Urea oxidation reaction(UOR) has been selected as substitution for oxygen evolution reaction ascribing to its low thermodynamic voltage as well as utilization of nickel as electrocatalyst.Herein,we report the formatio...Urea oxidation reaction(UOR) has been selected as substitution for oxygen evolution reaction ascribing to its low thermodynamic voltage as well as utilization of nickel as electrocatalyst.Herein,we report the formation of nickel single atoms(Ni-SAs) as exceptional bifunctional electrocatalyst toward UOR and hydrogen evolution reaction(HER) in urea-assisted water splitting.In UOR catalysis,Ni-SAs perform a superior catalytic performance than Ni-NP/NC and Pt/C ascribing to the formation of HOO-Ni-N_(4) structure evidenced by in-situ Raman spectroscopy,corresponding to a boosted mass activity by 175-fold at 1.4 V vs.RHE than Ni-NP/NC.Furthermore,Ni-SAs requires only 450 mV overpotential to obtain HER current density of 500 mA cm^(-2).136 mA cm^(-2) is achieved in urea-assisted water splitting at1.7 V for Ni-SAs,boosted by 5.7 times than Pt/C-IrO_(2) driven water splitting.展开更多
The development of efficient nonprecious bifunctional electrocatalysts for water electrolysis is crucial to enhance the sluggish kinetics of the oxygen evolution reaction(OER)and hydrogen evolution reaction(HER).A sel...The development of efficient nonprecious bifunctional electrocatalysts for water electrolysis is crucial to enhance the sluggish kinetics of the oxygen evolution reaction(OER)and hydrogen evolution reaction(HER).A self-supporting,multiscale porous NiFeZn/NiZn-Ni catalyst with a triple interface heterojunction on nickel foam(NF)(NiFeZn/NiZn-Ni/NF)was in-situ fabricated using an electroplating-annealing-etching strategy.The unique multiinterface engineering and three-dimensional porous scaffold significantly modify the mass transport and electron interaction,resulting in superior bifunctional electrocatalytic performance for water splitting.The NiFeZn/NiZn-Ni/NF catalyst demonstrates low overpotentials of 187 m V for HER and 320 mV for OER at a current density of 600 mA/cm^(2),along with high durability over 150 h in alkaline solution.Furthermore,an electrolytic cell assembled with NiFeZn/NiZn-Ni/NF as both the cathode and anode achieves the current densities of 600 and 1000 m A/cm^(2) at cell voltages of 1.796 and 1.901 V,respectively,maintaining the high stability at 50 mA/cm^(2) for over 100 h.These findings highlight the potential of NiFeZn/NiZn-Ni/NF as a cost-effective and highly efficient bifunctional electrocatalyst for overall water splitting.展开更多
This work reports the use of defect engineering and carbon supporting to achieve metal-doped phosphides with high activities and stabilities for the hydrogen evolution reaction(HER)and the oxygen evolution reaction(OE...This work reports the use of defect engineering and carbon supporting to achieve metal-doped phosphides with high activities and stabilities for the hydrogen evolution reaction(HER)and the oxygen evolution reaction(OER)in alkaline media.Specifically,the nitrogen-doped carbon nanofiber-supported Ni-doped CoP_(3) with rich P defects(Pv·)on the carbon cloth(p-NiCoP/NCFs@CC)is synthesized through a plasma-assisted phosphorization method.The p-NiCoP/NCFs@CC is an efficient and stable catalyst for the HER and the OER.It only needs overpotentials of 107 and 306 mV to drive 100 mA cm^(-2) for the HER and the OER,respectively.Its catalytic activities are higher than those of other catalysts reported recently.The high activities of the p-NiCoP/NCFs@CC mainly arise from its peculiar structural features.The density functional theory calculation indicates that the Pv·richness,the Ni doping,and the carbon supporting can optimize the adsorption of the H atoms at the catalyst surface and promote the strong electronic couplings between the carbon nanofiber-supported p-NiCoP with the surface oxide layer formed during the OER process.This gives the p-NiCoP/NCFs@CC with the high activities for the HER and the OER.When used in alkaline water electrolyzers,the p-NiCoP/NCFs@CC shows the superior activity and excellent stability for overall water splitting.展开更多
A two-stage catalytic membrane reactor(CMR)that couples CO_(2) splitting with methane oxidation reactions was constructed based on an oxygen-permeable perovskite asymmetric membrane.The asymmetric membrane comprises a...A two-stage catalytic membrane reactor(CMR)that couples CO_(2) splitting with methane oxidation reactions was constructed based on an oxygen-permeable perovskite asymmetric membrane.The asymmetric membrane comprises a dense SrFe_(0.9)Ta_(0.1)O_(3-σ)(SFT)separation layer and a porous Sr_(0.9)(Fe_(0.9)Ta_(0.1))_(0.9)Cu_(0.1)O_(3-σ)(SFTC)catalytic layer.In thefirst stage reactor,a CO_(2) splitting reaction(CDS:2CO_(2)→2CO+O_(2))occurs at the SFTC catalytic layer.Subsequently,the O_(2) product is selectively extracted through the SFT separation layer to the permeated side for the methane combustion reaction(MCR),which provides an extremely low oxygen partial pressure to enhance the oxygen extraction.In the second stage,a Sr_(0.9)(Fe_(0.9)Ta_(0.1))_(0.9)Ni_(0.1)O_(3-σ)(SFTN)catalyst is employed to reform the products derived from MCR.The two-stage CMR design results in a remarkable 35.4%CO_(2) conversion for CDS at 900℃.The two-stage CMR was extended to a hollowfiber configuration combining with solar irradiation.The solar-assisted two-stage CMR can operate stably for over 50 h with a high hydrogen yield of 18.1 mL min^(-1) cm^(-2).These results provide a novel strategy for reducing CO_(2) emissions,suggesting potential avenues for the design of the high-performance CMRs and catalysts based on perovskite oxides in the future.展开更多
Shear wave splitting(SWS)is regarded as the most effective geophysical method to delineate mantle flow fields by detecting seismic azimuthal anisotropy in the earth's upper mantle,especially in tectonically active...Shear wave splitting(SWS)is regarded as the most effective geophysical method to delineate mantle flow fields by detecting seismic azimuthal anisotropy in the earth's upper mantle,especially in tectonically active regions such as subduction zones.The Aleutian-Alaska subduction zone has a convergence rate of approximately 50 mm/yr,with a trench length reaching nearly 2800 km.Such a long subduction zone has led to intensive continental deformation and numerous strong earthquakes in southern and central Alaska,while northern Alaska is relatively inactive.The sharp contrast makes Alaska a favorable locale to investigate the impact of subduction on mantle dynamics.Moreover,the uniqueness of this subduction zone,including the unusual subducting type,varying slab geometry,and atypical magmatic activity and composition,has intrigued the curiosity of many geoscientists.To identify different sources of seismic anisotropy beneath the Alaska region and probe the influence of a geometrically varying subducting slab on mantle dynamics,extensive SWS analyses have been conducted in the past decades.However,the insufficient station and azimuthal coverage,especially in early studies,not only led to some conflicting results but also strongly limited the in-depth investigation of layered anisotropy and the estimation of anisotropy depth.With the completion of the Transportable Array project in Alaska,recent studies have revealed more detailed mantle structures and characteristics based on the dense station coverage and newly collected massive seismic data.In this study,we review significant regional-and continental-scale SWS studies in the Alaska region and conclude the mantle flow fields therein,to understand how a geometrically varying subducting slab alters the regional mantle dynamics.The summarized mantle flow mechanisms are believed to be conducive to the understanding of seismic anisotropy patterns in other subduction zones with a complicated tectonic setting.展开更多
The sluggish kinetics of both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)generate the large overpotential in water electrolysis and thus high-cost hydrogen production.Here,multidimensional nanop...The sluggish kinetics of both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)generate the large overpotential in water electrolysis and thus high-cost hydrogen production.Here,multidimensional nanoporous interpenetrating-phase FeNiZn alloy and FeNi_(3)intermetallic heterostructure is in situ constructed on NiFe foam(FeNiZn/FeNi_(3)@NiFe)by dealloying protocol.Coupling with the eminent synergism among specific constituents and the highly efficient mass transport from integrated porous backbone,FeNiZn/FeNi_(3)@NiFe depicts exceptional bifunctional activities for water splitting with extremely low overpotentials toward OER and HER(η_(1000)=367/245 mV)as well as the robust durability during the 400 h testing in alkaline solution.The as-built water electrolyzer with FeNiZn/FeNi_(3)@NiFe as both anode and cathode exhibits record-high performances for sustainable hydrogen output in terms of much lower cell voltage of 1.759 and 1.919 V to deliver the current density of 500 and 1000 mA cm^(-2)as well long working lives.Density functional theory calculations disclose that the interface interaction between FeNiZn alloy and FeNi_(3)intermetallic generates the modulated electron structure state and optimized intermediate chemisorption,thus diminishing the energy barriers for hydrogen production in water splitting.With the merits of fine performances,scalable fabrication,and low cost,FeNiZn/FeNi_(3)@NiFe holds prospective application potential as the bifunctional electrocatalyst for water splitting.展开更多
Bi-functional electrocatalysts for acid overall water splitting reactions are crucial but still challenging to the development of proton exchange membrane water electrolysis.Herein,an efficient bi-functional catalyst ...Bi-functional electrocatalysts for acid overall water splitting reactions are crucial but still challenging to the development of proton exchange membrane water electrolysis.Herein,an efficient bi-functional catalyst of Ir/MoS_(2) nanoflowers(Ir/MoS_(2) NFs) catalyst was reported for acidic water electrolysis which can be constructed by coupling three-dimensionally interconnected MoS_(2) NFs with ultrafine Ir nanoparticles.A more suitable adsorption ability for the H* and *OOH intermediates was revealed,where the Ir sites were proposed as the main active center and MoS_(2) promoted the charge relocation to electronically modify the interfacial structure.The significant interfacial charge redistribution between the MoS_(2) NFs and the Ir active sites synergistically induced excellent catalytic activity and stability for the water electrolysis reaction.Specifically,the catalyst required overpotentials of 270 and 35 mV to reach a kinetic current density of 10 mA cm^(-2)for OER and HER,respectively,loading on the glass carbon electrode,with high catalytic kinetics,stability,and catalytic efficiency.A two-electrode system constructed by Ir/MoS_(2) NFs drove 10 mA cm^(-2)at a cell voltage of 1.55 V,about 70 mV lower than that of the commercial Pt/C||IrO_(2) system.In addition,partial surface oxidation of Ir nanoparticles to generate high-valent Ir species was also found significant to accelerate OER.The enhanced catalytic performance was attributed to the strong metal-support interaction in the Ir/MoS_(2) NFs catalyst system that changed the electronic structure of Ir metal and promoted the synergistic catalytic effect between Ir and MoS_(2) NFs.The work presented a novel platform of Ir-catalyst for proton exchange membrane water electrolysis.展开更多
Conversion of solar energy into H_(2) by photoelectrochemical(PEC)water splitting is recognized as an ideal way to address the growing energy crisis and environmental issues.In a typical PEC cell,the construction of p...Conversion of solar energy into H_(2) by photoelectrochemical(PEC)water splitting is recognized as an ideal way to address the growing energy crisis and environmental issues.In a typical PEC cell,the construction of photoanodes is crucial to guarantee the high efficiency and stability of PEC reactions,which fundamentally rely on rationally designed semiconductors(as the active materials)and substrates(as the current collectors).In this review work,we start with a brief introduction of the roles of substrates in the PEC process.Then,we provide a systematic overview of representative strategies for the controlled fabrication of photoanodes on rationally designed substrates,including conductive glass,metal,sapphire,silicon,silicon carbide,and flexible substrates.Finally,some prospects concerning the challenges and research directions in this area are proposed.展开更多
Strong coupling between resonantly matched surface plasmons of metals and excitons of quantum emitters results in the formation of new plasmon-exciton hybridized energy states.In plasmon-exciton strong coupling,plasmo...Strong coupling between resonantly matched surface plasmons of metals and excitons of quantum emitters results in the formation of new plasmon-exciton hybridized energy states.In plasmon-exciton strong coupling,plasmonic nanocavities play a significant role due to their ability to confine light in an ultrasmall volume.Additionally,two-dimensional transition metal dichalcogenides(TMDCs) have a significant exciton binding energy and remain stable at ambient conditions,making them an excellent alternative for investigating light-matter interactions.As a result,strong plasmon-exciton coupling has been reported by introducing a single metallic cavity.However,single nanoparticles have lower spatial confinement of electromagnetic fields and limited tunability to match the excitonic resonance.Here,we introduce the concept of catenary-shaped optical fields induced by plasmonic metamaterial cavities to scale the strength of plasmon-exciton coupling.The demonstrated plasmon modes of metallic metamaterial cavities offer high confinement and tunability and can match with the excitons of TMDCs to exhibit a strong coupling regime by tuning either the size of the cavity gap or thickness.The calculated Rabi splitting of Au-MoSe_2 and Au-WSe_2 heterostructures strongly depends on the catenary-like field enhancement induced by the Au cavity,resulting in room-temperature Rabi splitting ranging between 77.86 and 320 me V.These plasmonic metamaterial cavities can pave the way for manipulating excitons in TMDCs and operating active nanophotonic devices at ambient temperature.展开更多
Electrochemical water splitting has long been considered an effective energy conversion technology for trans-ferring intermittent renewable electricity into hydrogen fuel,and the exploration of cost-effective and high...Electrochemical water splitting has long been considered an effective energy conversion technology for trans-ferring intermittent renewable electricity into hydrogen fuel,and the exploration of cost-effective and high-performance electrocatalysts is crucial in making electrolyzed water technology commercially viable.Cobalt phosphide(Co-P)has emerged as a catalyst of high potential owing to its high catalytic activity and durability in water splitting.This paper systematically reviews the latest advances in the development of Co-P-based materials for use in water splitting.The essential effects of P in enhancing the catalytic performance of the hydrogen evolution reaction and oxygen evolution reaction are first outlined.Then,versatile synthesis techniques for Co-P electrocatalysts are summarized,followed by advanced strategies to enhance the electrocatalytic performance of Co-P materials,including heteroatom doping,composite construction,integration with well-conductive sub-strates,and structure control from the viewpoint of experiment.Along with these optimization strategies,the understanding of the inherent mechanism of enhanced catalytic performance is also discussed.Finally,some existing challenges in the development of highly active and stable Co-P-based materials are clarified,and pro-spective directions for prompting the wide commercialization of water electrolysis technology are proposed.展开更多
Hydrogen production from electrochemical water splitting is a promising strategy to generate green energy,which requires the development of efficient and stable electrocatalysts for the hydrogen evolution reaction and...Hydrogen production from electrochemical water splitting is a promising strategy to generate green energy,which requires the development of efficient and stable electrocatalysts for the hydrogen evolution reaction and the oxygen evolution reaction(HER and OER).Ionic liquids(ILs)or poly(ionic liquids)(PILs),containing heteroatoms,metal-based anions,and various structures,have been frequently involved as precursors to prepare electrocatalysts for water splitting.Moreover,ILs/PILs possess high conductivity,wide electrochemical windows,and high thermal and chemical stability,which can be directly applied in the electrocatalysis process with high durability.In this review,we focus on the studies of ILs/PILs-derived electrocatalysts for HER and OER,where ILs/PILs are applied as heteroatom dopants and metal precursors to prepare catalysts or are directly utilized as the electrocatalysts.Due to those attractive properties,IL/PIL-derived electrocatalysts exhibit excellent performance for electrochemical water splitting.All these accomplishments and developments are systematically summarized and thoughtfully discussed.Then,the overall perspectives for the current challenges and future developments of ILs/PILs-derived electrocatalysts are provided.展开更多
In this study,the shear-wave splitting parameters of local seismic events from the source regions of the 2023 Türkiye MW7.7 and MW7.6 doublet earthquakes(event 1 and event 2,respectively)were measured from June 1...In this study,the shear-wave splitting parameters of local seismic events from the source regions of the 2023 Türkiye MW7.7 and MW7.6 doublet earthquakes(event 1 and event 2,respectively)were measured from June 1,2022,to April 25,2023,and their spatiotemporal characteristics were analyzed.The results revealed clear spatial and temporal differences.Spatially,the dominant fast-wave polarization direction at each station shows a strong correlation with the direction of the maximum horizontal principal compressive stress,as characterized by focal mechanism solutions of seismic events(MW≥3.5)near the station.The dominant fast-wave polarization direction and the regional stress field also showed a strong correlation with the intermovement of the Arabian Plate,African Plate,and Anatolian Block.Along the Nurdagi-Pazarcik fault zone,the seismic fault of event 1,stations closer to the middle of the fault where the mainshock occurred exhibited notably greater delay times than stations located towards the ends of the fault and far from the mainshock.In addition,the stations located to the east of the Nurdagi-Pazarcik fault and to the north of the Sürgüfault also exhibited large delay times.The spatial distribution of shear-wave splitting parameters obtained from each station indicates that the upper-crust anisotropy in the source area is mainly controlled by the regional stress field,which is closely related to the state of the block motion.During the seismogenic process of the MW7.7 earthquake,more stress accumulated in the middle of the Nurdagi-Pazarcik fault than at either end of the fault.Under the influence of the MW7.7 and MW7.6 events,the stress that accumulated during the seismogenic process of the earthquake doublet may have migrated towards some areas outside the aftershock intensive area after the earthquakes,and the crustal stress and its adjustment range near the outer stations increased significantly.With the exception of two stations with few effective events,all stations showed a consistent change in shear-wave splitting parameters over time.In particular,each station showed a decreasing trend in delay times after the doublet earthquakes,reflecting the obvious intensification of crustal stress adjustment in the seismogenic zone after the doublet earthquakes.With the occurrence of the earthquake doublet and a large number of aftershocks,the stress accumulated during the seismogenic process of the doublet earthquakes is gradually released,and then the adjustment range of crustal stress is also gradually reduced.展开更多
This paper discusses the two-block large-scale nonconvex optimization problem with general linear constraints.Based on the ideas of splitting and sequential quadratic optimization(SQO),a new feasible descent method fo...This paper discusses the two-block large-scale nonconvex optimization problem with general linear constraints.Based on the ideas of splitting and sequential quadratic optimization(SQO),a new feasible descent method for the discussed problem is proposed.First,we consider the problem of quadratic optimal(QO)approximation associated with the current feasible iteration point,and we split the QO into two small-scale QOs which can be solved in parallel.Second,a feasible descent direction for the problem is obtained and a new SQO-type method is proposed,namely,splitting feasible SQO(SF-SQO)method.Moreover,under suitable conditions,we analyse the global convergence,strong convergence and rate of superlinear convergence of the SF-SQO method.Finally,preliminary numerical experiments regarding the economic dispatch of a power system are carried out,and these show that the SF-SQO method is promising.展开更多
Based on the Bogoliubov-de Gennes equation and the extended McMillan’s Green’s function formalism,we study theoretically the Josephson effect between two d-wave superconductors bridged by a ballistic two-dimensional...Based on the Bogoliubov-de Gennes equation and the extended McMillan’s Green’s function formalism,we study theoretically the Josephson effect between two d-wave superconductors bridged by a ballistic two-dimensional electron gas with both Rashba spin-orbit coupling and Zeeman splitting.We show that due to the interplay of Rashba spin-orbit coupling and Zeeman splitting and d-wave pairing,the current-phase relation in such a heterostructure may exhibit a series of novel features and can change significantly as some relevant parameters are tuned.In particular,anomalous Josephson current may occur at zero phase bias under various different situations if both time reversal symmetry and inversion symmetry of the system are simultaneously broken,which can be realized by tuning some relevant parameters of the system,including the relative orientations and the strengths of the Zeeman field and the spin-orbit field in the bridge region,the relative orientations of the a axes in two superconductor leads,or the relative orientations between the Zeeman field in the bridge region and the a axes in the superconductor leads.We show that both the magnitude and the direction of the anomalous Josephson current may depend sensitively on these relevant parameters.展开更多
Hydrogen gas is widely regarded as an ideal green energy carrier and a potential alternative to fossil fuels for coping with the aggravating energy crisis and environmental pollution.Currently,the vast majority of the...Hydrogen gas is widely regarded as an ideal green energy carrier and a potential alternative to fossil fuels for coping with the aggravating energy crisis and environmental pollution.Currently,the vast majority of the world's hydrogen is produced by reforming fossil fuels;however,this hydrogen-making technology is not sustainable or environmentally friendly because ofits high energy consumption and large carbon emissions.Renewables-driven water splitting(2H_(2)0-2H_(2)+0_(2))becomes an extensively studied scheme for sustain-able hydrogen production.Conventional water electrolysis requires an input voltage higher than 1.23 V and forms a gas mixture of H_(2)/O_(2),which results in high electricity consumption,potential safety hazards,and harmful reactive oxygen species.By virtue of the auxiliary redox mediators(RMs)as the robust H^(+)/e^(-)reservoir,decoupled electrolysis splits water at a much lower potential and evolves O_(2)(H_(2)O+RMS_(ox)-O_(2)+H-RMS_(red))and H_(2)(H-RMS_(red)-H_(2)+RMS_(ox))at separate times,rates,and spaces,thus pro-ducing the puretarget hydrogen gas safely.Decoupled electrolysis has accelerated the development ofwater electrolysis technology for H_(2) production.However,itis still lack of a comprehensive and in-depth review in this field based on different types of RMs.This review highlights the basic principles and critical progress of this emerging water electrolysis mode over the past decade.Several representative examples are then dis-played in detail according to the differences in the RMs.The rational choice and design of RMs have also been emphasized.Subsequently,novel applications of decoupled water splitting are briefly discussed,including the manufacture of valuable chemicals,Cl_(2) production,pollutant degradation,and other half-reactions in artificial photosynthesis.Finally,thekey characteristics and disadvantages of each type of mediator are sum-marized in depth.In addition,we present an outlook for future directions in decoupled water splitting.Thus,the flexibility in the design of mediators provides huge space for improving this electrochemical technology.@2024 Science Press and Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by ELSEVIER B.V.and Science Press.All rights reserved.展开更多
The development of highly active,stable and inexpensive electrocatalysts for hydrogen production by defects and morphology engineering remains a great challenge.Herein,S vacancies-rich Ni_(3)S_(2)@Cu_(2)S nan-otube he...The development of highly active,stable and inexpensive electrocatalysts for hydrogen production by defects and morphology engineering remains a great challenge.Herein,S vacancies-rich Ni_(3)S_(2)@Cu_(2)S nan-otube heterojunction arrays were in-situ grown on copper foam(V_(s)-Ni_(3)S_(2)@V_(s)-Cu_(2)S NHAs/CF)for efficient electrocatalytic overall water splitting.With the merits of nanotube arrays and efficient electronic mod-ulation drived by the OD vacancy defect and 2D heterojunction defect,the resultant V_(s)-Ni_(3)S_(2)@V_(s)-Cu_(2)S NHAs/CF electrocatalyst exhibits excellent electrocatalytic activity with a low overpotential of 47 mV for the hydrogen evolution reaction(HER)at 10 mA cm^(-2) current density,and 263 mV for the oxygen evolution reaction(OER)at 50 mA cm^(-2) current density,as well as a cell voltage of 1.48 V at 10 mA cm^(-2).Moreover,the nanotube heterojunction arrays endows V_(s)-Ni_(3)S_(2)@V_(s)-Cu_(2)S NHAs/CF with outstanding stability in long-term catalytic processes,as confirmed by the continuous chronopotentiom-etry tests at current densities of 10 mA cm^(-2) for 100 h.展开更多
Cobalt-based electrocatalysts take advantage of potentially harmonizable microstructure and flexible coupling effects compared to commercial noble metal-based catalytic materials.However,conventional water electrolysi...Cobalt-based electrocatalysts take advantage of potentially harmonizable microstructure and flexible coupling effects compared to commercial noble metal-based catalytic materials.However,conventional water electrolysis systems based on cobalt-based monofunctional hydrogen evolution reaction(HER)or oxygen evolution reaction(OER)catalysts have certain shortcomings in terms of resource utilization and universality.In contrast,cobalt-based bifunctional catalysts(CBCs)have attracted much attention in recent years for overall water splitting systems because of their practicality and reduced preparation cost of electrolyzer.This review aims to address the latest development in CBCs for total hydrolysis.The main modification strategies of CBCs are systematically classified in water electrolysis to provide an overview of how to regulate their morphology and electronic configuration.Then,the catalytic performance of CBCs in total-hydrolysis is summarized according to the types of cobalt-based phosphides,sulfides and oxides,and the mechanism of strengthened electrocatalytic ability is emphasized through combining experiments and theoretical calculations.Future efforts are finally suggested to focus on exploring the dynamic conversion of reaction intermediates and building near-industrial CBCs,designing advanced CBC materials through micro-modulation,and addressing commercial applications.展开更多
Hydrogen(H_(2)) has been regarded as a promising alternative to fossil-fuel energy.Green H_(2) produced via water electrolysis(WE)powered by renewable energy could achieve a zero-carbon footprint.Considerable attentio...Hydrogen(H_(2)) has been regarded as a promising alternative to fossil-fuel energy.Green H_(2) produced via water electrolysis(WE)powered by renewable energy could achieve a zero-carbon footprint.Considerable attention has been focused on developing highly active catalysts to facilitate the reaction kinetics and improve the energy efficiency of WE.However,the stability of the electrocatalysts hampers the commercial viability of WE.Few studies have elucidated the origin of catalyst degradation.In this review,we first discuss the WE mechanism,including anodic oxygen evolution reaction(OER)and cathodic hydrogen evolution reaction(HER).Then,we provide strategies used to enhance the stability of electrocatalysts.After that,the deactivation mechanisms of the typical commercialized HER and OER catalysts,including Pt,Ni,RuO_(2),and IrO_(2),are summarized.Finally,the influence of fluctuating energy on catalyst degradation is highlighted and in situ characterization methodologies for understanding the dynamic deactivation processes are described.展开更多
Industrial water splitting has long been suppressed by the sluggish kinetics of the oxygen evolution reaction(OER),which requires a catalyst to be efficient.Herein,we propose a molecular-level proton acceptor strategy...Industrial water splitting has long been suppressed by the sluggish kinetics of the oxygen evolution reaction(OER),which requires a catalyst to be efficient.Herein,we propose a molecular-level proton acceptor strategy to produce an efficient OER catalyst that can boost industrial-scale water splitting.Molecular-level phosphate(-PO_(4))group is introduced to modify the surface of PrBa_(0.5)Ca_(0.5)Co_(2)O_(5)+δ(PBCC).The achieved catalyst(PO_(4)-PBCC)exhibits significantly enhanced catalytic performance in alkaline media.Based on the X-ray absorption spectroscopy results and density functional theory(DFT)calculations,the PO_(4)on the surface,which is regarded as the Lewis base,is the key factor to overcome the kinetic limitation of the proton transfer process during the OER.The use of the catalyst in a membrane electrode assembly(MEA)is further evaluated for industrial-scale water splitting,and it only needs a low voltage of 1.66 V to achieve a large current density of 1 A cm^(-2).This work provides a new molecular-level strategy to develop highly efficient OER electrocatalysts for industrial applications.展开更多
Electrocatalytic water splitting seems to be an efficient strategy to deal with increasingly serious environmental problems and energy crises but still suffers from the lack of stable and efficient electrocatalysts.De...Electrocatalytic water splitting seems to be an efficient strategy to deal with increasingly serious environmental problems and energy crises but still suffers from the lack of stable and efficient electrocatalysts.Designing practical electrocatalysts by introducing defect engineering,such as hybrid structure,surface vacancies,functional modification,and structural distortions,is proven to be a dependable solution for fabricating electrocatalysts with high catalytic activities,robust stability,and good practicability.This review is an overview of some relevant reports about the effects of defect engineering on the electrocatalytic water splitting performance of electrocatalysts.In detail,the types of defects,the preparation and characterization methods,and catalytic performances of electrocatalysts are presented,emphasizing the effects of the introduced defects on the electronic structures of electrocatalysts and the optimization of the intermediates'adsorption energy throughout the review.Finally,the existing challenges and personal perspectives of possible strategies for enhancing the catalytic performances of electrocatalysts are proposed.An in-depth understanding of the effects of defect engineering on the catalytic performance of electrocatalysts will light the way to design high-efficiency electrocatalysts for water splitting and other possible applications.展开更多
基金supported by the National Natural Science Foundation of China(No.22209126)。
文摘Urea oxidation reaction(UOR) has been selected as substitution for oxygen evolution reaction ascribing to its low thermodynamic voltage as well as utilization of nickel as electrocatalyst.Herein,we report the formation of nickel single atoms(Ni-SAs) as exceptional bifunctional electrocatalyst toward UOR and hydrogen evolution reaction(HER) in urea-assisted water splitting.In UOR catalysis,Ni-SAs perform a superior catalytic performance than Ni-NP/NC and Pt/C ascribing to the formation of HOO-Ni-N_(4) structure evidenced by in-situ Raman spectroscopy,corresponding to a boosted mass activity by 175-fold at 1.4 V vs.RHE than Ni-NP/NC.Furthermore,Ni-SAs requires only 450 mV overpotential to obtain HER current density of 500 mA cm^(-2).136 mA cm^(-2) is achieved in urea-assisted water splitting at1.7 V for Ni-SAs,boosted by 5.7 times than Pt/C-IrO_(2) driven water splitting.
基金financially supported from the National Natural Science Foundation of China(No.52201254)the Natural Science Foundation of Shandong Province,China(Nos.ZR2023ME155,ZR2020MB090,ZR2020QE012,ZR2020MB027)+1 种基金the Project of“20 Items of University”of Jinan,China(No.202228046)the Taishan Scholar Project of Shandong Province,China(No.tsqn202306226)。
文摘The development of efficient nonprecious bifunctional electrocatalysts for water electrolysis is crucial to enhance the sluggish kinetics of the oxygen evolution reaction(OER)and hydrogen evolution reaction(HER).A self-supporting,multiscale porous NiFeZn/NiZn-Ni catalyst with a triple interface heterojunction on nickel foam(NF)(NiFeZn/NiZn-Ni/NF)was in-situ fabricated using an electroplating-annealing-etching strategy.The unique multiinterface engineering and three-dimensional porous scaffold significantly modify the mass transport and electron interaction,resulting in superior bifunctional electrocatalytic performance for water splitting.The NiFeZn/NiZn-Ni/NF catalyst demonstrates low overpotentials of 187 m V for HER and 320 mV for OER at a current density of 600 mA/cm^(2),along with high durability over 150 h in alkaline solution.Furthermore,an electrolytic cell assembled with NiFeZn/NiZn-Ni/NF as both the cathode and anode achieves the current densities of 600 and 1000 m A/cm^(2) at cell voltages of 1.796 and 1.901 V,respectively,maintaining the high stability at 50 mA/cm^(2) for over 100 h.These findings highlight the potential of NiFeZn/NiZn-Ni/NF as a cost-effective and highly efficient bifunctional electrocatalyst for overall water splitting.
基金supports from the Zhejiang Provincial Natural Science Foundation(No.LR22E070001)the National Natural Science Foundation of China(Nos.12275239 and 11975205)+1 种基金the Guangdong Basic and Applied Basic Research Foundation(No.2020B1515120048)the Fundamental Research Funds of Zhejiang Sci-Tech University(No.23062096-Y).
文摘This work reports the use of defect engineering and carbon supporting to achieve metal-doped phosphides with high activities and stabilities for the hydrogen evolution reaction(HER)and the oxygen evolution reaction(OER)in alkaline media.Specifically,the nitrogen-doped carbon nanofiber-supported Ni-doped CoP_(3) with rich P defects(Pv·)on the carbon cloth(p-NiCoP/NCFs@CC)is synthesized through a plasma-assisted phosphorization method.The p-NiCoP/NCFs@CC is an efficient and stable catalyst for the HER and the OER.It only needs overpotentials of 107 and 306 mV to drive 100 mA cm^(-2) for the HER and the OER,respectively.Its catalytic activities are higher than those of other catalysts reported recently.The high activities of the p-NiCoP/NCFs@CC mainly arise from its peculiar structural features.The density functional theory calculation indicates that the Pv·richness,the Ni doping,and the carbon supporting can optimize the adsorption of the H atoms at the catalyst surface and promote the strong electronic couplings between the carbon nanofiber-supported p-NiCoP with the surface oxide layer formed during the OER process.This gives the p-NiCoP/NCFs@CC with the high activities for the HER and the OER.When used in alkaline water electrolyzers,the p-NiCoP/NCFs@CC shows the superior activity and excellent stability for overall water splitting.
基金supported by the National Key Research and Development Program of China(2022YFE0101600)the National Natural Science Foundation of China(U23A20117)+2 种基金the Natural Science Foundation of Jiangsu Province(BK20220002,BE2022024)the Leading Talents Program of Zhejiang Province(2024C03223)Topnotch Academic Programs Project of Jiangsu Higher Education Institutions(TAPP).
文摘A two-stage catalytic membrane reactor(CMR)that couples CO_(2) splitting with methane oxidation reactions was constructed based on an oxygen-permeable perovskite asymmetric membrane.The asymmetric membrane comprises a dense SrFe_(0.9)Ta_(0.1)O_(3-σ)(SFT)separation layer and a porous Sr_(0.9)(Fe_(0.9)Ta_(0.1))_(0.9)Cu_(0.1)O_(3-σ)(SFTC)catalytic layer.In thefirst stage reactor,a CO_(2) splitting reaction(CDS:2CO_(2)→2CO+O_(2))occurs at the SFTC catalytic layer.Subsequently,the O_(2) product is selectively extracted through the SFT separation layer to the permeated side for the methane combustion reaction(MCR),which provides an extremely low oxygen partial pressure to enhance the oxygen extraction.In the second stage,a Sr_(0.9)(Fe_(0.9)Ta_(0.1))_(0.9)Ni_(0.1)O_(3-σ)(SFTN)catalyst is employed to reform the products derived from MCR.The two-stage CMR design results in a remarkable 35.4%CO_(2) conversion for CDS at 900℃.The two-stage CMR was extended to a hollowfiber configuration combining with solar irradiation.The solar-assisted two-stage CMR can operate stably for over 50 h with a high hydrogen yield of 18.1 mL min^(-1) cm^(-2).These results provide a novel strategy for reducing CO_(2) emissions,suggesting potential avenues for the design of the high-performance CMRs and catalysts based on perovskite oxides in the future.
基金supported by the Outstanding Youth Project of Natural Science Foundation of Heilongjiang(YQ2023D006).
文摘Shear wave splitting(SWS)is regarded as the most effective geophysical method to delineate mantle flow fields by detecting seismic azimuthal anisotropy in the earth's upper mantle,especially in tectonically active regions such as subduction zones.The Aleutian-Alaska subduction zone has a convergence rate of approximately 50 mm/yr,with a trench length reaching nearly 2800 km.Such a long subduction zone has led to intensive continental deformation and numerous strong earthquakes in southern and central Alaska,while northern Alaska is relatively inactive.The sharp contrast makes Alaska a favorable locale to investigate the impact of subduction on mantle dynamics.Moreover,the uniqueness of this subduction zone,including the unusual subducting type,varying slab geometry,and atypical magmatic activity and composition,has intrigued the curiosity of many geoscientists.To identify different sources of seismic anisotropy beneath the Alaska region and probe the influence of a geometrically varying subducting slab on mantle dynamics,extensive SWS analyses have been conducted in the past decades.However,the insufficient station and azimuthal coverage,especially in early studies,not only led to some conflicting results but also strongly limited the in-depth investigation of layered anisotropy and the estimation of anisotropy depth.With the completion of the Transportable Array project in Alaska,recent studies have revealed more detailed mantle structures and characteristics based on the dense station coverage and newly collected massive seismic data.In this study,we review significant regional-and continental-scale SWS studies in the Alaska region and conclude the mantle flow fields therein,to understand how a geometrically varying subducting slab alters the regional mantle dynamics.The summarized mantle flow mechanisms are believed to be conducive to the understanding of seismic anisotropy patterns in other subduction zones with a complicated tectonic setting.
基金supported by National Science Foundation of China(52201254)Shandong Province(ZR2020MB090,ZR2020QE012)the project of“20 Items of University”of Jinan(202228046)。
文摘The sluggish kinetics of both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)generate the large overpotential in water electrolysis and thus high-cost hydrogen production.Here,multidimensional nanoporous interpenetrating-phase FeNiZn alloy and FeNi_(3)intermetallic heterostructure is in situ constructed on NiFe foam(FeNiZn/FeNi_(3)@NiFe)by dealloying protocol.Coupling with the eminent synergism among specific constituents and the highly efficient mass transport from integrated porous backbone,FeNiZn/FeNi_(3)@NiFe depicts exceptional bifunctional activities for water splitting with extremely low overpotentials toward OER and HER(η_(1000)=367/245 mV)as well as the robust durability during the 400 h testing in alkaline solution.The as-built water electrolyzer with FeNiZn/FeNi_(3)@NiFe as both anode and cathode exhibits record-high performances for sustainable hydrogen output in terms of much lower cell voltage of 1.759 and 1.919 V to deliver the current density of 500 and 1000 mA cm^(-2)as well long working lives.Density functional theory calculations disclose that the interface interaction between FeNiZn alloy and FeNi_(3)intermetallic generates the modulated electron structure state and optimized intermediate chemisorption,thus diminishing the energy barriers for hydrogen production in water splitting.With the merits of fine performances,scalable fabrication,and low cost,FeNiZn/FeNi_(3)@NiFe holds prospective application potential as the bifunctional electrocatalyst for water splitting.
基金supported by the National Natural Science Foundation of China (21972124, 22272148)the Priority Academic Program Development of Jiangsu Higher Education Institution。
文摘Bi-functional electrocatalysts for acid overall water splitting reactions are crucial but still challenging to the development of proton exchange membrane water electrolysis.Herein,an efficient bi-functional catalyst of Ir/MoS_(2) nanoflowers(Ir/MoS_(2) NFs) catalyst was reported for acidic water electrolysis which can be constructed by coupling three-dimensionally interconnected MoS_(2) NFs with ultrafine Ir nanoparticles.A more suitable adsorption ability for the H* and *OOH intermediates was revealed,where the Ir sites were proposed as the main active center and MoS_(2) promoted the charge relocation to electronically modify the interfacial structure.The significant interfacial charge redistribution between the MoS_(2) NFs and the Ir active sites synergistically induced excellent catalytic activity and stability for the water electrolysis reaction.Specifically,the catalyst required overpotentials of 270 and 35 mV to reach a kinetic current density of 10 mA cm^(-2)for OER and HER,respectively,loading on the glass carbon electrode,with high catalytic kinetics,stability,and catalytic efficiency.A two-electrode system constructed by Ir/MoS_(2) NFs drove 10 mA cm^(-2)at a cell voltage of 1.55 V,about 70 mV lower than that of the commercial Pt/C||IrO_(2) system.In addition,partial surface oxidation of Ir nanoparticles to generate high-valent Ir species was also found significant to accelerate OER.The enhanced catalytic performance was attributed to the strong metal-support interaction in the Ir/MoS_(2) NFs catalyst system that changed the electronic structure of Ir metal and promoted the synergistic catalytic effect between Ir and MoS_(2) NFs.The work presented a novel platform of Ir-catalyst for proton exchange membrane water electrolysis.
基金Natural Science Foundation of Zhejiang Province,Grant/Award Number:LY23E020002National Natural Science Foundation of China,Grant/Award Number:52272085 and 51972178+1 种基金Natural Science Foundation of Ningbo,Grant/Award Number:2021J145China Postdoctoral Science Foundation,Grant/Award Number:2020M681966。
文摘Conversion of solar energy into H_(2) by photoelectrochemical(PEC)water splitting is recognized as an ideal way to address the growing energy crisis and environmental issues.In a typical PEC cell,the construction of photoanodes is crucial to guarantee the high efficiency and stability of PEC reactions,which fundamentally rely on rationally designed semiconductors(as the active materials)and substrates(as the current collectors).In this review work,we start with a brief introduction of the roles of substrates in the PEC process.Then,we provide a systematic overview of representative strategies for the controlled fabrication of photoanodes on rationally designed substrates,including conductive glass,metal,sapphire,silicon,silicon carbide,and flexible substrates.Finally,some prospects concerning the challenges and research directions in this area are proposed.
基金supported by the Australian Research Council (DP200101353)。
文摘Strong coupling between resonantly matched surface plasmons of metals and excitons of quantum emitters results in the formation of new plasmon-exciton hybridized energy states.In plasmon-exciton strong coupling,plasmonic nanocavities play a significant role due to their ability to confine light in an ultrasmall volume.Additionally,two-dimensional transition metal dichalcogenides(TMDCs) have a significant exciton binding energy and remain stable at ambient conditions,making them an excellent alternative for investigating light-matter interactions.As a result,strong plasmon-exciton coupling has been reported by introducing a single metallic cavity.However,single nanoparticles have lower spatial confinement of electromagnetic fields and limited tunability to match the excitonic resonance.Here,we introduce the concept of catenary-shaped optical fields induced by plasmonic metamaterial cavities to scale the strength of plasmon-exciton coupling.The demonstrated plasmon modes of metallic metamaterial cavities offer high confinement and tunability and can match with the excitons of TMDCs to exhibit a strong coupling regime by tuning either the size of the cavity gap or thickness.The calculated Rabi splitting of Au-MoSe_2 and Au-WSe_2 heterostructures strongly depends on the catenary-like field enhancement induced by the Au cavity,resulting in room-temperature Rabi splitting ranging between 77.86 and 320 me V.These plasmonic metamaterial cavities can pave the way for manipulating excitons in TMDCs and operating active nanophotonic devices at ambient temperature.
基金the National Natural Science Foundation of China(21962008)Yunnan Province Excellent Youth Fund Project(202001AW070005)+1 种基金Candidate Talents Training Fund of Yunnan Province(2017PY269SQ,2018HB007)Yunnan Ten Thousand Talents Plan Young&Elite Talents Project(YNWR-QNBJ-2018-346).
文摘Electrochemical water splitting has long been considered an effective energy conversion technology for trans-ferring intermittent renewable electricity into hydrogen fuel,and the exploration of cost-effective and high-performance electrocatalysts is crucial in making electrolyzed water technology commercially viable.Cobalt phosphide(Co-P)has emerged as a catalyst of high potential owing to its high catalytic activity and durability in water splitting.This paper systematically reviews the latest advances in the development of Co-P-based materials for use in water splitting.The essential effects of P in enhancing the catalytic performance of the hydrogen evolution reaction and oxygen evolution reaction are first outlined.Then,versatile synthesis techniques for Co-P electrocatalysts are summarized,followed by advanced strategies to enhance the electrocatalytic performance of Co-P materials,including heteroatom doping,composite construction,integration with well-conductive sub-strates,and structure control from the viewpoint of experiment.Along with these optimization strategies,the understanding of the inherent mechanism of enhanced catalytic performance is also discussed.Finally,some existing challenges in the development of highly active and stable Co-P-based materials are clarified,and pro-spective directions for prompting the wide commercialization of water electrolysis technology are proposed.
基金supported by the Natural Science Founda-tion of Chongqing(cstc2021jcyj-msxmX0420)Natural Science Foundation of Sichuan(2023NSFSC0088)。
文摘Hydrogen production from electrochemical water splitting is a promising strategy to generate green energy,which requires the development of efficient and stable electrocatalysts for the hydrogen evolution reaction and the oxygen evolution reaction(HER and OER).Ionic liquids(ILs)or poly(ionic liquids)(PILs),containing heteroatoms,metal-based anions,and various structures,have been frequently involved as precursors to prepare electrocatalysts for water splitting.Moreover,ILs/PILs possess high conductivity,wide electrochemical windows,and high thermal and chemical stability,which can be directly applied in the electrocatalysis process with high durability.In this review,we focus on the studies of ILs/PILs-derived electrocatalysts for HER and OER,where ILs/PILs are applied as heteroatom dopants and metal precursors to prepare catalysts or are directly utilized as the electrocatalysts.Due to those attractive properties,IL/PIL-derived electrocatalysts exhibit excellent performance for electrochemical water splitting.All these accomplishments and developments are systematically summarized and thoughtfully discussed.Then,the overall perspectives for the current challenges and future developments of ILs/PILs-derived electrocatalysts are provided.
基金supported by the National Natural Science Foundation of China(Nos.42074053 and 42374079)the Fundamental Research Funds from the Institute of Geophysics,China Earthquake Administration(Nos.DQJB19B30 and JY2022Z02).
文摘In this study,the shear-wave splitting parameters of local seismic events from the source regions of the 2023 Türkiye MW7.7 and MW7.6 doublet earthquakes(event 1 and event 2,respectively)were measured from June 1,2022,to April 25,2023,and their spatiotemporal characteristics were analyzed.The results revealed clear spatial and temporal differences.Spatially,the dominant fast-wave polarization direction at each station shows a strong correlation with the direction of the maximum horizontal principal compressive stress,as characterized by focal mechanism solutions of seismic events(MW≥3.5)near the station.The dominant fast-wave polarization direction and the regional stress field also showed a strong correlation with the intermovement of the Arabian Plate,African Plate,and Anatolian Block.Along the Nurdagi-Pazarcik fault zone,the seismic fault of event 1,stations closer to the middle of the fault where the mainshock occurred exhibited notably greater delay times than stations located towards the ends of the fault and far from the mainshock.In addition,the stations located to the east of the Nurdagi-Pazarcik fault and to the north of the Sürgüfault also exhibited large delay times.The spatial distribution of shear-wave splitting parameters obtained from each station indicates that the upper-crust anisotropy in the source area is mainly controlled by the regional stress field,which is closely related to the state of the block motion.During the seismogenic process of the MW7.7 earthquake,more stress accumulated in the middle of the Nurdagi-Pazarcik fault than at either end of the fault.Under the influence of the MW7.7 and MW7.6 events,the stress that accumulated during the seismogenic process of the earthquake doublet may have migrated towards some areas outside the aftershock intensive area after the earthquakes,and the crustal stress and its adjustment range near the outer stations increased significantly.With the exception of two stations with few effective events,all stations showed a consistent change in shear-wave splitting parameters over time.In particular,each station showed a decreasing trend in delay times after the doublet earthquakes,reflecting the obvious intensification of crustal stress adjustment in the seismogenic zone after the doublet earthquakes.With the occurrence of the earthquake doublet and a large number of aftershocks,the stress accumulated during the seismogenic process of the doublet earthquakes is gradually released,and then the adjustment range of crustal stress is also gradually reduced.
基金supported by the National Natural Science Foundation of China(12171106)the Natural Science Foundation of Guangxi Province(2020GXNSFDA238017 and 2018GXNSFFA281007)the Shanghai Sailing Program(21YF1430300)。
文摘This paper discusses the two-block large-scale nonconvex optimization problem with general linear constraints.Based on the ideas of splitting and sequential quadratic optimization(SQO),a new feasible descent method for the discussed problem is proposed.First,we consider the problem of quadratic optimal(QO)approximation associated with the current feasible iteration point,and we split the QO into two small-scale QOs which can be solved in parallel.Second,a feasible descent direction for the problem is obtained and a new SQO-type method is proposed,namely,splitting feasible SQO(SF-SQO)method.Moreover,under suitable conditions,we analyse the global convergence,strong convergence and rate of superlinear convergence of the SF-SQO method.Finally,preliminary numerical experiments regarding the economic dispatch of a power system are carried out,and these show that the SF-SQO method is promising.
文摘Based on the Bogoliubov-de Gennes equation and the extended McMillan’s Green’s function formalism,we study theoretically the Josephson effect between two d-wave superconductors bridged by a ballistic two-dimensional electron gas with both Rashba spin-orbit coupling and Zeeman splitting.We show that due to the interplay of Rashba spin-orbit coupling and Zeeman splitting and d-wave pairing,the current-phase relation in such a heterostructure may exhibit a series of novel features and can change significantly as some relevant parameters are tuned.In particular,anomalous Josephson current may occur at zero phase bias under various different situations if both time reversal symmetry and inversion symmetry of the system are simultaneously broken,which can be realized by tuning some relevant parameters of the system,including the relative orientations and the strengths of the Zeeman field and the spin-orbit field in the bridge region,the relative orientations of the a axes in two superconductor leads,or the relative orientations between the Zeeman field in the bridge region and the a axes in the superconductor leads.We show that both the magnitude and the direction of the anomalous Josephson current may depend sensitively on these relevant parameters.
基金the financial support from the National Natural Science Foundation of China(52002146).
文摘Hydrogen gas is widely regarded as an ideal green energy carrier and a potential alternative to fossil fuels for coping with the aggravating energy crisis and environmental pollution.Currently,the vast majority of the world's hydrogen is produced by reforming fossil fuels;however,this hydrogen-making technology is not sustainable or environmentally friendly because ofits high energy consumption and large carbon emissions.Renewables-driven water splitting(2H_(2)0-2H_(2)+0_(2))becomes an extensively studied scheme for sustain-able hydrogen production.Conventional water electrolysis requires an input voltage higher than 1.23 V and forms a gas mixture of H_(2)/O_(2),which results in high electricity consumption,potential safety hazards,and harmful reactive oxygen species.By virtue of the auxiliary redox mediators(RMs)as the robust H^(+)/e^(-)reservoir,decoupled electrolysis splits water at a much lower potential and evolves O_(2)(H_(2)O+RMS_(ox)-O_(2)+H-RMS_(red))and H_(2)(H-RMS_(red)-H_(2)+RMS_(ox))at separate times,rates,and spaces,thus pro-ducing the puretarget hydrogen gas safely.Decoupled electrolysis has accelerated the development ofwater electrolysis technology for H_(2) production.However,itis still lack of a comprehensive and in-depth review in this field based on different types of RMs.This review highlights the basic principles and critical progress of this emerging water electrolysis mode over the past decade.Several representative examples are then dis-played in detail according to the differences in the RMs.The rational choice and design of RMs have also been emphasized.Subsequently,novel applications of decoupled water splitting are briefly discussed,including the manufacture of valuable chemicals,Cl_(2) production,pollutant degradation,and other half-reactions in artificial photosynthesis.Finally,thekey characteristics and disadvantages of each type of mediator are sum-marized in depth.In addition,we present an outlook for future directions in decoupled water splitting.Thus,the flexibility in the design of mediators provides huge space for improving this electrochemical technology.@2024 Science Press and Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by ELSEVIER B.V.and Science Press.All rights reserved.
基金supported by the National Natural Science Foundation of China under Grant No.52072196,52002200,52102106,52202262,22379081,22379080Major Basic Research Program of Natural Science Foundation of Shandong Province under Grant No.ZR2020zD09the Natural Science Foundation of Shandong Province under Grant No.ZR2020QE063,ZR202108180009,ZR2023QE059.
文摘The development of highly active,stable and inexpensive electrocatalysts for hydrogen production by defects and morphology engineering remains a great challenge.Herein,S vacancies-rich Ni_(3)S_(2)@Cu_(2)S nan-otube heterojunction arrays were in-situ grown on copper foam(V_(s)-Ni_(3)S_(2)@V_(s)-Cu_(2)S NHAs/CF)for efficient electrocatalytic overall water splitting.With the merits of nanotube arrays and efficient electronic mod-ulation drived by the OD vacancy defect and 2D heterojunction defect,the resultant V_(s)-Ni_(3)S_(2)@V_(s)-Cu_(2)S NHAs/CF electrocatalyst exhibits excellent electrocatalytic activity with a low overpotential of 47 mV for the hydrogen evolution reaction(HER)at 10 mA cm^(-2) current density,and 263 mV for the oxygen evolution reaction(OER)at 50 mA cm^(-2) current density,as well as a cell voltage of 1.48 V at 10 mA cm^(-2).Moreover,the nanotube heterojunction arrays endows V_(s)-Ni_(3)S_(2)@V_(s)-Cu_(2)S NHAs/CF with outstanding stability in long-term catalytic processes,as confirmed by the continuous chronopotentiom-etry tests at current densities of 10 mA cm^(-2) for 100 h.
基金financially supported by the National Natural Science Foundation of China(51572166,52102070)the Program for Professor of Special Appointment at Shanghai Institutions of Higher Learning(GZ2020012)+4 种基金the Key Research Project of Zhejiang Laboratory(2021PE0AC02)the China Postdoctoral Science Foundation(2021M702073)BAJC R&D Fund Projects(BA23011)Australian Research Council Future Fellowships(FT230100436)the Shanghai Technical Service Center for Advanced Ceramics Structure Design and Precision Manufacturing(20DZ2294000)。
文摘Cobalt-based electrocatalysts take advantage of potentially harmonizable microstructure and flexible coupling effects compared to commercial noble metal-based catalytic materials.However,conventional water electrolysis systems based on cobalt-based monofunctional hydrogen evolution reaction(HER)or oxygen evolution reaction(OER)catalysts have certain shortcomings in terms of resource utilization and universality.In contrast,cobalt-based bifunctional catalysts(CBCs)have attracted much attention in recent years for overall water splitting systems because of their practicality and reduced preparation cost of electrolyzer.This review aims to address the latest development in CBCs for total hydrolysis.The main modification strategies of CBCs are systematically classified in water electrolysis to provide an overview of how to regulate their morphology and electronic configuration.Then,the catalytic performance of CBCs in total-hydrolysis is summarized according to the types of cobalt-based phosphides,sulfides and oxides,and the mechanism of strengthened electrocatalytic ability is emphasized through combining experiments and theoretical calculations.Future efforts are finally suggested to focus on exploring the dynamic conversion of reaction intermediates and building near-industrial CBCs,designing advanced CBC materials through micro-modulation,and addressing commercial applications.
基金financially supported by the Science Foundation of Donghai Laboratory (Grant No.DH-2022ZY0010)the R&D Project of State Grid Corporation of China (No.5108-202218280A-2-439-XG).
文摘Hydrogen(H_(2)) has been regarded as a promising alternative to fossil-fuel energy.Green H_(2) produced via water electrolysis(WE)powered by renewable energy could achieve a zero-carbon footprint.Considerable attention has been focused on developing highly active catalysts to facilitate the reaction kinetics and improve the energy efficiency of WE.However,the stability of the electrocatalysts hampers the commercial viability of WE.Few studies have elucidated the origin of catalyst degradation.In this review,we first discuss the WE mechanism,including anodic oxygen evolution reaction(OER)and cathodic hydrogen evolution reaction(HER).Then,we provide strategies used to enhance the stability of electrocatalysts.After that,the deactivation mechanisms of the typical commercialized HER and OER catalysts,including Pt,Ni,RuO_(2),and IrO_(2),are summarized.Finally,the influence of fluctuating energy on catalyst degradation is highlighted and in situ characterization methodologies for understanding the dynamic deactivation processes are described.
基金supported by the National Natural Sci-ence Foundation of China(22272081),Jiangsu Provincial Specially Appointed Professors Foundation.
文摘Industrial water splitting has long been suppressed by the sluggish kinetics of the oxygen evolution reaction(OER),which requires a catalyst to be efficient.Herein,we propose a molecular-level proton acceptor strategy to produce an efficient OER catalyst that can boost industrial-scale water splitting.Molecular-level phosphate(-PO_(4))group is introduced to modify the surface of PrBa_(0.5)Ca_(0.5)Co_(2)O_(5)+δ(PBCC).The achieved catalyst(PO_(4)-PBCC)exhibits significantly enhanced catalytic performance in alkaline media.Based on the X-ray absorption spectroscopy results and density functional theory(DFT)calculations,the PO_(4)on the surface,which is regarded as the Lewis base,is the key factor to overcome the kinetic limitation of the proton transfer process during the OER.The use of the catalyst in a membrane electrode assembly(MEA)is further evaluated for industrial-scale water splitting,and it only needs a low voltage of 1.66 V to achieve a large current density of 1 A cm^(-2).This work provides a new molecular-level strategy to develop highly efficient OER electrocatalysts for industrial applications.
基金National Natural Science Foundation of China,Grant/Award Number:52271200Scientific and Technological Innovation Foundation of Foshan,Grant/Award Number:BK20BE009+1 种基金the Fundamental Research Funds for the Central Universities,Grant/Award Number:FRF-TP-18-079A1Guangdong Basic and Applied Basic Research Foundation,Grant/Award Number:2020A1515110460,ORCID:http://orcid.org/0000-0002-0870-2248。
文摘Electrocatalytic water splitting seems to be an efficient strategy to deal with increasingly serious environmental problems and energy crises but still suffers from the lack of stable and efficient electrocatalysts.Designing practical electrocatalysts by introducing defect engineering,such as hybrid structure,surface vacancies,functional modification,and structural distortions,is proven to be a dependable solution for fabricating electrocatalysts with high catalytic activities,robust stability,and good practicability.This review is an overview of some relevant reports about the effects of defect engineering on the electrocatalytic water splitting performance of electrocatalysts.In detail,the types of defects,the preparation and characterization methods,and catalytic performances of electrocatalysts are presented,emphasizing the effects of the introduced defects on the electronic structures of electrocatalysts and the optimization of the intermediates'adsorption energy throughout the review.Finally,the existing challenges and personal perspectives of possible strategies for enhancing the catalytic performances of electrocatalysts are proposed.An in-depth understanding of the effects of defect engineering on the catalytic performance of electrocatalysts will light the way to design high-efficiency electrocatalysts for water splitting and other possible applications.