Green hydrogen(H_(2))produced by renewable energy powered alkaline water electrolysis is a promising alternative to fossil fuels due to its high energy density with zero-carbon emissions.However,efficient and economic...Green hydrogen(H_(2))produced by renewable energy powered alkaline water electrolysis is a promising alternative to fossil fuels due to its high energy density with zero-carbon emissions.However,efficient and economic H_(2) production by alkaline water electrolysis is hindered by the sluggish hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).Therefore,it is imperative to design and fabricate high-active and low-cost non-precious metal catalysts to improve the HER and OER performance,which affects the energy efficiency of alkaline water electrolysis.Ni_(3)S_(2) with the heazlewoodite structure is a potential electrocatalyst with near-metal conductivity due to the Ni–Ni metal network.Here,the review comprehensively presents the recent progress of Ni_(3)S_(2)-based electrocatalysts for alkaline water electrocatalysis.Herein,the HER and OER mechanisms,performance evaluation criteria,preparation methods,and strategies for performance improvement of Ni_(3)S_(2)-based electrocatalysts are discussed.The challenges and perspectives are also analyzed.展开更多
An advantageous porous architecture of electrodes is pivotal in significantly enhancing alkaline water electrolysis(AWE)efficiency by optimizing the mass transport mechanisms.This effect becomes even more pronounced w...An advantageous porous architecture of electrodes is pivotal in significantly enhancing alkaline water electrolysis(AWE)efficiency by optimizing the mass transport mechanisms.This effect becomes even more pronounced when aiming to achieve elevated current densities.Herein,we employed a rapid and scalable laser texturing process to craft novel multi-channel porous electrodes.Particularly,the obtained electrodes exhibit the lowest Tafel slope of 79 mV dec^(-1)(HER)and 49 mV dec^(-1)(OER).As anticipated,the alkaline electrolyzer(AEL)cell incorporating multi-channel porous electrodes(NP-LT30)exhibited a remarkable improvement in cell efficiency,with voltage drops(from 2.28 to 1.97 V)exceeding 300 mV under 1 A cm^(-1),compared to conventional perforated Ni plate electrodes.This enhancement mainly stemmed from the employed multi-channel porous structure,facilitating mass transport and bubble dynamics through an innovative convection mode,surpassing the traditional convection mode.Furthermore,the NP-LT30-based AEL cell demonstrated exceptional durability for 300 h under 1.0 A cm^(-2).This study underscores the capability of the novel multi-channel porous electrodes to expedite mass transport in practical AWE applications.展开更多
Electrochemical water splitting has attracted considerable attention for the production of hydrogen fuel by using renewable energy resources.However,the sluggish reaction kinetics make it essential to explore precious...Electrochemical water splitting has attracted considerable attention for the production of hydrogen fuel by using renewable energy resources.However,the sluggish reaction kinetics make it essential to explore precious-metal-free electrocatalysts with superior activity and long-term stability.Tremendous efforts have been made in exploring electrocatalysts to reduce the energy barriers and improve catalytic efficiency.This review summarizes different categories of precious-metal-free electrocatalysts developed in the past 5 years for alkaline water splitting.The design strategies for optimizing the electronic and geometric structures of electrocatalysts with enhanced catalytic performance are discussed,including composition modulation,defect engineering,and structural engineering.Particularly,the advancement of operando/in situ characterization techniques toward the understanding of structural evolution,reaction intermediates,and active sites during the water splitting process are summarized.Finally,current challenges and future perspectives toward achieving efficient catalyst systems for industrial applications are proposed.This review will provide insights and strategies to the design of precious-metalfree electrocatalysts and inspire future research in alkaline water splitting.展开更多
The epitaxial heterostructure can be rationally designed based on the in situ growth of two compatible phases with lattice similarity,in which the modulated electronic states and tuned adsorption behaviors are conduci...The epitaxial heterostructure can be rationally designed based on the in situ growth of two compatible phases with lattice similarity,in which the modulated electronic states and tuned adsorption behaviors are conducive to the enhancement of electrocatalytic activity.Herein,theoretical simulations first disclose the charge transfer trend and reinforced inherent electron conduction around the epitaxial heterointerface between Ru clusters and Ni_(3)N substrate(cRu-Ni_(3)N),thus leading to the optimized adsorption behaviors and reduced activation energy barriers.Subsequently,the defectrich nanosheets with the epitaxially grown cRu-Ni_(3)N heterointerface are successfully constructed.Impressively,by virtue of the superiority of intrinsic activity and reaction kinetics,such unique epitaxial heterostructure exhibits remarkable bifunctional catalytic activity toward electrocatalytic OER(226 mV@20 mA cm^(−2))and HER(32 mV@10 mA cm^(−2))in alkaline media.Furthermore,it also shows great application prospect in alkaline freshwater and seawater splitting,as well as solar-to-hydrogen integrated system.This work could provide beneficial enlightenment for the establishment of advanced electrocatalysts with epitaxial heterointerfaces.展开更多
Alkaline electrolyzers for water splitting under the industrial current densities are always burdened with huge energy consumption due to the high overpotential and poor stability of the anode nanocatalysts for oxygen...Alkaline electrolyzers for water splitting under the industrial current densities are always burdened with huge energy consumption due to the high overpotential and poor stability of the anode nanocatalysts for oxygen evolution reaction(OER).Inspired by the interfacial charge transfer for enhancing the performance,a series of in-situ grown interfacial Mn-NiFe lactate dehydrogenase(LDH)was designed on the Fe_(0.64)Ni_(0.36)/NM(nickel mesh)alloy layer.The optimized Mn_(0.15)-NiFe LDH/Fe_(0.64)Ni_(0.36)/NM exhibited an ultralow overpotential of 295 mV to drive 500 mA·cm^(-2)and an incredible stability under large current density.The interfacial space and heteroatom doping synergistically triggered the electronic structure optimization to promote electron transfer and ensure the durability of the high-current reaction.Notably,the designed Mn_(0.15)-NiFe LDH/Fe_(0.64)Ni_(0.36)/NM as an anode in an integral alkaline electrolyzer exhibited a cell voltage of 1.78 V at 500 mA·cm^(-2) with a stability of 366 h.Density functional theory(DFT)calculations further demonstrated the synergistic effect of alloy layer introduction and Mn doping could accelerate electron transfer and stabilize the charged active center to activate the NiFe LDH and reduce the OER energy barrier.Our work offers new insights into developing efficient self-supported catalysts for high-current alkaline water oxidation.展开更多
Recently,considerable attention has been paid to the installation of renewable energy capacity to mitigate global CO_(2) emissions.H_(2) produced using water electrolysis and renewable energy is regarded as a clean en...Recently,considerable attention has been paid to the installation of renewable energy capacity to mitigate global CO_(2) emissions.H_(2) produced using water electrolysis and renewable energy is regarded as a clean energy carrier,generating electricity without CO_(2) emissions,called‘Green H 2’.In this paper,a prognostics and health man-agement model for an alkaline water electrolyzer was proposed to predict the load voltage on the electrolyzer to obtain the state of health information.The prognostics and health management model was developed by training historical operating data via machine learning models,support vector machine and gaussian process regression,showing the root mean square error of 1.28×10^(−3) and 8.03×10^(−6).In addition,a techno-economic analysis was performed for a green H_(2) production system,composed of 1 MW of photovoltaic plant and 1 MW of alkaline water electrolyzer,to provide economic insights and feasibility of the system.A levelized cost of H_(2) of$6.89 kgH_(2)−1 was calculated and the potential to reach the levelized cost of H_(2) from steam methane reforming with carbon capture and storage was shown by considering the learning rate of the photovoltaic module and elec-trolyzer.Finally,the replacement of the alkaline water electrolyzer at around 10 years was preferred to increase the net present value from the green H_(2) production system when capital expenditure and replacement cost are low enough.展开更多
High-entropy materials(HEMs),which are newly manufactured compounds that contain five or more metal cations,can be a platform with desired properties,including improved electrocatalytic performance owing to the inhere...High-entropy materials(HEMs),which are newly manufactured compounds that contain five or more metal cations,can be a platform with desired properties,including improved electrocatalytic performance owing to the inherent complexity.Here,a strain engineering methodology is proposed to design transition-metal-based HEM by Li manipulation(LiTM)with tunable lattice strain,thus tailoring the electronic structure and boosting electrocatalytic performance.As confirmed by the experiments and calculation results,tensile strain in the LiTM after Li manipulation can optimize the d-band center and increase the electrical conductivity.Accordingly,the asprepared LiTM-25 demonstrates optimized oxygen evolution reaction and hydrogen evolution reaction activity in alkaline saline water,requiring ultralow overpotentials of 265 and 42 mV at 10 mA cm−2,respectively.More strikingly,LiTM-25 retains 94.6%activity after 80 h of a durability test when assembled as an anion-exchange membrane water electrolyzer.Finally,in order to show the general efficacy of strain engineering,we incorporate Li into electrocatalysts with higher entropies as well.展开更多
The key challenge of industrial water electrolysis is to design catalytic electrodes that can stabilize high current density with low power consumption(i.e.,overpotential),while industrial harsh conditions make the ba...The key challenge of industrial water electrolysis is to design catalytic electrodes that can stabilize high current density with low power consumption(i.e.,overpotential),while industrial harsh conditions make the balance between electrode activity and stability more difficult.Here,we develop an efficient and durable electrode for water oxidation reaction(WOR),which yields a high current density of 1000 mA cm−2 at an overpotential of only 284 mV in 1M KOH at 25°C and shows robust stability even in 6M KOH strong alkali with an elevated temperature up to 80°C.This electrode is fabricated from a cheap nickel foam(NF)substrate through a simple one-step solution etching method,resulting in the growth of ultrafine phosphorus doped nickel-iron(oxy)hydroxide[P-(Ni,Fe)O_(x)H_(y)]nanoparticles embedded into abundant micropores on the surface,featured as a self-stabilized catalyst–substrate fusion electrode.Such self-stabilizing effect fastens highly active P-(Ni,Fe)O_(x)H_(y)species on conductive NF substrates with significant contribution to catalyst fixation and charge transfer,realizing a win–win tactics for WOR activity and durability at high current densities in harsh environments.This work affords a cost-effective WOR electrode that can well work at large current densities,suggestive of the rational design of catalyst electrodes toward industrial-scale water electrolysis.展开更多
The strength and durability of concrete will be significantly reduced at high volume of mineral admixture,and the poor early strength of concrete also still needs to be solved.In this investigation,a highly active alk...The strength and durability of concrete will be significantly reduced at high volume of mineral admixture,and the poor early strength of concrete also still needs to be solved.In this investigation,a highly active alkaline electrolyzed waters was used as mixing water to improve the early strength and enhance the durability of green concrete with high volume mineral admixture,the influences of alkaline electrolyzed water(AEW)on hydration activity of mineral admixture and durability of concrete were determined.The results showed that compared with natural tap water,AEW can accelerate early hydration process of cement in concrete and produce comparatively more hydrated products,leading to a 13.6%higher compressive strength than that of ordinary concrete at early age,but the improvement effect of AEW concrete was relatively reduced at long-term age.Meanwhile,the activity of mineral admixtures could be stimulated by AEW to some extent,the strength and durability performance of AEW concrete after double doping 25%slag and 25%fly ash can still reach the level of ordinary cement concrete without mineral admixtures.The SEM micromorphology of 7 d hydrated natural tap water cement paste was observed to be flaky and tabular,but the AEW cement pastes present obvious cluster and granulation phenomenon.The SEM microstructure of AEW concrete with mineral admixtures is more developed and denser than ordinary tap water concrete with mineral admixtures.Therefore,the AEW probably could realize the effective utilization of about 50%mineral admixture amount of concrete without strength loss,the cement production cost and associated CO_(2) emission reduced,which has a good economic and environmental benefit.展开更多
The use of abundant elements in the earth as electrocatalytic hydrogen production catalysts is of great significance for hydrogen energy cycling.Herein,we report amorphous TiO_(2)-decorated CoP/NF(TiO_(2)–CoP/NF)as a...The use of abundant elements in the earth as electrocatalytic hydrogen production catalysts is of great significance for hydrogen energy cycling.Herein,we report amorphous TiO_(2)-decorated CoP/NF(TiO_(2)–CoP/NF)as an excellent electrocatalyst for alkaline hydrogen evolution reaction(HER).The welldispersed amorphous TiO_(2)on nanoneedle-like CoP arrays preserves the crystal structure of CoP and changes its electronic structure by interfacial charge transfer.Compared to CoP/NF catalyst,the Ti O_(2)–CoP/NF composite catalyst exhibits high HER activity with an overpotential of 61 mV at 10 mA cm^(-2)and high stability.Importantly,it almost maintains the Volmer step as a rate-determining step(RDS)and the Tafel slope at a wide cathodic potential range showing the fast kinetics under large polarization regions.Theoretical simulations reveal that the combination of TiO_(2)and CoP selectively accelerates the hydrated K+diffusion,regulates the interfacial water orientation to adapt to the subsequent smooth water dissociation,and optimizes*H adsorption/H_(2)desorption.The strengthened coupling of HER multi-scale-processes on transition metal compound composites catalysts is the underlying mechanism for improving HER activity.展开更多
Design of the catalyst for efficient water dissociation and hydrogen recombination is paramount in enhancement of the alkaline water electrolysis kinetics.Herein,we reported a delicate hierarchical(VO)_(2) P_(2)O_(7)-...Design of the catalyst for efficient water dissociation and hydrogen recombination is paramount in enhancement of the alkaline water electrolysis kinetics.Herein,we reported a delicate hierarchical(VO)_(2) P_(2)O_(7)-Ni_(2) P@NF(VPO-Ni_(2) P@NF)hybrid catalyst that operated efficiently in alkaline media.The VPO and Ni_(2) P respectively act as the water dissociation promoter and the hydrogen recombination center,which synergistically propel water adsorption/dissociation and H intermediates recombination.The resulting synergistic interfaces between VPO and Ni_(2) P are verified to afford the catalyst an outstanding performance for hydrogen evolution reaction in alkaline media with an overpotential of 154 mV at 10 mA cm^(-2),Tafel slope of 65 mV dec^(-1),and remarkable durability.Furthermore,the catalyst presents the potential for overall water splitting.This work may shed fresh light on the high-performance electrocatalyst design and the application of VPO on water electrolysis.展开更多
The Yellow Sea is located between the China Mainland and the Korean Peninsula, representing a typical shallow epicontinental sea. The Yellow Sea Cold Water Mass(YSCWM) is one of the most important physical features ...The Yellow Sea is located between the China Mainland and the Korean Peninsula, representing a typical shallow epicontinental sea. The Yellow Sea Cold Water Mass(YSCWM) is one of the most important physical features in the Yellow Sea. The characteristics of vertical profiles and seasonal variations of biogenic elements in the YSCWM may lead the variations of nutrient availability(e.g., phosphorus) and phosphorus stress of phytoplankton. In this study, the authors surveyed the seasonal variations of phytoplankton phosphorus stress with emphasis on the effect of the YSCWM during the four cruises in April and October 2006, March and August 2007. Using both bulk and single-cell alkaline phosphatase activity(APA) assays, this study evaluated phosphorus status of phytoplankton community, succession of phytoplankton community and ecophysiological responses of phytoplankton to phosphorus in the typical region of the YSCWM. With the occurrence of the YSCWM, especially the variations of concentration of dissolved inorganic phosphorus(DIP), the results of bulk APA appeared corresponding seasonal variations. Along Transects A and B, the mean APA in August was the highest, and that in March was the lowest. According to the ELF-labeled assay's results, seasonal variations of the ELF-labeled percentages within dominant species indicated that diatoms were dominant in March, April and October, while dinoflagellates were dominant in August. During the four cruises, the ELF-labeled percentages of diatoms except Paralia sulcata showed that diatoms were not phosphorus deficient in April 2006 at all, but suffered from severe phosphorus stress in August 2007. In comparison, the ELF-labeled percentages of dinoflagellates were all above 50% during the four time series, which meant dinoflagellates such as Alexandrium and Scrippsiella, sustained perennial phosphorus stress.展开更多
The development of single electrode with multifunctional purposes for electrochemical devices remains a symbolic challenge in recent technology.This work explores interfacially-rich transition metal nitride hybrid tha...The development of single electrode with multifunctional purposes for electrochemical devices remains a symbolic challenge in recent technology.This work explores interfacially-rich transition metal nitride hybrid that consist of nickel nitride and vanadium oxynitride(VO_(0.26)N_(0.52))on robust carbon fiber(denoted CF/Ni_(3)N/VON)as trifunctional electrode for hydrogen evolution reaction(HER),oxygen evolution reaction(OER),and sodium ion batteries(SIBs).The as-prepared CF/Ni_(3)N/VON exhibits low HER overpotential of 48 m V@10 m A cm^(-2),OER overpotential of 287 m V@10 m A cm^(-2),and sodium-ion anode storage reversible capacity of 555 m A h g^(-1)@0.2 C.Theoretical analyses reveal that the Ni_(3)N effectively facilitates hydrogen desorption for HER,increases the electrical conductivity for OER,and promotes the Na-ion storage intercalation process,while the VON substantially elevates the water dissociation kinetics for HER,accelerates the adsorption of OH*intermediate for OER and enhances the Na-ion surface adsorption storage process.Owing to the excellent HER and OER performances of the CF/Ni_(3)N/VON electrode,an overall water splitting device denoted as CF/Ni_(3)N/VON//CF/Ni_(3)N/VON was not only assembled showing an operating voltage of 1.63 V at current density of 10 m A cm^(-2)but was also successfully self-powered by the assembled CF/Ni_(3)N/VON//CF/Na_(3)V_(2)(PO_(4))_(3) flexible sodium ion battery.This work will contribute to the development of efficient and cost-effective flexible integrated electrochemical energy devices.展开更多
Surface distribution and seasonal variation of alkalinity and specific alkalinity in Kuroshio area of the East ChinaSea and their application to the water mass tracing are discussed in this paper. Results show a disti...Surface distribution and seasonal variation of alkalinity and specific alkalinity in Kuroshio area of the East ChinaSea and their application to the water mass tracing are discussed in this paper. Results show a distinct seasonal variation of the alkalinity, which is concerned with the process of vertical mixing. Different specific alkalinity in various water masses has been found. On the basis of the difference of the specific alkalinity and the distribution of alkalinity, two water fronts in summer season, located at 27°-30°N and 124°-1 27°E, (Ⅰ), and at the northern waters about one latitude from the Taiwan Island, (Ⅱ); one in winter season at about one longitude from coast of mainland of China and 26°-30°N were found. In summer season, about 1-2 longitudes eastward shift of front (Ⅰ) is found by comparison of data in May and August. And the high alkalinity of the northern East China Sea in summer season may be caused by the Huanghe River runoff flowing southward along with the Huanghai Sea Coastal Current.展开更多
The groundwaters within the ophiolite nappes in the southwestern part of Turkey have different physical and geochemical characteristics and are divided into five different groundwater facies.These are(1) Mg-HCO_(3),(2...The groundwaters within the ophiolite nappes in the southwestern part of Turkey have different physical and geochemical characteristics and are divided into five different groundwater facies.These are(1) Mg-HCO_(3),(2) Mg-HCO_(3)-CO_(3),(3) Mg-CO_(3)-HCO_(3),(4) Na-Ca-Cl-CO_(3),and(5) Ca-MgHCO_(3).The waters interact with ophiolites,mainly made up of basic-ultrabasic rocks,are characterized by alkaline and hyperalkaline character.Alkaline waters have high Mg,HCO_(3)contents and Mg/Ca ratio,and hyperalkaline water has high Na,Ca contents,and low Mg/Ca ratio.The waters in the study area formed by the interaction of meteoric waters with variously serpentinized ultramafic rocks under low-temperature conditions.Silicate weathering is the main hydrogeochemical process that plays a role in the chemical composition of water.Mg-HCO_(3)-type groundwaters are produced under open-system conditions with respect to CO_(2)due to meteoric water-serpentinized peridotite interactions in a shallow environment.Deep-seated groundwaters are Na-Ca-Cl-CO_(3)-type waters with high pH(TN-8 sample with p H 10.72),depleted in terms of Mg due to water-peridotite interaction under closed-system conditions with respect to CO_(2).Salda Lake with an alkaline character and high Mg and Na content is characterized by high evaporation and hydromagnesite deposition.展开更多
Efficient,durable and economic electrocatalysts are crucial for commercializing water electrolysis technology.Herein,we report an advanced bifunctional electrocatalyst for alkaline water splitting by growing NiFe-laye...Efficient,durable and economic electrocatalysts are crucial for commercializing water electrolysis technology.Herein,we report an advanced bifunctional electrocatalyst for alkaline water splitting by growing NiFe-layered double hydroxide(NiFe-LDH)nanosheet arrays on the conductive NiMo-based nanorods deposited on Ni foam to form a three-dimensional(3D)architecture,which exhibits exceptional performances for both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).In overall water splitting,only the low operation voltages of 1.45/1.61 V are required to reach the current density of 10/500 mA·cm^(-2),and the continuous water splitting at an industrial-level current density of 500 mA·cm^(-2) shows a negligible degradation(1.8%)of the cell voltage over 1000 h.The outstanding performance is ascribed to the synergism of the HER-active NiMo-based nanorods and the OER-active NiFe-LDH nanosheet arrays of the hybridized 3D architecture.Specifically,the dense NiFe-LDH nanosheet arrays enhance the local pH on cathode by retarding OH-diffusion and enlarge the electrochemically active surface area on anode,while the conductive NiMo-based nanorods on Ni foam much decrease the charge-transfer resistances of both electrodes.This study provides an efficient strategy to explore advanced bifunctional electrocatalysts for overall water splitting by rationally hybridizing HER-and OER-active components.展开更多
The electrodeposition approach is significant in electrode fabrication for practical application.Herein,the electrodeposited amorphous NiFe hydroxide species for oxygen evolution reaction (OER) in water splitting reac...The electrodeposition approach is significant in electrode fabrication for practical application.Herein,the electrodeposited amorphous NiFe hydroxide species for oxygen evolution reaction (OER) in water splitting reaction is demonstrated by revealing the synergistic effect influenced by the support electrode of Fe and Ni foil and the contents of Fe and Ni in the electrolyte.All the electrodeposited samples have an amorphous structure and similar profiles of binding energy and chemical states for Fe and Ni as characterized by the spectroscopic techniques.While the support effect and Fe/Ni synergistic effect are indeed observed for the varied catalytic performances observed for the different electrodes;the Ni foil supported catalyst exhibits much higher performance than that of the Fe foil supported catalyst,and the different redox potentials of Ni species in the different Fe/Ni electrode resulting from the Fe–Ni synergism are observed in the cyclic voltammetry curve analysis.The surface roughness and the electrochemical surface area are also influenced by the support effect and the Fe/Ni ratio in the plating electrolyte.The optimal electrode shows a very low overpotential of~200 mV to reach 10 mA cm^(-2),and very high catalytic stability by the consecutive cyclic voltammetry measurements and 20 h stability test.Though it has the largest electrochemical surface area,the highest catalytic efficiency for these active sites is also indicated by the specific activity and turnover frequency polarization curves.The current work shows the effective experience for the electrodeposited Fe/Ni based catalysts in large-scale fabrication,which can be more practical for hydrogen generation in the alkaline water electrolysis.展开更多
The effects of three environmental factors,salinity,carbonate alkalinity,and pH,on the survival,feeding,and respiratory metabolism of Eogammarus possjeticus(Amphipoda:Gammaridae)were investigated experimentally.The re...The effects of three environmental factors,salinity,carbonate alkalinity,and pH,on the survival,feeding,and respiratory metabolism of Eogammarus possjeticus(Amphipoda:Gammaridae)were investigated experimentally.The results show that E.possjeticus could tolerate a broad salinity range.The 24-h lowest median lethal salinity was 2.70,and the highest was 47.33.The 24-h median lethal alkalinity and pH were 23.05 mmol/L and 9.91,respectively;both values decreased gradually with time.Different values of salinity,carbonate alkalinity,and pH resulted in significant differences in the cumulative mortality(P<0.05).The ingestion rate and feed absorption efficiency were significantly affected by the coupling of the three environmental factors(P<0.05).With increases in carbonate alkalinity,salinity,and pH,both ingestion rate and feed absorption efficiency exhibited a downward trend,indicating a decline in feeding ability under high salinity and more alkaline water conditions.The coupling of salinity,carbonate alkalinity,and pH also had a significant effect on respiration and excretion(P<0.05).The oxygen consumption rate increased first and then decreased with increasing carbonate alkalinity.Under the same carbonate alkalinity values,the oxygen consumption rate increased with increasing salinity.Under the same carbonate alkalinity and salinity,the oxygen consumption rate initially increased and then decreased with increasing pH.The O:N ratio first increased and then decreased with increasing carbonate alkalinity.When carbonate alkalinity was less than 6 mmol/L,the O:N ratio increased with increasing salinity and decreased with increasing pH.The results demonstrate that changes in salinity,carbonate alkalinity,and pH had a measurable impact on the osmotic pressure equilibrium in E.possjeticus and affected the energy supply mode(i.e.ratio of metabolic substrate).展开更多
Residual H_(2)O_(2)from UV/H_(2)O_(2)treatment can be quenched by thiosulfate,bisulfite,and chlorine,but the kinetics of these reactions have not been reported under the full range of practical conditions.In this stud...Residual H_(2)O_(2)from UV/H_(2)O_(2)treatment can be quenched by thiosulfate,bisulfite,and chlorine,but the kinetics of these reactions have not been reported under the full range of practical conditions.In this study,the rates of H_(2)O_(2)quenching by these compounds were compared in different water matrices,temperatures,pH,and when using different forms of bisulfite and chlorine.In general,it was confirmed that thiosulfate would be too slow to serve as a quenching agent in most practical scenarios.At pH 7-8.5,chlorine tends to quench H_(2)O_(2)more than 20 times faster than bisulfite in the various conditions tested.An important observation was that in lightly-buffered water(e.g.,alkalinity of 20 mg/L as CaCO_(3)),the form of chlorine can have a large impact on quenching rate,with gaseous chlorine slowing the reaction due to its lowering of the pH,and hypochlorite having the opposite effect.These impacts will become less significant when water buffer capacity(i.e.,alkalinity)increases(e.g.,to 80 mg/L as CaCO_(3)).In addition,water temperature should be considered as the time required to quench H_(2)O_(2)by chlorine at 4℃is up to 3 times longer than at 20℃.展开更多
Devising an electrocatalyst with brilliant efficiency and satisfactory durability for hydrogen production is of considerable demand,especially for large-scale application.Herein,we adopt a multi-step consequential ind...Devising an electrocatalyst with brilliant efficiency and satisfactory durability for hydrogen production is of considerable demand,especially for large-scale application.Herein,we adopt a multi-step consequential induced strategy to construct a bifunctional electrocatalyst for the overall water splitting.Graphene oxide(GO)was used as a carbon matrix and in situ oxygen source,which was supported by the octahedral PtNi alloy to form the PtxNiy-GO precursor.When calcinating in Ar atmosphere,the oxygen in GO induced the surface segregation of Ni from the PtNi octahedron to form a core-shell structure of Ptx@Niy.Then,the surface-enriched Ni continuously induced the reformation of C in reduced graphene oxide(rGO)to enhance the degree of graphitization.This multi-step induction formed a nanocatalyst Pt_(x)@Ni_(y)-rGO which has very high catalytic efficiency and stability.By optimizing the feeding ratio of PtNi(Pt:Ni=1:2),the electrolytic overall water splitting at 10 mA·cm^(-2) can be driven by an electrolytic voltage of as low as 1.485 V,and hydrogen evolution reaction(HER)only needs an overpotential of 37 mV in 1.0 M KOH aqueous solution.Additionally,the catalyst exhibited consistent existence form in both HER and oxygen evolution reaction(OER),which was verified by switching the anode and cathode of the cell in the electrolysis of water.This work provides a new idea for the synthesis and evaluation of the bifunctional catalysts for water splitting.展开更多
基金supported by the National Key Research and Development Program(No.2022YFB4202200)the Fundamental Research Funds for the Central Universities.
文摘Green hydrogen(H_(2))produced by renewable energy powered alkaline water electrolysis is a promising alternative to fossil fuels due to its high energy density with zero-carbon emissions.However,efficient and economic H_(2) production by alkaline water electrolysis is hindered by the sluggish hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).Therefore,it is imperative to design and fabricate high-active and low-cost non-precious metal catalysts to improve the HER and OER performance,which affects the energy efficiency of alkaline water electrolysis.Ni_(3)S_(2) with the heazlewoodite structure is a potential electrocatalyst with near-metal conductivity due to the Ni–Ni metal network.Here,the review comprehensively presents the recent progress of Ni_(3)S_(2)-based electrocatalysts for alkaline water electrocatalysis.Herein,the HER and OER mechanisms,performance evaluation criteria,preparation methods,and strategies for performance improvement of Ni_(3)S_(2)-based electrocatalysts are discussed.The challenges and perspectives are also analyzed.
基金financial support from the National Key R&D Program(2023YFE0108000)the Academy of Sciences Project of Guangdong Province(2019GDASYL-0102007,2021GDASYL-20210103063)+1 种基金GDAS’Project of Science and Technology Development(2022GDASZH-2022010203-003)financial support from the China Scholarship Council(202108210128)。
文摘An advantageous porous architecture of electrodes is pivotal in significantly enhancing alkaline water electrolysis(AWE)efficiency by optimizing the mass transport mechanisms.This effect becomes even more pronounced when aiming to achieve elevated current densities.Herein,we employed a rapid and scalable laser texturing process to craft novel multi-channel porous electrodes.Particularly,the obtained electrodes exhibit the lowest Tafel slope of 79 mV dec^(-1)(HER)and 49 mV dec^(-1)(OER).As anticipated,the alkaline electrolyzer(AEL)cell incorporating multi-channel porous electrodes(NP-LT30)exhibited a remarkable improvement in cell efficiency,with voltage drops(from 2.28 to 1.97 V)exceeding 300 mV under 1 A cm^(-1),compared to conventional perforated Ni plate electrodes.This enhancement mainly stemmed from the employed multi-channel porous structure,facilitating mass transport and bubble dynamics through an innovative convection mode,surpassing the traditional convection mode.Furthermore,the NP-LT30-based AEL cell demonstrated exceptional durability for 300 h under 1.0 A cm^(-2).This study underscores the capability of the novel multi-channel porous electrodes to expedite mass transport in practical AWE applications.
基金This study was funded by the Australian Research Council(FT170100224)the Australian Renewable Energy Agency+1 种基金National Natural Science Foundation of China(21825501)the Tsinghua University Initiative Scientific Research Program.
文摘Electrochemical water splitting has attracted considerable attention for the production of hydrogen fuel by using renewable energy resources.However,the sluggish reaction kinetics make it essential to explore precious-metal-free electrocatalysts with superior activity and long-term stability.Tremendous efforts have been made in exploring electrocatalysts to reduce the energy barriers and improve catalytic efficiency.This review summarizes different categories of precious-metal-free electrocatalysts developed in the past 5 years for alkaline water splitting.The design strategies for optimizing the electronic and geometric structures of electrocatalysts with enhanced catalytic performance are discussed,including composition modulation,defect engineering,and structural engineering.Particularly,the advancement of operando/in situ characterization techniques toward the understanding of structural evolution,reaction intermediates,and active sites during the water splitting process are summarized.Finally,current challenges and future perspectives toward achieving efficient catalyst systems for industrial applications are proposed.This review will provide insights and strategies to the design of precious-metalfree electrocatalysts and inspire future research in alkaline water splitting.
基金financially sponsored by the National Natural Science Foundation of China(Grant No.22075223,22179104)the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing(Wuhan University of Technology)(2021-ZD-4)the Fundamental Research Funds for the Central Universities(No.2020-YB-012)。
文摘The epitaxial heterostructure can be rationally designed based on the in situ growth of two compatible phases with lattice similarity,in which the modulated electronic states and tuned adsorption behaviors are conducive to the enhancement of electrocatalytic activity.Herein,theoretical simulations first disclose the charge transfer trend and reinforced inherent electron conduction around the epitaxial heterointerface between Ru clusters and Ni_(3)N substrate(cRu-Ni_(3)N),thus leading to the optimized adsorption behaviors and reduced activation energy barriers.Subsequently,the defectrich nanosheets with the epitaxially grown cRu-Ni_(3)N heterointerface are successfully constructed.Impressively,by virtue of the superiority of intrinsic activity and reaction kinetics,such unique epitaxial heterostructure exhibits remarkable bifunctional catalytic activity toward electrocatalytic OER(226 mV@20 mA cm^(−2))and HER(32 mV@10 mA cm^(−2))in alkaline media.Furthermore,it also shows great application prospect in alkaline freshwater and seawater splitting,as well as solar-to-hydrogen integrated system.This work could provide beneficial enlightenment for the establishment of advanced electrocatalysts with epitaxial heterointerfaces.
文摘Alkaline electrolyzers for water splitting under the industrial current densities are always burdened with huge energy consumption due to the high overpotential and poor stability of the anode nanocatalysts for oxygen evolution reaction(OER).Inspired by the interfacial charge transfer for enhancing the performance,a series of in-situ grown interfacial Mn-NiFe lactate dehydrogenase(LDH)was designed on the Fe_(0.64)Ni_(0.36)/NM(nickel mesh)alloy layer.The optimized Mn_(0.15)-NiFe LDH/Fe_(0.64)Ni_(0.36)/NM exhibited an ultralow overpotential of 295 mV to drive 500 mA·cm^(-2)and an incredible stability under large current density.The interfacial space and heteroatom doping synergistically triggered the electronic structure optimization to promote electron transfer and ensure the durability of the high-current reaction.Notably,the designed Mn_(0.15)-NiFe LDH/Fe_(0.64)Ni_(0.36)/NM as an anode in an integral alkaline electrolyzer exhibited a cell voltage of 1.78 V at 500 mA·cm^(-2) with a stability of 366 h.Density functional theory(DFT)calculations further demonstrated the synergistic effect of alloy layer introduction and Mn doping could accelerate electron transfer and stabilize the charged active center to activate the NiFe LDH and reduce the OER energy barrier.Our work offers new insights into developing efficient self-supported catalysts for high-current alkaline water oxidation.
基金This research was supported by the Hydrogen Energy Innovation Technology Development Program of the National Research Foundation of Korea(NRF)funded by the Korean government(Ministry of Science and ICT(MSIT))(NRF-2019M3E6A1064290)supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(NRF-2019M1A2A2065614).
文摘Recently,considerable attention has been paid to the installation of renewable energy capacity to mitigate global CO_(2) emissions.H_(2) produced using water electrolysis and renewable energy is regarded as a clean energy carrier,generating electricity without CO_(2) emissions,called‘Green H 2’.In this paper,a prognostics and health man-agement model for an alkaline water electrolyzer was proposed to predict the load voltage on the electrolyzer to obtain the state of health information.The prognostics and health management model was developed by training historical operating data via machine learning models,support vector machine and gaussian process regression,showing the root mean square error of 1.28×10^(−3) and 8.03×10^(−6).In addition,a techno-economic analysis was performed for a green H_(2) production system,composed of 1 MW of photovoltaic plant and 1 MW of alkaline water electrolyzer,to provide economic insights and feasibility of the system.A levelized cost of H_(2) of$6.89 kgH_(2)−1 was calculated and the potential to reach the levelized cost of H_(2) from steam methane reforming with carbon capture and storage was shown by considering the learning rate of the photovoltaic module and elec-trolyzer.Finally,the replacement of the alkaline water electrolyzer at around 10 years was preferred to increase the net present value from the green H_(2) production system when capital expenditure and replacement cost are low enough.
基金support provided by the National Natural Science Foundation of China(Grant Nos.51972048,U23A20605)support provided by the Performance subsidy fund for Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province(Grant No.22567627H)the additional data in the revised manuscriptsupported by the National Key Research and Development Program of China(No.2022YFB3706300).
文摘High-entropy materials(HEMs),which are newly manufactured compounds that contain five or more metal cations,can be a platform with desired properties,including improved electrocatalytic performance owing to the inherent complexity.Here,a strain engineering methodology is proposed to design transition-metal-based HEM by Li manipulation(LiTM)with tunable lattice strain,thus tailoring the electronic structure and boosting electrocatalytic performance.As confirmed by the experiments and calculation results,tensile strain in the LiTM after Li manipulation can optimize the d-band center and increase the electrical conductivity.Accordingly,the asprepared LiTM-25 demonstrates optimized oxygen evolution reaction and hydrogen evolution reaction activity in alkaline saline water,requiring ultralow overpotentials of 265 and 42 mV at 10 mA cm−2,respectively.More strikingly,LiTM-25 retains 94.6%activity after 80 h of a durability test when assembled as an anion-exchange membrane water electrolyzer.Finally,in order to show the general efficacy of strain engineering,we incorporate Li into electrocatalysts with higher entropies as well.
基金National Natural Science Foundation of China,Grant/Award Numbers:11974303,12074332Qinglan Project of Jiangsu Province,Grant/Award Number:137050317the Interdisciplinary Research Project of Chemistry Discipline,Grant/Award Number:yzuxk202014 and High‐End Talent Program of Yangzhou University,Grant/Award Number:137080051。
文摘The key challenge of industrial water electrolysis is to design catalytic electrodes that can stabilize high current density with low power consumption(i.e.,overpotential),while industrial harsh conditions make the balance between electrode activity and stability more difficult.Here,we develop an efficient and durable electrode for water oxidation reaction(WOR),which yields a high current density of 1000 mA cm−2 at an overpotential of only 284 mV in 1M KOH at 25°C and shows robust stability even in 6M KOH strong alkali with an elevated temperature up to 80°C.This electrode is fabricated from a cheap nickel foam(NF)substrate through a simple one-step solution etching method,resulting in the growth of ultrafine phosphorus doped nickel-iron(oxy)hydroxide[P-(Ni,Fe)O_(x)H_(y)]nanoparticles embedded into abundant micropores on the surface,featured as a self-stabilized catalyst–substrate fusion electrode.Such self-stabilizing effect fastens highly active P-(Ni,Fe)O_(x)H_(y)species on conductive NF substrates with significant contribution to catalyst fixation and charge transfer,realizing a win–win tactics for WOR activity and durability at high current densities in harsh environments.This work affords a cost-effective WOR electrode that can well work at large current densities,suggestive of the rational design of catalyst electrodes toward industrial-scale water electrolysis.
基金funded by National Natural Science Foundation of China(Grant Nos.51808310,51878366)Natural Science Foundation of Shandong Province(Grant Nos.ZR2019PEE007,ZR2020ME036)High-level Scientific Research Foundation for the introduction of talent of Qingdao Agricultural University(Grant No.1118034).
文摘The strength and durability of concrete will be significantly reduced at high volume of mineral admixture,and the poor early strength of concrete also still needs to be solved.In this investigation,a highly active alkaline electrolyzed waters was used as mixing water to improve the early strength and enhance the durability of green concrete with high volume mineral admixture,the influences of alkaline electrolyzed water(AEW)on hydration activity of mineral admixture and durability of concrete were determined.The results showed that compared with natural tap water,AEW can accelerate early hydration process of cement in concrete and produce comparatively more hydrated products,leading to a 13.6%higher compressive strength than that of ordinary concrete at early age,but the improvement effect of AEW concrete was relatively reduced at long-term age.Meanwhile,the activity of mineral admixtures could be stimulated by AEW to some extent,the strength and durability performance of AEW concrete after double doping 25%slag and 25%fly ash can still reach the level of ordinary cement concrete without mineral admixtures.The SEM micromorphology of 7 d hydrated natural tap water cement paste was observed to be flaky and tabular,but the AEW cement pastes present obvious cluster and granulation phenomenon.The SEM microstructure of AEW concrete with mineral admixtures is more developed and denser than ordinary tap water concrete with mineral admixtures.Therefore,the AEW probably could realize the effective utilization of about 50%mineral admixture amount of concrete without strength loss,the cement production cost and associated CO_(2) emission reduced,which has a good economic and environmental benefit.
基金financially supported by the National Key Research and Development Program of China(2021YFB4000301)the National Natural Science Foundation of China(21822803,22090030,and 21576032)。
文摘The use of abundant elements in the earth as electrocatalytic hydrogen production catalysts is of great significance for hydrogen energy cycling.Herein,we report amorphous TiO_(2)-decorated CoP/NF(TiO_(2)–CoP/NF)as an excellent electrocatalyst for alkaline hydrogen evolution reaction(HER).The welldispersed amorphous TiO_(2)on nanoneedle-like CoP arrays preserves the crystal structure of CoP and changes its electronic structure by interfacial charge transfer.Compared to CoP/NF catalyst,the Ti O_(2)–CoP/NF composite catalyst exhibits high HER activity with an overpotential of 61 mV at 10 mA cm^(-2)and high stability.Importantly,it almost maintains the Volmer step as a rate-determining step(RDS)and the Tafel slope at a wide cathodic potential range showing the fast kinetics under large polarization regions.Theoretical simulations reveal that the combination of TiO_(2)and CoP selectively accelerates the hydrated K+diffusion,regulates the interfacial water orientation to adapt to the subsequent smooth water dissociation,and optimizes*H adsorption/H_(2)desorption.The strengthened coupling of HER multi-scale-processes on transition metal compound composites catalysts is the underlying mechanism for improving HER activity.
基金supported by the National Natural Science Foundation of China(No.51902232)。
文摘Design of the catalyst for efficient water dissociation and hydrogen recombination is paramount in enhancement of the alkaline water electrolysis kinetics.Herein,we reported a delicate hierarchical(VO)_(2) P_(2)O_(7)-Ni_(2) P@NF(VPO-Ni_(2) P@NF)hybrid catalyst that operated efficiently in alkaline media.The VPO and Ni_(2) P respectively act as the water dissociation promoter and the hydrogen recombination center,which synergistically propel water adsorption/dissociation and H intermediates recombination.The resulting synergistic interfaces between VPO and Ni_(2) P are verified to afford the catalyst an outstanding performance for hydrogen evolution reaction in alkaline media with an overpotential of 154 mV at 10 mA cm^(-2),Tafel slope of 65 mV dec^(-1),and remarkable durability.Furthermore,the catalyst presents the potential for overall water splitting.This work may shed fresh light on the high-performance electrocatalyst design and the application of VPO on water electrolysis.
基金The National Natural Science Foundation of China under contract Nos 41206106 and 41222038the National Basic Research Program of China under contract No.2006CB400604+1 种基金the National High Technology Research and Development Program under contract No.2007AA092003-01Cooperation on the Development of Basic Technologies for the Yellow Sea and East China Sea Operational Oceanographic System(YOOS)
文摘The Yellow Sea is located between the China Mainland and the Korean Peninsula, representing a typical shallow epicontinental sea. The Yellow Sea Cold Water Mass(YSCWM) is one of the most important physical features in the Yellow Sea. The characteristics of vertical profiles and seasonal variations of biogenic elements in the YSCWM may lead the variations of nutrient availability(e.g., phosphorus) and phosphorus stress of phytoplankton. In this study, the authors surveyed the seasonal variations of phytoplankton phosphorus stress with emphasis on the effect of the YSCWM during the four cruises in April and October 2006, March and August 2007. Using both bulk and single-cell alkaline phosphatase activity(APA) assays, this study evaluated phosphorus status of phytoplankton community, succession of phytoplankton community and ecophysiological responses of phytoplankton to phosphorus in the typical region of the YSCWM. With the occurrence of the YSCWM, especially the variations of concentration of dissolved inorganic phosphorus(DIP), the results of bulk APA appeared corresponding seasonal variations. Along Transects A and B, the mean APA in August was the highest, and that in March was the lowest. According to the ELF-labeled assay's results, seasonal variations of the ELF-labeled percentages within dominant species indicated that diatoms were dominant in March, April and October, while dinoflagellates were dominant in August. During the four cruises, the ELF-labeled percentages of diatoms except Paralia sulcata showed that diatoms were not phosphorus deficient in April 2006 at all, but suffered from severe phosphorus stress in August 2007. In comparison, the ELF-labeled percentages of dinoflagellates were all above 50% during the four time series, which meant dinoflagellates such as Alexandrium and Scrippsiella, sustained perennial phosphorus stress.
基金supported by the Hunan Provincial Natural Science Foundation (2021JJ30087)the Science and Technology Innovation Program of Hunan Province (2022WZ1012)the Fundamental Research Funds for the Central Universities and Guangxi Key Laboratory of Information Materials&Guilin University of Electronic Technology,China (211011K)。
文摘The development of single electrode with multifunctional purposes for electrochemical devices remains a symbolic challenge in recent technology.This work explores interfacially-rich transition metal nitride hybrid that consist of nickel nitride and vanadium oxynitride(VO_(0.26)N_(0.52))on robust carbon fiber(denoted CF/Ni_(3)N/VON)as trifunctional electrode for hydrogen evolution reaction(HER),oxygen evolution reaction(OER),and sodium ion batteries(SIBs).The as-prepared CF/Ni_(3)N/VON exhibits low HER overpotential of 48 m V@10 m A cm^(-2),OER overpotential of 287 m V@10 m A cm^(-2),and sodium-ion anode storage reversible capacity of 555 m A h g^(-1)@0.2 C.Theoretical analyses reveal that the Ni_(3)N effectively facilitates hydrogen desorption for HER,increases the electrical conductivity for OER,and promotes the Na-ion storage intercalation process,while the VON substantially elevates the water dissociation kinetics for HER,accelerates the adsorption of OH*intermediate for OER and enhances the Na-ion surface adsorption storage process.Owing to the excellent HER and OER performances of the CF/Ni_(3)N/VON electrode,an overall water splitting device denoted as CF/Ni_(3)N/VON//CF/Ni_(3)N/VON was not only assembled showing an operating voltage of 1.63 V at current density of 10 m A cm^(-2)but was also successfully self-powered by the assembled CF/Ni_(3)N/VON//CF/Na_(3)V_(2)(PO_(4))_(3) flexible sodium ion battery.This work will contribute to the development of efficient and cost-effective flexible integrated electrochemical energy devices.
文摘Surface distribution and seasonal variation of alkalinity and specific alkalinity in Kuroshio area of the East ChinaSea and their application to the water mass tracing are discussed in this paper. Results show a distinct seasonal variation of the alkalinity, which is concerned with the process of vertical mixing. Different specific alkalinity in various water masses has been found. On the basis of the difference of the specific alkalinity and the distribution of alkalinity, two water fronts in summer season, located at 27°-30°N and 124°-1 27°E, (Ⅰ), and at the northern waters about one latitude from the Taiwan Island, (Ⅱ); one in winter season at about one longitude from coast of mainland of China and 26°-30°N were found. In summer season, about 1-2 longitudes eastward shift of front (Ⅰ) is found by comparison of data in May and August. And the high alkalinity of the northern East China Sea in summer season may be caused by the Huanghe River runoff flowing southward along with the Huanghai Sea Coastal Current.
文摘The groundwaters within the ophiolite nappes in the southwestern part of Turkey have different physical and geochemical characteristics and are divided into five different groundwater facies.These are(1) Mg-HCO_(3),(2) Mg-HCO_(3)-CO_(3),(3) Mg-CO_(3)-HCO_(3),(4) Na-Ca-Cl-CO_(3),and(5) Ca-MgHCO_(3).The waters interact with ophiolites,mainly made up of basic-ultrabasic rocks,are characterized by alkaline and hyperalkaline character.Alkaline waters have high Mg,HCO_(3)contents and Mg/Ca ratio,and hyperalkaline water has high Na,Ca contents,and low Mg/Ca ratio.The waters in the study area formed by the interaction of meteoric waters with variously serpentinized ultramafic rocks under low-temperature conditions.Silicate weathering is the main hydrogeochemical process that plays a role in the chemical composition of water.Mg-HCO_(3)-type groundwaters are produced under open-system conditions with respect to CO_(2)due to meteoric water-serpentinized peridotite interactions in a shallow environment.Deep-seated groundwaters are Na-Ca-Cl-CO_(3)-type waters with high pH(TN-8 sample with p H 10.72),depleted in terms of Mg due to water-peridotite interaction under closed-system conditions with respect to CO_(2).Salda Lake with an alkaline character and high Mg and Na content is characterized by high evaporation and hydromagnesite deposition.
基金supported by the National Key Research and Development Program of China(No.2021YFA1500900)the National Natural Science Foundation of China(Nos.52071174,21832003,21972061)+1 种基金the Natural Science Foundation of Jiangsu Province,Major Project(No.BK20212005)the Foundation of Science and Technology of Suzhou(No.SYC2022102).
文摘Efficient,durable and economic electrocatalysts are crucial for commercializing water electrolysis technology.Herein,we report an advanced bifunctional electrocatalyst for alkaline water splitting by growing NiFe-layered double hydroxide(NiFe-LDH)nanosheet arrays on the conductive NiMo-based nanorods deposited on Ni foam to form a three-dimensional(3D)architecture,which exhibits exceptional performances for both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).In overall water splitting,only the low operation voltages of 1.45/1.61 V are required to reach the current density of 10/500 mA·cm^(-2),and the continuous water splitting at an industrial-level current density of 500 mA·cm^(-2) shows a negligible degradation(1.8%)of the cell voltage over 1000 h.The outstanding performance is ascribed to the synergism of the HER-active NiMo-based nanorods and the OER-active NiFe-LDH nanosheet arrays of the hybridized 3D architecture.Specifically,the dense NiFe-LDH nanosheet arrays enhance the local pH on cathode by retarding OH-diffusion and enlarge the electrochemically active surface area on anode,while the conductive NiMo-based nanorods on Ni foam much decrease the charge-transfer resistances of both electrodes.This study provides an efficient strategy to explore advanced bifunctional electrocatalysts for overall water splitting by rationally hybridizing HER-and OER-active components.
基金supported by the National Natural Science Foundation of China (21972124, U2002213)the Double Tops Joint Fund of the Yunnan Science and Technology Bureau and Yunnan University (2019FY003025)+1 种基金the Priority Academic Program Development of Jiangsu Higher Education Institutionthe financial support of national local joint engineering laboratory to functional adsorption material technology for the environmental protection, Soochow University (SDGC2124)。
文摘The electrodeposition approach is significant in electrode fabrication for practical application.Herein,the electrodeposited amorphous NiFe hydroxide species for oxygen evolution reaction (OER) in water splitting reaction is demonstrated by revealing the synergistic effect influenced by the support electrode of Fe and Ni foil and the contents of Fe and Ni in the electrolyte.All the electrodeposited samples have an amorphous structure and similar profiles of binding energy and chemical states for Fe and Ni as characterized by the spectroscopic techniques.While the support effect and Fe/Ni synergistic effect are indeed observed for the varied catalytic performances observed for the different electrodes;the Ni foil supported catalyst exhibits much higher performance than that of the Fe foil supported catalyst,and the different redox potentials of Ni species in the different Fe/Ni electrode resulting from the Fe–Ni synergism are observed in the cyclic voltammetry curve analysis.The surface roughness and the electrochemical surface area are also influenced by the support effect and the Fe/Ni ratio in the plating electrolyte.The optimal electrode shows a very low overpotential of~200 mV to reach 10 mA cm^(-2),and very high catalytic stability by the consecutive cyclic voltammetry measurements and 20 h stability test.Though it has the largest electrochemical surface area,the highest catalytic efficiency for these active sites is also indicated by the specific activity and turnover frequency polarization curves.The current work shows the effective experience for the electrodeposited Fe/Ni based catalysts in large-scale fabrication,which can be more practical for hydrogen generation in the alkaline water electrolysis.
基金Supported by the Youth Talent Support Program of the Laboratory for Marine Ecology and Environmental Science,Pilot National Laboratory for Marine Science and Technology(Qingdao)(No.LMEESYTSP-2018-04-02)the Creative Team Project of the Laboratory for Marine Ecology and Environmental Science,Pilot National Laboratory for Marine Science and Technology(Qingdao)(No.LMEES-CTSP-2018-4)+1 种基金the Central Public-interest Scientific Institution Basal Research Fund,CAFS(No.2020TD50)the Central Public-interest Scientific Institution Basal Research Fund,YSFRI,CAFS(No.20603022018003)。
文摘The effects of three environmental factors,salinity,carbonate alkalinity,and pH,on the survival,feeding,and respiratory metabolism of Eogammarus possjeticus(Amphipoda:Gammaridae)were investigated experimentally.The results show that E.possjeticus could tolerate a broad salinity range.The 24-h lowest median lethal salinity was 2.70,and the highest was 47.33.The 24-h median lethal alkalinity and pH were 23.05 mmol/L and 9.91,respectively;both values decreased gradually with time.Different values of salinity,carbonate alkalinity,and pH resulted in significant differences in the cumulative mortality(P<0.05).The ingestion rate and feed absorption efficiency were significantly affected by the coupling of the three environmental factors(P<0.05).With increases in carbonate alkalinity,salinity,and pH,both ingestion rate and feed absorption efficiency exhibited a downward trend,indicating a decline in feeding ability under high salinity and more alkaline water conditions.The coupling of salinity,carbonate alkalinity,and pH also had a significant effect on respiration and excretion(P<0.05).The oxygen consumption rate increased first and then decreased with increasing carbonate alkalinity.Under the same carbonate alkalinity values,the oxygen consumption rate increased with increasing salinity.Under the same carbonate alkalinity and salinity,the oxygen consumption rate initially increased and then decreased with increasing pH.The O:N ratio first increased and then decreased with increasing carbonate alkalinity.When carbonate alkalinity was less than 6 mmol/L,the O:N ratio increased with increasing salinity and decreased with increasing pH.The results demonstrate that changes in salinity,carbonate alkalinity,and pH had a measurable impact on the osmotic pressure equilibrium in E.possjeticus and affected the energy supply mode(i.e.ratio of metabolic substrate).
基金supported through the Natural Sciences and Engineering Grant CRDPJ-542302-2019,by AECOM and by the City of Toronto.
文摘Residual H_(2)O_(2)from UV/H_(2)O_(2)treatment can be quenched by thiosulfate,bisulfite,and chlorine,but the kinetics of these reactions have not been reported under the full range of practical conditions.In this study,the rates of H_(2)O_(2)quenching by these compounds were compared in different water matrices,temperatures,pH,and when using different forms of bisulfite and chlorine.In general,it was confirmed that thiosulfate would be too slow to serve as a quenching agent in most practical scenarios.At pH 7-8.5,chlorine tends to quench H_(2)O_(2)more than 20 times faster than bisulfite in the various conditions tested.An important observation was that in lightly-buffered water(e.g.,alkalinity of 20 mg/L as CaCO_(3)),the form of chlorine can have a large impact on quenching rate,with gaseous chlorine slowing the reaction due to its lowering of the pH,and hypochlorite having the opposite effect.These impacts will become less significant when water buffer capacity(i.e.,alkalinity)increases(e.g.,to 80 mg/L as CaCO_(3)).In addition,water temperature should be considered as the time required to quench H_(2)O_(2)by chlorine at 4℃is up to 3 times longer than at 20℃.
基金supported by the National Natural Science Foundation of China(No.21872020)1226 Engineering Health Major Project(Nos.BWS17J028 and AWS16J018)Fundamental Research Funds for the Central Universities(No.N180705004).
文摘Devising an electrocatalyst with brilliant efficiency and satisfactory durability for hydrogen production is of considerable demand,especially for large-scale application.Herein,we adopt a multi-step consequential induced strategy to construct a bifunctional electrocatalyst for the overall water splitting.Graphene oxide(GO)was used as a carbon matrix and in situ oxygen source,which was supported by the octahedral PtNi alloy to form the PtxNiy-GO precursor.When calcinating in Ar atmosphere,the oxygen in GO induced the surface segregation of Ni from the PtNi octahedron to form a core-shell structure of Ptx@Niy.Then,the surface-enriched Ni continuously induced the reformation of C in reduced graphene oxide(rGO)to enhance the degree of graphitization.This multi-step induction formed a nanocatalyst Pt_(x)@Ni_(y)-rGO which has very high catalytic efficiency and stability.By optimizing the feeding ratio of PtNi(Pt:Ni=1:2),the electrolytic overall water splitting at 10 mA·cm^(-2) can be driven by an electrolytic voltage of as low as 1.485 V,and hydrogen evolution reaction(HER)only needs an overpotential of 37 mV in 1.0 M KOH aqueous solution.Additionally,the catalyst exhibited consistent existence form in both HER and oxygen evolution reaction(OER),which was verified by switching the anode and cathode of the cell in the electrolysis of water.This work provides a new idea for the synthesis and evaluation of the bifunctional catalysts for water splitting.