strategy to reduce the amount of computation and the controller's frequent actions.The experimental results show that the optimization control method proposed in this paper obtains a smaller degree of fluctuation in the air flow set value,which can ensure the tracking control performance of the gas oxygen content while reducing the amount of calculation.
基金supported by the National Natural Science Foundation of China (No.51901018)the Young Elite Scientists Sponsorship Program by the China Association for Science and Technology (YESS,2019QNRC001)+1 种基金the Natural Science Foundation of Beijing Municipality (No.2212037)the National Science and Technology Resources Investigation Program of China (No.2019FY 101400)。
文摘Seawater splitting is a prospective approach to yield renewable and sustainable hydrogen energy.Complex preparation processes and poor repeatability are currently considered to be an insuperable impediment to the promotion of the large-scale production and application of electrocatalysts.Avoiding the use of intricate instruments,corrosion engineering is an intriguing strategy to reduce the cost and presents considerable potential for electrodes with catalytic performance.An anode comprising quinary AlCoCrFeNi layered double hydroxides uniformly decorated on an AlCoCrFeNi high-entropy alloy is proposed in this paper via a one-step corrosion engineering method,which directly serves as a remarkably active catalyst for boosting the oxygen evolution reaction(OER)in alkaline seawater.Notably,the best-performing catalyst exhibited oxygen evolution reaction activity with overpotential values of 272.3 and 332 mV to achieve the current densities of 10 and100 mA·cm^(-2),respectively.The failure mechanism of the obtained catalyst was identified for advancing the development of multicomponent catalysts.
基金supported by the National Key Research and Development Program of China(2022YFB4002100)the Key Program of the National Natural Science Foundation of China(22090032,22090030)。
文摘Direct seawater electrolysis for hydrogen production has been regarded as a viable route to utilize surplus renewable energy and address the climate crisis.However,the harsh electrochemical environment of seawater,particularly the presence of aggressive Cl^(-),has been proven to be prone to parasitic chloride ion oxidation and corrosion reactions,thus restricting seawater electrolyzer lifetime.Herein,hierarchical structure(Ni,Fe)O(OH)@NiCoS nanorod arrays(NAs)catalysts with heterointerfaces and localized oxygen vacancies were synthesized at nickel foam substrates via the combination of hydrothermal and annealing methods to boost seawater dissociation.The hiera rchical nanostructure of NiCoS NAs enhanced electrode charge transfer rate and active surface area to accelerate oxygen evolution reaction(OER)and generated sulfate gradient layers to repulsive aggressive Cl^(-).The fabricated heterostructure and vacancies of(Ni,Fe)O(OH)tuned catalyst electronic structure into an electrophilic state to enhance the binding affinity of hydroxyl intermediates and facilitate the structural transformation into amorphousγ-NiFeOOH for promoting OER.Furthermore,through operando electrochemistry techniques,we found that theγ-NiFeOOH possessing an unsaturated coordination environment and lattice-oxygen-participated OER mechanism can minimize electrode Cl^(-)corrosion enabled by stabilizing the adsorption of OH*intermediates,making it one of the best OER catalysts in the seawater medium reported to date.Consequently,these catalysts can deliver current densities of 100 and 500 mA cm-2for boosting OER at minimal overpotentials of 245and 316 mV,respectively,and thus prevent chloride ion oxidation simultaneously.Impressively,a highly stable anion exchange membrane(AEM)seawater electrolyzer based on the non-noble metal heterostructure electrodes reached a record low degradation rate under 100μV h-1at constant industrial current densities of 400 and 600 mA cm-2over 300 h,which exhibits a promising future for the nonprecious and stable AEMWE in the direct seawater electrolysis industry.
基金the funding support from the National Natural Science Foundation of China (U22A2078)the Fundamental Research Funds of Central Universities (2022CDJQY-007 and 2022CDJJCLK001)
文摘The development of efficient and robust anode materials for stable alkaline seawater electrolysis is severely limited by chlorine evolution reaction and chloride corrosion.Here,the sulfur-doped cobalt-nickel bimetallic phosphides(CoNiPS)are specifically designed as a pre-catalyst for navigating a surface reconstruction to fabricate the anions(PO^(3-)_(4) and SO^(2-)_(4))-decorated Co(Ni)OOH catalyst(R-CoNiPS)with exceptional durability and high activity for stable alkaline seawater oxidation(ASO).Various experiment techniques together with theoretical simulations both demonstrate that the in situ-generated PO^(3-)_(4) and SO^(2-)_(4) anions on catalyst surface can improve the oxygen evolution reaction(OER)activity,regulating and stabilizing the catalytic active species Co(Ni)OOH,as well as make a critical role in inhibiting the adsorp-tion of chloride ions and extending the service life of electrode.Therefore,this R-CoNiPS electrode exhi-bits superb OER activity toward AsO and stands out among the non-precious ASO electrocatalysts reported recently,requiring low overpotentials of 420 and 440 mV to attain large current densities of 500 and 1000 mA cm^(-2) in an alkaline natural seawater electrolyte,respectively.Particularly,the catalyst displays a negligible chloride corrosion at room temperature during ASO operation(>200 h)at 500 mA cm^(-2).This work opens up a new viewpoint for designing high-activity and durable electrocata-lystsforseawaterelectrolysis.
基金Project(2014CB644002) supported by the National Key Fundamental Research and Development of ChinaProject(2017JJ2311) supported by the Natural Science Foundation of Hunan Province,ChinaProject(KFJJ11-7M) supported by the State Key Laboratory of Explosion Science and Technology,China
文摘Isothermal oxidation behaviors of Ti-45Al-2Fe-2Mo-1Cr intermetallics with different oxygen contents were studied under the condition of 950 °C, 100 h in air, and the oxidation kinetic parameters were also evaluated. The results show that the oxidation resistance of the TiAl intermetallics is negatively related to the oxygen content, and both the mass gain and thickness of oxide scale increase with the oxygen content. The sub-surface microstructure of the oxide scales varies with the oxygen content. Z phase is observed in the sub-surface area of the low-oxygen-content alloy, while the τ2(Al2FeTi) phase is found in the medium-oxygen-content and the high-oxygen-content alloys. The deterioration of oxidation resistance is due to the enhanced internal oxidation with the increase of oxygen content. It is possible to improve the oxidation resistance by controlling the oxygen content.
基金supported by the National Natural Science Foundation of China (21872040)the Natural Science Foundation of Guangxi (2016GXNSFCB380002)+1 种基金the Hundred Talents Program of Guangxi Universitiesthe Excellence Scholars and Innovation Team of Guangxi Universities。
文摘Although Pt Ni catalyst possesses good oxygen reduction activity, its poor stability is the main obstacle for the commercialization of proton exchange membrane fuel cells(PEMFCs). In this work, we introduce the acid-resistant refractory Mo to enhance the structure stability and modify the electronic structure of Pt in the prepared PtNi catalyst, improving the catalytic activity for oxygen reduction reaction(ORR). In addition, near-surface Pt content in the nanoparticle is also optimized to balance the ORR activity and stability. The electrochemical results show that the alloy formed by Mo and Pt Ni is obviously more stable than the PtNi alloy alone, because the acid-resistant Mo and its oxides effectively prevent the dissolution of Pt. Especially, the Pt3 Ni3 MoN/C exhibits the optimal ORR catalytic performance in O2-saturated 0.1 mol L^(-1) HClO4 aqueous solutions, with mass activity(MA) of 900 m A mg^(-1) Pt at 0.90 V vs. RHE, which is 3.75 times enhancement compared with the commercial Pt/C(240 mA mg^(-1) Pt). After 30 k accelerated durability tests, its MA(690 m A mg^(-1) Pt) is still 2.88 times higher than the pristine Pt/C. This study thus provides a valuable method to design stable ORR catalysts with high efficiency and has great significance for the commercialization of PEMFCs.
基金Supported by the National Natural Science Foundation of China(No.20671069)
文摘The complex fluoride, KNiF3, with perovskite structure was synthesized by refluxing KF and Ni(NO3)2·6H20 in ethanediol. The samples were characterized by X-ray diffraction(XRD), transmission electron microscopy(TEM), X-ray photoelectron spectroscopy(XPS), and ultraviolet-visible diffuse reflectance speetroseopy(UV-Vis DRS). The results indicate that the mean diameter of KNiF3 particles is about 30-60 nm and the oxygen content in the samples is ≤5%. The prepared KNiF3 shows obvious absorption peaks at 400-830 nm.
基金the National Natural Science Foundation of China(No.51774145).The“Minjiang Scholar”Program of Department of Education,Fujian Province,China was also acknowledged.
文摘The oxidation of oxygen ions and the generation of an anode effect at a low oxygen content of 150 mg/kg were discussed in this paper.Cyclic voltammetry and square-wave voltammetry tests were conducted to explore the anodic processes of LiF-NdF_(3)melt after a lengthy period of pre-electrolysis purification at 1000℃(during which the oxygen content reduced from 413 to 150 mg/kg).The oxidation process of oxygen ions was found to have two stages:oxidation product adsorption and CO/CO_(2)gas evolution.The adsorption stage was controlled by diffusion,whereas the gas evolution was controlled by the electrochemical reaction.In comparison with oxygen content of 413 mg/kg,the decrease in the amplitude of the current at low oxygen content of 150 mg/kg was much gentler during the forward scanning process when the anode effect occurred.Fluorine-ion oxidation peaks that occurred at about 4.2 V vs.Li/Li+could be clearly observed in the reverse scanning processes,in which fluorine ions were oxidized and perfluorocarbons were produced,which resulted in an anode effect.
基金financially supported by the National Natural Science Foundation of China(No.51274154)The Major Projects of Technology Innovation of Hubei Province,China(No.2017AAA116)the Special Fund of Wuhan University of Science and Technology for Master Student’s Short-Term Studying Abroad
文摘The oxidizing behavior of Si-containing steel was investigated in an O2 and N2 binary-component gas with oxygen contents ranging between 0.5 vol% and 4.0 vol% under anisothermal-oxidation conditions. A simultaneous thermal analyzer was employed to simulate the heating process of Si-containing steel in industrial reheating furnaces. The oxidation gas mixtures were introduced from the commencement of heating. The results show that the oxidizing rate remains constant in the isothermal holding process at high temperatures; therefore, the mass change versus time presents a linear law. A linear relation also exists between the oxidizing rate and the oxygen content. Using the linear regression equation, the oxidation rate at different oxygen contents can be predicted. In addition, the relationship between the total mass gain and the oxygen content is linear; thus, the total mass gain at oxygen contents between 0.5 vol%–4.0 vol% can be determined. These results enrich the theoretical studies of the oxidation process in Si-containing steels.
文摘By measuring the content of oxygen and nitrogen in welds of six kinds of self-shielded flux-cored wires,the effect of oxygen on nitrogen content in weld is studied and the different absorptive mechanisms of nitrogen at a low oxygen level([O] lower than 0.02%) and a high oxygen level ([O] higher than 0.03%) have been discovered.The results indicate that the content of nitrogen in weld can be made lowest by modifying the composition of flux and controlling the content of oxygen to the range of 0.02%~0.03%.
基金supported by National Natural Science Foundation of China (21773128)。
文摘Heteroatom-doped carbon-based transition-metal single-atom catalysts(SACs) are promising electrocatalysts for oxygen reduction reaction(ORR). Herein, with the aid of hierarchically porous silica as hard template, a facile and general melting perfusion and mesopore-confined pyrolysis method was reported to prepare single-atomic Fe/N–S-doped carbon catalyst(FeNx/NC-S) with hierarchically porous structure and well-defined morphology. The FeNx/NC-S exhibited excellent ORR activity with a half-wave potential(E_(1/2)) of 0.92 V, and a lower overpotential of 320 mV at a current density of 10 mA cm^(-2)for OER under alkaline condition. The remarkable electrocatalysis performance can be attributed to the hierarchically porous carbon nanospheres with S doping and high content of Fe-Nx sites(up to 3.7 wt% of Fe), resulting from the nano-confinement effect of the hierarchically porous silica spheres(NKM-5) during the pyrolysis process. The rechargeable Zn-air battery with FeNx/NC-S as a cathode catalyst demonstrated a superior power density of 194.5 mW cm-2charge–discharge stability. This work highlights a new avenue to design advanced SACs for efficient sustainable energy storage and conversion.
基金the financial support of this project by the National Basic Research Program of China(973 Project,No.2014CB643300)National Environmental Corrosion Platform(NECP)
文摘The influence of dissolved oxygen on calcareous deposits formed under galvanostatic polarization mode was studied.When the dissolved oxygen concentration was less than 7 mg L^(-1),the cathodic protection potential showed a plateau at the initial polarization,and then quickly shifted negatively.While the dissolved oxygen was more than 9 mg L^(-1),the potential shifted negatively in a linear form.After 168 h of polarization,the final protection potential shifted negatively with the decreasing dissolved oxygen concentration.The deposition progress was monitored by electrochemical impedance spectroscopy,and only one single loop was found in Nyquist diagram,indicating deposits of ineffective protectiveness precipitation under the experimental conditions.The protection factor of deposits increased with the decreasing dissolved oxygen concentration which was detected by linear polarization resistance technique.The cathodic electrochemical reaction could change very shortly from oxygen reduction to hydrogen evolution after cathodic protection under very low dissolved oxygen concentration,such as 1 mg L^(-1),resulting in the hydrogen bubbling from the metallic surface and the decrease of deposits protection factor.Observation by scanning electron microscopy and X-ray diffraction analysis demonstrated that the deposits were mainly of calcite under the experimental conditions,and that dissolved oxygen had no effect on the crystalline types of calcium carbonate.
文摘The influence of dissolved oxygen content on the oxidative stability of a linked polymer solution (LPS) was studied by micro-filtration, dynamic light scattering and viscosity measurements. The results showed that at the same temperature, the degree of the oxidative degradation of the LPS increased and the rapidity of the oxidative degradation was accelerated with the increase of the dissolved oxygen content. Consequently, the size of linked polymer coils (LPCs) of the LPS became small, and the plugging capability of the LPS decreased. At a fixed content of dissolved oxygen, with increasing degradation temperature, almost the same results were observed, namely, an increased degree of oxidative degradation, accelerated rapidity of the oxidative degradation and decreased plugging capacity, with decreased oxidative stability of LPS. At 90 °C, in the presence of oxygen, LPS lost its plugging capability after having been degraded for a period of time. But at 40 °C, LPS with low dissolved oxygen content could be stable for a long time. The decreased plugging ability of LPS after oxidative degradation is mainly caused by the decreased size and number of the LPCs due to the breaking of hydrolyzed polyacrylamide (HPAM) molecule segments and the structural changing of HPAM molecules.
基金supported by the National Natural Science Foundation of China(NSFC,No.22078052)the Fundamental Research Funds for the Central Universities(DUT22ZD207,DUT22LAB612)。
文摘Seawater splitting into hydrogen,a promising technology,is seriously limited by the durability and tolerance of electrocatalysts for chlorine ions in seawater at large current densities due to chloride oxidation and corrosion.Here,we present a robust and weak-nucleophilicity nickel-iron hydroxide electrocatalyst with excellent selectivity for oxygen evolution and an inert response for chlorine ion oxidation which are key and highly desired for efficient seawater electrolysis.Such a weak-nucleophilicity electrocatalyst can well match with strong-nucleophilicity OH-compared with the weak-nucleophilicity Cl^(-),resultantly,the oxidation of OH-in electrolyte can be more easily achieved relative to chlorine ion oxidation,confirmed by ethylenediaminetetraacetic acid disodium probing test.Further,no strongly corrosive hypochlorite is produced when the operating voltage reaches about 2.1 V vs.RHE,a potential that is far beyond the thermodynamic potential of chlorine ion oxidatio n.This concept and approach to reasonably designing weaknucleophilicity electrocatalysts that can greatly avoid chlorine ion oxidation under alkaline seawater environments can push forward the seawater electrolysis technology and also accelerate the development of green hydrogen technique.
基金supported by the National Natural Science Foundation of China(22102076,21925503,21871149)the Ministry of Science and Technology of the People’s Republic of China(2017YFA0206700)+1 种基金the China Postdoctoral Science Foundation(2020M670621)the Ministry of Education of the People’s Republic of China(B12015)。
文摘Hydrogen generation through seawater electrolysis provides a promising,attractive pathway towards the utilization of sustainable energy.However,the catalytic activity and stability of oxygen evolution anode are severely limited by the chloride-induced corrosion and competitive oxidation reactions.In this work,we demonstrate an anion-assisted performance improvement strategy by quick and universal screening of electrolyte additive via correlating Cl-repellency with the anionic properties.Particularly,the addition of phosphate ions is found to enable highly stable alkaline seawater splitting at industry-level current density(0.5 A cm^(-2))over 500 h using transition metal hydroxides as anodic electrocatalysts.In situ experiments and theoretical simulations further reveal that the dynamic anti-corrosion behaviors of surface-adsorbed phosphate ions are attributed to three factors including repelling Cl-ions without significantly blocking OH-diffusion,preventing transition metal dissolution and acting as a local pH buffer to compensate the fast OH-consumption under high current electrolysis.
基金Funded by National Natural Science Foundation of China(No.51301070)Scientific and Technological Project of Henan Province(No.182102210068)
文摘To improve both oxygen evolution efficiency and stability at high temperatures, Mn, Mn+Mo, Mn+Mo+V, and Mn+Fe+V oxide electrodes were prepared on a Ti substrate, with an intermediate layer of IrO_2, by an anodic deposition method. The crystal structure, surface morphology, pore size distribution, specific surface area, and voltammetric charge were then characterized for each electrode. The results demonstrated that for Mn-O electrodes, the preferential orientation of the(100) crystal plane and the mesopore structure played negative roles in the oxygen evolution reaction. On the basis of the electrocatalytic properties of MnO2-based electrodes in seawater, the outer surface voltammetric charge at a scan rate of 500 mV·s-1 was shown to effectively indicate whether oxygen evolution reactions were preferred over chlorine evolution reactions. The Mn-O electrode exhibited oxygen evolution efficiency of only 47.27%, whereas the Mn+Mo, Mn+Mo+V and Mn+Fe+V oxide electrodes displayed oxygen evolution efficiency of nearly 100%. This means that adding Mo, V, and Fe elements to the electrode can improve its crystal structure and morphology as well as further enhancing its oxygen evolution efficiency.
文摘The metallurgical properties and fatigue life of bearing steel processed by electric furnace (EAF), ladle refining (LF-VD), continous casting (CC) and electroslag remelting (ESR) have been investigated. The main results obtained are as follows: (1) Due to low oxygen content and dispersion inclusions in steel, the fatigue Life of LF-VD-IC or CC is three times as high as that of EAF steel; (2) The oxygen content in steel produced by CC process is about 9.0x10(-6), the carbon segregation (C/C(0)) is from 0.92 to 1.10 and the fatigue life of CC steel is equal to that of ladle refining ingot casting steel; (3) Although the amount of inclusion and oxygen in ESR steel is higher than that of LF-VD-IC or CC steel, the fatigue life of ESR steel is higher than that of the latter because of its fine and well dispersed inclusions.
文摘-During the multi-disciplinary investigations on the waters of Nansa Islands for three cruises respectively in 1985. 1986. 1987. it is found that the dissolved oxygen maximum (DOmax) in its vertical distribution usually exists between 20m and 75m deep. The deep position of O2 maximum is near the thermocline below and above the deep chlorophyll maximum, as well as above the light-beam attenuation coefficient maximum. In the parts of O2 maximum occurring, the minimum of CO2 partial pressure and the maximum of pH value are also found at the same depth. It is still difficult to explain the features exactly by using the published research results about the oxygen maximum in its vertical distribution on the waters of middle and high latitude.In the present paper, the dissolved oxygen maximum in its vertical distribution on the waters of low latitude is described. It is made by an internal wave which holds eddy mixture. The feature appears to arise from the biological photosynthesis with stratification, from the action of the thermocline preventing oxygen from escaping to the atmosphere, when the environment is suitable for organisms to grow.
基金The work was financially supported by the National Key Research and Development Program of China(Grant Nos.2018YFA0703600,2021YFA0716302,and 2021YFA0718703)the National Natural Science Foundation of China(Grant Nos.51825104 and 52192602)China Postdoctoral Science Foundation(Grant No.2022T150691).
文摘Melt treatment is well known to have an important influence on the properties of metallic glasses(MGs).However,for the MGs quenched from different melt temperatures with a quartz tube,the underlying physical origin responsible for the variation of properties remains poorly understood.In the present work,we systematically studied the influence of melt treatment on the thermal properties of a Zr50Cu36Al14 glass-forming alloy and unveiled the microscopic origins.Specifically,we quenched the melt at different temperatures ranging from 1.1Tl to 1.5Tl(Tl is the liquidus temperature)to obtain melt-spun MG ribbons and investigated the variation of thermal properties of the MGs upon heating.We found that glass transition temperature,Tg,increases by as much as 36 K,and the supercooled liquid region disappears in the curve of differential scanning calorimetry when the melt is quenched at a high temperature up to 1.5Tl.The careful chemical analyses indicate that the change in glass transition behavior originates from the incorporation of oxygen and silicon in the molten alloys.The incorporated oxygen and silicon can both enhance the interactions between atoms,which renders the cooperative rearrangements of atoms difficult,and thus enhances the kinetic stability of the MGs.