The electrocatalytic reduction of carbon dioxide(CO_(2)RR)to valuable products presents a promising solution for addressing global warming and enhancing renewable energy storage.Herein,we construct a novel Ni_(3)ZnC_(...The electrocatalytic reduction of carbon dioxide(CO_(2)RR)to valuable products presents a promising solution for addressing global warming and enhancing renewable energy storage.Herein,we construct a novel Ni_(3)ZnC_(0.7)/Ni heterostructure electrocatalyst,using an electrospinning strategy to prepare metal particles uniformly loaded on nitrogen-doped carbon nanofibers(CNFs).The incorporation of zinc(Zn)into nickel(Ni)catalysts optimizes the adsorption of CO_(2)intermediates,balancing the strong binding affinity of Ni with the comparatively weaker affinity of Zn,which mitigates over-activation.The electron transfer within the Ni_(3)ZnC_(0.7)/Ni@CNFs system facilitates rapid electron transfer to CO_(2),resulting in great performance with a faradaic efficiency for CO(FECO)of nearly 90%at−0.86 V versus the reversible hydrogen electrode(RHE)and a current density of 17.51 mA cm^(−2)at−1.16 V versus RHE in an H-cell.Furthermore,the catalyst exhibits remarkable stability,maintaining its crystal structure and morphology after 50 h of electrolysis.Moreover,the Ni_(3)ZnC_(0.7)/Ni@CNFs is used in the membrane electrode assembly reactor(MEA),which can achieve a FECO of 91.7%at a cell voltage of−3 V and a current density of 200 mA cm−2 at−3.9 V,demonstrating its potential for practical applications in CO_(2)reduction.展开更多
The rise of Zn-ion hybrid capacitor(ZHC)has imposed high requirements on carbon cathodes,including reasonable configuration,high specific surface area,multiscale pores,and abundant defects.To achieve this objective,a ...The rise of Zn-ion hybrid capacitor(ZHC)has imposed high requirements on carbon cathodes,including reasonable configuration,high specific surface area,multiscale pores,and abundant defects.To achieve this objective,a template-oriented strategy coupled with multi-heteroatom modification is proposed to precisely synthesize a three-dimensional boron/nitrogen-rich carbon nanoflake-interconnected micro/nano superstructure,referred to as BNPC.The hierarchically porous framework of BNPC shares short channels for fast Zn2+transport,increased adsorption-site accessibility,and structural robustness.Additionally,the boron/nitrogen incorporation effect significantly augments Zn2+adsorption capability and more distinctive pseudocapacitive nature,notably enhancing Zn-ion storage and transmission kinetics by performing the dual-storage mechanism of the electric double-layer capacitance and Faradaic redox process in BNPC cathode.These merits contribute to a high capacity(143.7 mAh g^(-1)at 0.2 A g^(-1))and excellent rate capability(84.5 mAh g^(-1)at 30 A g^(-1))of BNPC-based aqueous ZHC,and the ZHC still shows an ultrahigh capacity of 108.5 mAh g^(-1)even under a high BNPC mass loading of 12 mg cm^(-2).More critically,the BNPC-based flexible device also sustains notable cyclability over 30,000 cycles and low-rate self-discharge of 2.13 mV h-1 along with a preeminent energy output of 117.15 Wh kg^(-1)at a power density of 163.15Wkg^(-1),favoring a creditable applicability in modern electronics.In/ex-situ analysis and theoretical calculations elaborately elucidate the enhanced charge storage mechanism in depth.The findings offer a promising platform for the development of advanced carbon cathodes and corresponding electrochemical devices.展开更多
The development of flexible supercapacitors(FSCs) capable of operating at high temperatures is crucial for expanding the application areas and operating conditions of supercapacitors. Gel polymer electrolytes and elec...The development of flexible supercapacitors(FSCs) capable of operating at high temperatures is crucial for expanding the application areas and operating conditions of supercapacitors. Gel polymer electrolytes and electrode materials stand as two key components that significantly impact the efficacy of hightemperature-tolerant FSCs(HT-FSCs). They should not only exhibit high electrochemical performance and excellent flexibility, but also withstand intense thermal stress. Considerable efforts have been devoted to enhancing their thermal stability while maintaining high electrochemical and mechanical performance. In this review, the fundamentals of HT-FSCs are outlined. A comprehensive overview of state-of-the-art progress and achievements in HT-FSCs, with a focus on thermally stable gel polymer electrolytes and electrode materials is provided. Finally, challenges and future perspectives regarding HT-FSCs are discussed, alongside strategies for elevating operational temperatures and performance.This review offers both theoretical foundations and practical guidelines for designing and manufacturing HT-FSCs, further promoting their widespread adoption across diverse fields.展开更多
Hydrogen peroxide(H_(2)O_(2))is a high-demand organic chemical reagent and has been widely used in various modern industrial applications.Currently,the prominent method for the preparation of H_(2)O_(2)is the anthraqu...Hydrogen peroxide(H_(2)O_(2))is a high-demand organic chemical reagent and has been widely used in various modern industrial applications.Currently,the prominent method for the preparation of H_(2)O_(2)is the anthraquinone oxidation.Unfortunately,it is not conducive to economic and sustainable development since it is a complex process and involves unfriendly environment and potential hazards.In this context,numerous approaches have been developed to synthesize H_(2)O_(2).Among them,photo/electro-catalytic ones are considered as two of the most promising manners for on-site synthesis of H_(2)O_(2).These alternatives are sustainable in that only water or O_(2)is required.Namely,water oxidation(WOR)or oxygen reduction(ORR)reactions can be further coupled with clean and sustainable energy.For photo/electro-catalytic reactions for H_(2)O_(2)generation,the design of the catalysts is extremely important and has been extensively conducted with an aim to obtain ultimate catalytic performance.This article overviews the basic principles of WOR and ORR,followed by the summary of recent progresses and achievements on the design and performance of various photo/electro-catalysts for H_(2)O_(2)generation.The related mechanisms for these approaches are highlighted from theoretical and experimental aspects.Scientific challenges and opportunities of engineering photo/electro-catalysts for H_(2)O_(2)generation are also outlined and discussed.展开更多
Bladder cancer is the most common malignant tumours with high morbidity, mortality and recurrence.However, currently developed detection methods for bladder cancer-associated urine biomarkers are hindered by their ext...Bladder cancer is the most common malignant tumours with high morbidity, mortality and recurrence.However, currently developed detection methods for bladder cancer-associated urine biomarkers are hindered by their extremely low abundance. Hence, the exploration of a highly sensitive and selective approach for the detection of trace bladder cancer-associated biomarkers in human urine is of vital importance for the diagnosis of bladder cancer. Herein, we developed a highly reliable indium gallium zinc oxide field effect transistor(IGZO FET) biosensor for the detection of bladder cancer-related biomarker micro RNA. The single-stranded DNA-functionalized IGZO FET biosensors exhibit high sensing reproducibility and stability with an ultralow detection limit of 19.8 amol/L. The device could also be used for quantitative detection of trace micro RNA in human urine samples and can effectively distinguish bladder cancer patients from healthy donors. The development of high performance IGZO FET biosensors presents new opportunities for the achievement of early-stage diagnosis of bladder cancer.展开更多
Exploring highly active earth-abundant bifu nctional electrocatalysts for water splitting at a high output is essential for the forthcoming hydrogen economy.Non-noble Fe_(3)O_(4) catalyst owns outstanding conductivity...Exploring highly active earth-abundant bifu nctional electrocatalysts for water splitting at a high output is essential for the forthcoming hydrogen economy.Non-noble Fe_(3)O_(4) catalyst owns outstanding conductivity and its octahedral Fe sites can markedly promote water dissociation.However,it lacks active centers on the surface,resulting in its poor activity when used as a catalyst for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).Herein,an electron redistribution strategy is proposed by introducing Ni sites onto the surface of Fe_(3)O_(4)(Ni/Fe_(3)O_(4)).The abundant delocalized electrons,derived from the electronic interaction of Ni and Fe_(3)O_(4) species,significantly optimize the electronic structure of the Ni/Fe_(3)O_(4) catalyst,leading to its improved adsorption behavior.This Ni/Fe_(3)O_(4) catalyst exhibits remarkable bifunctional activity,steadily outputting 1000 mA cm^(-2)at the low overpotential of 387 mV for HER and 338 mV for OER,respectively.Using Ni/Fe_(3)O_(4) as a bifunctional catalyst for overall water splitting reaction exhibits the optimal performance with outstanding stability,obtaining a current density of1000 mA cm^(-2)at 1.98 V,much superior to a Pt/C‖IrO_(2)cell.Experimental analysis and theoretical calculations collectively corroborate that the electron redistribution of Fe_(3)O_(4) is activated by coupling Ni species,leading to the promoted HER and OER kinetics.This electron redistribution strategy provides an effective method to activate transition metal-based catalysts which are promising to be utilized as superior electrocatalysts for the industrial overall water splitting reaction.展开更多
Multidimensional integration and multifunctional com-ponent assembly have been greatly explored in recent years to extend Moore’s Law of modern microelectronics.However,this inevitably exac-erbates the inhomogeneity ...Multidimensional integration and multifunctional com-ponent assembly have been greatly explored in recent years to extend Moore’s Law of modern microelectronics.However,this inevitably exac-erbates the inhomogeneity of temperature distribution in microsystems,making precise temperature control for electronic components extremely challenging.Herein,we report an on-chip micro temperature controller including a pair of thermoelectric legs with a total area of 50×50μm^(2),which are fabricated from dense and flat freestanding Bi2Te3-based ther-moelectric nano films deposited on a newly developed nano graphene oxide membrane substrate.Its tunable equivalent thermal resistance is controlled by electrical currents to achieve energy-efficient temperature control for low-power electronics.A large cooling temperature difference of 44.5 K at 380 K is achieved with a power consumption of only 445μW,resulting in an ultrahigh temperature control capability over 100 K mW^(-1).Moreover,an ultra-fast cooling rate exceeding 2000 K s^(-1) and excellent reliability of up to 1 million cycles are observed.Our proposed on-chip temperature controller is expected to enable further miniaturization and multifunctional integration on a single chip for microelectronics.展开更多
Aqueous Zn-ion energy storage systems,which are expected to be integrated into intelligent electronics as a secure power supply,suffer poor reversibility of Zn anodes,predominantly associated with dendritic growth and...Aqueous Zn-ion energy storage systems,which are expected to be integrated into intelligent electronics as a secure power supply,suffer poor reversibility of Zn anodes,predominantly associated with dendritic growth and side reactions.This study introduces a polyanionic strategy to address these formidable issues by developing a hydrogel electrolyte(PACXHE)with carboxyl groups.Notably,the carboxyl groups within the hydrogel structure establish favorable channels to promote the transport of Zn^(2+)ions.They also expedite the desolvation of hydrated Zn^(2+)ions,leading to enhanced deposition kinetics.Additionally,these functional groups confine interfacial planar diffusion and promote preferential deposition along the(002)plane of Zn,enabling a smooth surface texture of the Zn anode.This multifaceted regulation successfully achieves the suppression of Zn dendrites and side reactions,thereby enhancing the electrochemical reversibility and service life during plating/stripping cycles.Therefore,such an electrolyte demonstrates a high average Coulombic efficiency of 97.7%for 500 cycles in the Zn‖Cu cell and exceptional cyclability with a duration of 480 h at 1 mA cm^(-2)/1 mA h cm^(-2)in the Zn‖Zn cell.Beyond that,the Zn-ion hybrid micro-capacitor employing PACXHE exhibits satisfactory cycling stability,energy density,and practicality for energy storage in flexible,intelligent electronics.The present polyanionic-based hydrogel strategy and the development of PACXHE represent significant advancements in the design of hydrogel electrolytes,paving the way for a more sustainable and efficient future in the energy storage field.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 application of electrochemical technologies for chemical and fuel synthesis offers a significantly more eco-friendly method than traditional industrial practice.However,electrochemical synthesis in aqueous solutio...The application of electrochemical technologies for chemical and fuel synthesis offers a significantly more eco-friendly method than traditional industrial practice.However,electrochemical synthesis in aqueous solutions often involves a sluggish oxygen evolution reaction(OER)at the anode,yielding products that are less economically viable and leading to inefficient energy use.This challenge has prompted extensive research into replacing the OER with fast,value-added oxidation reactions(OER alternatives)in electrolysis systems.In this review,we summarize the latest research progress in coupled electrochemical systems that integrate OER al-ternatives with reduction reactions,beyond hydrogen evolution reactions,in aqueous solutions to synthesize dual value-added products.After providing a general overview,we start by introducing two key factors:(i)electrolytic devices and(ii)advanced characterization techniques for mechanism investigation.The focus then shifts to catalysts developed so far and their corresponding catalytic mechanisms,and to the electrochemical performance of these hybrid electrolysis systems.Finally,we outline and discuss the challenges and prospects for these inte-grated electrochemical systems to offer insights into future research directions and applications.We envision that this review will provide a panorama of electrolysis systems for dual value-added products,thereby fostering the development of green synthesis with zero carbon emissions.展开更多
Highly active,stable,and cut-price(photo-)electrocatalysts are desired to overwhelm high energy barriers for anodic oxygen evolution reaction processes.Herein,a heterostructure of cobalt-iron oxide/black phosphorus na...Highly active,stable,and cut-price(photo-)electrocatalysts are desired to overwhelm high energy barriers for anodic oxygen evolution reaction processes.Herein,a heterostructure of cobalt-iron oxide/black phosphorus nanosheets is in-situ synthesized via a facile and novel three-electrode electrolysis method.Bulky black phosphorus is exfoliated into its nanosheets at the cathode while the CoFe oxide is derived directly from the metal wire anode during the electrolysis process.This heterostructure exhibits excellent electrocatalytic oxygen evolution reaction(OER)performance,and the overpotential at 10 mA·cm^(−2)is 51 mV lower than that of the commercial RuO_(2)catalyst.Its superior OER performance stems from the favorable adsorption behavior and an enlarged electrochemical active surface area of the catalyst.To reveal the origin of excellent OER performance from the point of adsorption strength of OH*,methanol oxidation reaction(MOR)test is applied under the identified OER operating conditions.Further introduction of light illumination enhances the OER activity of this heterostructure.The overpotential drops down to 280 mV,benefiting from pronounced photochemical response of black phosphorus nanosheets and iron oxide inside the heterostructure.This work develops a new electrochemical method to construct high performance and light-sensitive heterostructures from black phosphorus nanosheets for the OER.展开更多
Optimizing the structure of an electrocatalyst is critical to achieve its outstand-ing performance as well as to establish relationships between its composition and its performance.In this work,a series of mesoporous ...Optimizing the structure of an electrocatalyst is critical to achieve its outstand-ing performance as well as to establish relationships between its composition and its performance.In this work,a series of mesoporous RhPt electrocatalysts(RhPt-MPS)with different compositions are designed and synthesized toward the ethanol oxidation reaction(EOR).The mesoporous structure of RhPt-MPS exposes abundant surface sites and channels for mass transfer of ethanol,and thus boosts the catalytic EOR performance.It has been confirmed that Rh not only reduces the oxidation potential of EOR,but also effectively facilitates the breakage of C-C bond.Stemming from structural and compositional advantages of the RhPt 0.6-MPS electrocatalyst,it exhibits the highest activity(2846.0 mA mg^(–1))for the EOR when compared with other RhPt-MPS,Rh-MPS,and Pt-MPS electrocatalysts.It also delivers excellent stability and high selectivity than other electrocatalysts.展开更多
The present work is focused on developing a novel biomaterial platform to achieve enhanced direct electron transfer （DET） of hemoprotein and higher biosensor performance on vertically aligned carbon hybrid TiO2 nano...The present work is focused on developing a novel biomaterial platform to achieve enhanced direct electron transfer （DET） of hemoprotein and higher biosensor performance on vertically aligned carbon hybrid TiO2 nanotubes （C-TiO2 NTs）. Using a simple surfactant-assisted method, controllable hybridization of TiO2 NTs with conductive amorphous carbon species is realized. The obtained C-TiO2 NTs is ingeniously chosen to serve as an ideal ＂vessel＂ for protein immobilization and biosensor applications. Results show that the appropriate hybridization of C into TiO2 NTs leads to a much better conductivity of TiO2 NTs without destroying their preponderant tubular structures or damaging their excellent biocompatibility and hydrophilicity. When used in loading proteins, the C-TiO2 NTs can be used as a super vessel for rapid and substantive immobilization of hemoglobin （Hb）, with a large surface electroactive Hb coverage （I＊） of 3.3 × 10 9 mol·cm^-2. Enhanced DET of Hb is commendably observed on the constructed Hb/C-TiO2 NTs biosensor with a couple of well-defined redox peaks in a fast electron transfer process. The biosensor further exhibits fast response, high sensitivity and stability for the amperometric biosensing of H202 with the detection limit as low as 3.1 × 10^-8 mol/L.展开更多
Developing high-activity and low-cost catalysts is the key to eliminate the limitation of sluggish anodic oxygen evolution reaction(OER)during electrocatalytic overall water splitting.Herein,Ni‒Fe/black phosphorous(BP...Developing high-activity and low-cost catalysts is the key to eliminate the limitation of sluggish anodic oxygen evolution reaction(OER)during electrocatalytic overall water splitting.Herein,Ni‒Fe/black phosphorous(BP)composites are synthesized using a simple three-electrode system,where exfoliation of bulky BP and synthesis of NiFe composites are simultaneously achieved.Under light illumination,the optimized Ni‒Fe/BP composite exhibits excellent photoelectrocatalytic OER performance(e.g.,the overpotential is 58 mV lower than a commercial RuO_(2) electrocatalyst at a current density of 10 mA·cm^(-2)).The electron transfer on this composite is proved to follow a Ni‒BP‒Fe pathway.The electronic structure of this Ni‒Fe/BP composite is effectively regulated,leading to optimized adsorption strength of the intermediate OH*and improved intrinsic activity for the OER.Together with active sites on the support,this Ni‒Fe/BP composite possesses abundant electrochemical active sites and a bug surface area for the OER.The introduction of light further accelerates the electrocatalytic OER.This work provides a novel and facile method to synthesize high-performance metal/BP composites as well as the approaches to reveal their OER mechanisms.展开更多
CONSPECTUS:Hydrogen generation from electrocatalytic water splitting is widely regarded as an important energy conversion process based on its high compatibility with clean and renewable energy sources.It thus has the...CONSPECTUS:Hydrogen generation from electrocatalytic water splitting is widely regarded as an important energy conversion process based on its high compatibility with clean and renewable energy sources.It thus has the potential to help society achieve cleanness and sustainability.For the long-term production of highly purified hydrogen for industrial applications,it is preferred for the hydrogen evolution reaction(HER)to occur under mild working conditions or in alkaline media.However,such practical reaction efficiencies are hindered by additional water dissociation and multistep electron transfer.This stems from the sluggish kinetics of the HER in alkaline media,where the reaction rate is 2 to 3 orders of magnitude lower than in acidic media.Up to now,Pt has been extensively accepted as the symbolic catalyst for HER thanks to its appropriate hydrogen adsorption capability.Unfortunately,its activity is not acceptable due to its poor efficiency for water dissociation in alkaline solutions.In this regard,advanced catalysts that have both high catalytic activity for water dissociation and an appropriate hydrogen adsorption capacity are highly desired.Among the reported Pt-free catalysts for alkaline HER,Rh-based electrocatalysts exhibit obviously enhanced performances.It has been experimentally and theoretically confirmed that the Rh catalyst is located near the top of the Trasatti volcano plot for the HER,indicating its suitable adsorption energy of H*to facilitate the HER.In addition,the Rh catalyst possesses stronger competence for water dissociation than the Pt catalyst,which is a prerequisite for highly effective alkaline HER.In this context,a series of experiments with Rh-based electrocatalysts toward the alkaline HER have been actualized over the past decades.These proposed Rhbased catalysts have displayed impressive performances and promising prospects for hydrogen production.To realize the industrial application of hydrogen generation,Rh-based catalysts still require development,such as with the conceptual design of the catalysts and corresponding advanced synthesis methods.In short,further improvement of the catalytic performances of Rh-based catalysts depends on the development of various regulation strategies.In this Account,we highlight the recent progress and achievements of the regulation strategies for Rh-based catalysts and the corresponding enhancement principle for alkaline HER.We start with an introduction and comparison of the different mechanisms in acidic versus alkaline HER processes,emphasizing the principles of designing highly efficient catalysts toward alkaline HER.On the basis of previously reported studies,we conduct an in-depth discussion about the regulation strategies for Rh-based electrocatalysts and the performance optimization toward alkaline HER.This part is divided into three sections:structural engineering(e.g.,size,alloy,and morphology regulation),surface engineering(e.g.,element doping,facet controlling,and compound constructing),and interface engineering(e.g.,Rh/compound and Rh/carbon interfaces).The effective electronic modulation of Rhbased catalysts in these strategies is also outlined.At the end of this Account,some insights regarding the current challenges of Rhbased catalysts for alkaline HER and future research directions in this exciting field are provided.展开更多
CONSPECTUS:Diamond composite(DC)refers to a system which consists of diamond(Dia)and other components.Various interactions between diamond and other components exist.The first DC,Dia/β-silicon carbide(β-SiC)composit...CONSPECTUS:Diamond composite(DC)refers to a system which consists of diamond(Dia)and other components.Various interactions between diamond and other components exist.The first DC,Dia/β-silicon carbide(β-SiC)composite,was grown in 1992 by means of chemical vapor deposition(CVD)technique.展开更多
Highly electrocatalytic and durable Co-Nx-C frameworks containing carbon nanofibers(CNFs)/carbon nitrides(CNs)are vital materials for rechargeable zinc-air batteries(RZABs).However,the existing Co-Nx-C frameworks expe...Highly electrocatalytic and durable Co-Nx-C frameworks containing carbon nanofibers(CNFs)/carbon nitrides(CNs)are vital materials for rechargeable zinc-air batteries(RZABs).However,the existing Co-Nx-C frameworks experience severe agglomeration during synthesis and limited active site accessibility/mechanical robustness.In this work,a photo-enhanced bifunctional catalyst with a type II p-n heterojunction(g-C_(3)N_(4)-Co@CNT/Co-N_(4)/C@CNF)is achieved through a combined“electrospinning+calcination+ball milling”approach.The composite integrates graphitic carbon nitride(g-C_(3)N_(4))nanosheets with dual active Co sites(nanoparticles and Co-N_(4)single atoms)anchored on conductive carbon nanofibers.This architecture enables efficient charge separation,enhanced light absorption,and accelerated oxygen redox kinetics.DFT calculations reveal that g-C_(3)N_(4)modulates the electronic structure and lowers the reaction free-energy barriers,leading the d-band center closer to the Fermi level.Under light irradiation,the g-C_(3)N_(4)-Co@CNT/Co-N_(4)/C@CNF exhibits outstanding ORR/OER catalytic performance,with a small overpotential gap of 0.684 V(E_(1/2)=0.930 V,E_(j:10)=1.614 V).In practical application:1)light-enhanced liquid ZABs with g-C_(3)N_(4)-Co@CNT/Co-N_(4)/C@CNF photoactive catalysts manifest a peak power density of 310 mW cm^(-2)and a long cycle life exceeding 1100 h.2)Light-enhanced flexible ZABs also can reach a peak power density of 96 mW cm^(-2)and tolerate a wide range of bending angles(0°-180°-0°)during harsh operation.This work offers a new platform for designing efficient photo-electrocatalysts and advancing next-generation solar-electrochemical energy conversion systems.展开更多
基金financial support from the Natural Science Foundation of Yancheng(YCBK2024004)the Basic Research Program of Jiangsu(BK20251089)the“Scientific and Technical Innovation Action Plan”Basic Research Field of Shanghai Science and Technology Committee(19JC1410500).
文摘The electrocatalytic reduction of carbon dioxide(CO_(2)RR)to valuable products presents a promising solution for addressing global warming and enhancing renewable energy storage.Herein,we construct a novel Ni_(3)ZnC_(0.7)/Ni heterostructure electrocatalyst,using an electrospinning strategy to prepare metal particles uniformly loaded on nitrogen-doped carbon nanofibers(CNFs).The incorporation of zinc(Zn)into nickel(Ni)catalysts optimizes the adsorption of CO_(2)intermediates,balancing the strong binding affinity of Ni with the comparatively weaker affinity of Zn,which mitigates over-activation.The electron transfer within the Ni_(3)ZnC_(0.7)/Ni@CNFs system facilitates rapid electron transfer to CO_(2),resulting in great performance with a faradaic efficiency for CO(FECO)of nearly 90%at−0.86 V versus the reversible hydrogen electrode(RHE)and a current density of 17.51 mA cm^(−2)at−1.16 V versus RHE in an H-cell.Furthermore,the catalyst exhibits remarkable stability,maintaining its crystal structure and morphology after 50 h of electrolysis.Moreover,the Ni_(3)ZnC_(0.7)/Ni@CNFs is used in the membrane electrode assembly reactor(MEA),which can achieve a FECO of 91.7%at a cell voltage of−3 V and a current density of 200 mA cm−2 at−3.9 V,demonstrating its potential for practical applications in CO_(2)reduction.
基金Natural Science Foundation of Xinjiang Uygur Autonomous Region,Grant/Award Number:2023D01C11National Natural Science Foundation of China,Grant/Award Numbers:22369019,U2003216+2 种基金Special Projects on Regional Collaborative Innovation-SCO Science and Technology Partnership Program,International Science and Technology Cooperation Program,Grant/Award Number:2022E01020Tianshan Talent Training Program,Grant/Award Number:2023TSYCLJ0019National Key Research and Development Program of China,Grant/Award Numbers:2022YFB4101600,2022YFB4101601。
文摘The rise of Zn-ion hybrid capacitor(ZHC)has imposed high requirements on carbon cathodes,including reasonable configuration,high specific surface area,multiscale pores,and abundant defects.To achieve this objective,a template-oriented strategy coupled with multi-heteroatom modification is proposed to precisely synthesize a three-dimensional boron/nitrogen-rich carbon nanoflake-interconnected micro/nano superstructure,referred to as BNPC.The hierarchically porous framework of BNPC shares short channels for fast Zn2+transport,increased adsorption-site accessibility,and structural robustness.Additionally,the boron/nitrogen incorporation effect significantly augments Zn2+adsorption capability and more distinctive pseudocapacitive nature,notably enhancing Zn-ion storage and transmission kinetics by performing the dual-storage mechanism of the electric double-layer capacitance and Faradaic redox process in BNPC cathode.These merits contribute to a high capacity(143.7 mAh g^(-1)at 0.2 A g^(-1))and excellent rate capability(84.5 mAh g^(-1)at 30 A g^(-1))of BNPC-based aqueous ZHC,and the ZHC still shows an ultrahigh capacity of 108.5 mAh g^(-1)even under a high BNPC mass loading of 12 mg cm^(-2).More critically,the BNPC-based flexible device also sustains notable cyclability over 30,000 cycles and low-rate self-discharge of 2.13 mV h-1 along with a preeminent energy output of 117.15 Wh kg^(-1)at a power density of 163.15Wkg^(-1),favoring a creditable applicability in modern electronics.In/ex-situ analysis and theoretical calculations elaborately elucidate the enhanced charge storage mechanism in depth.The findings offer a promising platform for the development of advanced carbon cathodes and corresponding electrochemical devices.
基金Fundamental Research Funds for the Central Universities of China(Grant No. SWU-KT22030)Scientific and Technological Research Program of Chongqing Municipal Education Commission of China (No.KJQN202300205)financial support from the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under the project of 457444676。
文摘The development of flexible supercapacitors(FSCs) capable of operating at high temperatures is crucial for expanding the application areas and operating conditions of supercapacitors. Gel polymer electrolytes and electrode materials stand as two key components that significantly impact the efficacy of hightemperature-tolerant FSCs(HT-FSCs). They should not only exhibit high electrochemical performance and excellent flexibility, but also withstand intense thermal stress. Considerable efforts have been devoted to enhancing their thermal stability while maintaining high electrochemical and mechanical performance. In this review, the fundamentals of HT-FSCs are outlined. A comprehensive overview of state-of-the-art progress and achievements in HT-FSCs, with a focus on thermally stable gel polymer electrolytes and electrode materials is provided. Finally, challenges and future perspectives regarding HT-FSCs are discussed, alongside strategies for elevating operational temperatures and performance.This review offers both theoretical foundations and practical guidelines for designing and manufacturing HT-FSCs, further promoting their widespread adoption across diverse fields.
基金supported by Shanxi Province Science Foundation(20210302124446202102070301018)+1 种基金the National Natural Science Joint Foundation(U1710112)Basic Research Project from the Institute of Coal Chemistry,CAS(SCJC-HN-2022-17)。
文摘Hydrogen peroxide(H_(2)O_(2))is a high-demand organic chemical reagent and has been widely used in various modern industrial applications.Currently,the prominent method for the preparation of H_(2)O_(2)is the anthraquinone oxidation.Unfortunately,it is not conducive to economic and sustainable development since it is a complex process and involves unfriendly environment and potential hazards.In this context,numerous approaches have been developed to synthesize H_(2)O_(2).Among them,photo/electro-catalytic ones are considered as two of the most promising manners for on-site synthesis of H_(2)O_(2).These alternatives are sustainable in that only water or O_(2)is required.Namely,water oxidation(WOR)or oxygen reduction(ORR)reactions can be further coupled with clean and sustainable energy.For photo/electro-catalytic reactions for H_(2)O_(2)generation,the design of the catalysts is extremely important and has been extensively conducted with an aim to obtain ultimate catalytic performance.This article overviews the basic principles of WOR and ORR,followed by the summary of recent progresses and achievements on the design and performance of various photo/electro-catalysts for H_(2)O_(2)generation.The related mechanisms for these approaches are highlighted from theoretical and experimental aspects.Scientific challenges and opportunities of engineering photo/electro-catalysts for H_(2)O_(2)generation are also outlined and discussed.
基金supported by the National Key Research and Development Program of China (No.2017YFA0208000)the Natural Science Foundation of China (Nos.21904100,21904033)financial support from Wuhan University。
文摘Bladder cancer is the most common malignant tumours with high morbidity, mortality and recurrence.However, currently developed detection methods for bladder cancer-associated urine biomarkers are hindered by their extremely low abundance. Hence, the exploration of a highly sensitive and selective approach for the detection of trace bladder cancer-associated biomarkers in human urine is of vital importance for the diagnosis of bladder cancer. Herein, we developed a highly reliable indium gallium zinc oxide field effect transistor(IGZO FET) biosensor for the detection of bladder cancer-related biomarker micro RNA. The single-stranded DNA-functionalized IGZO FET biosensors exhibit high sensing reproducibility and stability with an ultralow detection limit of 19.8 amol/L. The device could also be used for quantitative detection of trace micro RNA in human urine samples and can effectively distinguish bladder cancer patients from healthy donors. The development of high performance IGZO FET biosensors presents new opportunities for the achievement of early-stage diagnosis of bladder cancer.
基金supported by the National Natural Science Foundation of China(U1864207)。
文摘Exploring highly active earth-abundant bifu nctional electrocatalysts for water splitting at a high output is essential for the forthcoming hydrogen economy.Non-noble Fe_(3)O_(4) catalyst owns outstanding conductivity and its octahedral Fe sites can markedly promote water dissociation.However,it lacks active centers on the surface,resulting in its poor activity when used as a catalyst for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).Herein,an electron redistribution strategy is proposed by introducing Ni sites onto the surface of Fe_(3)O_(4)(Ni/Fe_(3)O_(4)).The abundant delocalized electrons,derived from the electronic interaction of Ni and Fe_(3)O_(4) species,significantly optimize the electronic structure of the Ni/Fe_(3)O_(4) catalyst,leading to its improved adsorption behavior.This Ni/Fe_(3)O_(4) catalyst exhibits remarkable bifunctional activity,steadily outputting 1000 mA cm^(-2)at the low overpotential of 387 mV for HER and 338 mV for OER,respectively.Using Ni/Fe_(3)O_(4) as a bifunctional catalyst for overall water splitting reaction exhibits the optimal performance with outstanding stability,obtaining a current density of1000 mA cm^(-2)at 1.98 V,much superior to a Pt/C‖IrO_(2)cell.Experimental analysis and theoretical calculations collectively corroborate that the electron redistribution of Fe_(3)O_(4) is activated by coupling Ni species,leading to the promoted HER and OER kinetics.This electron redistribution strategy provides an effective method to activate transition metal-based catalysts which are promising to be utilized as superior electrocatalysts for the industrial overall water splitting reaction.
基金The authors thank D.Berger,D.Hofmann and C.Kupka in IFW Dresden for helpful technical support.H.R.acknowledges funding from the DFG(Deutsche Forschungsgemeinschaft)within grant number RE3973/1-1.Q.J.,H.R.and K.N.conceived the work.With the support from N.Y.and X.J.,Q.J.and T.G.fabricated the thermoelectric films and conducted the structural and compositional characterizations.Q.J.prepared microchips and fabricated the on-chip micro temperature controllers.Q.J.and N.P.carried out the temperature-dependent material and device performance measurements.Q.J.and H.R.performed the simulation and analytical calculations.Q.J.,H.R.and K.N.wrote the manuscript with input from the other coauthors.All the authors discussed the results and commented on the manuscript.
文摘Multidimensional integration and multifunctional com-ponent assembly have been greatly explored in recent years to extend Moore’s Law of modern microelectronics.However,this inevitably exac-erbates the inhomogeneity of temperature distribution in microsystems,making precise temperature control for electronic components extremely challenging.Herein,we report an on-chip micro temperature controller including a pair of thermoelectric legs with a total area of 50×50μm^(2),which are fabricated from dense and flat freestanding Bi2Te3-based ther-moelectric nano films deposited on a newly developed nano graphene oxide membrane substrate.Its tunable equivalent thermal resistance is controlled by electrical currents to achieve energy-efficient temperature control for low-power electronics.A large cooling temperature difference of 44.5 K at 380 K is achieved with a power consumption of only 445μW,resulting in an ultrahigh temperature control capability over 100 K mW^(-1).Moreover,an ultra-fast cooling rate exceeding 2000 K s^(-1) and excellent reliability of up to 1 million cycles are observed.Our proposed on-chip temperature controller is expected to enable further miniaturization and multifunctional integration on a single chip for microelectronics.
基金funded by the National Natural Science Foundation of China(U2003216)the National Key Research and Development Program of China(2022YFB4101600)+1 种基金the Shanghai Cooperation Organisation Project(2022E01020)the Scientific Research Program of the Higher Education Institution of Xinjiang(XJEDU2022P004)。
文摘Aqueous Zn-ion energy storage systems,which are expected to be integrated into intelligent electronics as a secure power supply,suffer poor reversibility of Zn anodes,predominantly associated with dendritic growth and side reactions.This study introduces a polyanionic strategy to address these formidable issues by developing a hydrogel electrolyte(PACXHE)with carboxyl groups.Notably,the carboxyl groups within the hydrogel structure establish favorable channels to promote the transport of Zn^(2+)ions.They also expedite the desolvation of hydrated Zn^(2+)ions,leading to enhanced deposition kinetics.Additionally,these functional groups confine interfacial planar diffusion and promote preferential deposition along the(002)plane of Zn,enabling a smooth surface texture of the Zn anode.This multifaceted regulation successfully achieves the suppression of Zn dendrites and side reactions,thereby enhancing the electrochemical reversibility and service life during plating/stripping cycles.Therefore,such an electrolyte demonstrates a high average Coulombic efficiency of 97.7%for 500 cycles in the Zn‖Cu cell and exceptional cyclability with a duration of 480 h at 1 mA cm^(-2)/1 mA h cm^(-2)in the Zn‖Zn cell.Beyond that,the Zn-ion hybrid micro-capacitor employing PACXHE exhibits satisfactory cycling stability,energy density,and practicality for energy storage in flexible,intelligent electronics.The present polyanionic-based hydrogel strategy and the development of PACXHE represent significant advancements in the design of hydrogel electrolytes,paving the way for a more sustainable and efficient future in the energy storage field.
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supported by the National Natural Science Foundation of China(No.22209183,22225902,U22A20436,52436005)the National key Research&Development Program of China(2022YFE0115900,2021YFA1501500)+2 种基金the CAS-Commonwealth Scientific and Industrial Research Organization(CSIRO)Joint Research Projects(121835KYSB20200039)Advanced Talents of Jiangsu University,China(Grant No.23JDG027)Natural Science Foundation of Fujian Province(2021J05100).
文摘The application of electrochemical technologies for chemical and fuel synthesis offers a significantly more eco-friendly method than traditional industrial practice.However,electrochemical synthesis in aqueous solutions often involves a sluggish oxygen evolution reaction(OER)at the anode,yielding products that are less economically viable and leading to inefficient energy use.This challenge has prompted extensive research into replacing the OER with fast,value-added oxidation reactions(OER alternatives)in electrolysis systems.In this review,we summarize the latest research progress in coupled electrochemical systems that integrate OER al-ternatives with reduction reactions,beyond hydrogen evolution reactions,in aqueous solutions to synthesize dual value-added products.After providing a general overview,we start by introducing two key factors:(i)electrolytic devices and(ii)advanced characterization techniques for mechanism investigation.The focus then shifts to catalysts developed so far and their corresponding catalytic mechanisms,and to the electrochemical performance of these hybrid electrolysis systems.Finally,we outline and discuss the challenges and prospects for these inte-grated electrochemical systems to offer insights into future research directions and applications.We envision that this review will provide a panorama of electrolysis systems for dual value-added products,thereby fostering the development of green synthesis with zero carbon emissions.
基金the National Natural Science Foundation of China(No.21571119)the Applied Basic Research Project of Shanxi Province(Nos.201901D211393 and 201901D211398)+3 种基金Scientific and Technological Innovation Programs of Higher Education Institution in Shanxi(No.2019L0466)the Graduate Education Innovation Project of Shanxi Province(No.2021Y480)the Graduate Education Innovation Project of Shanxi Normal University(No.2021XSY038)1331 Engineering of Shanxi Province.
文摘Highly active,stable,and cut-price(photo-)electrocatalysts are desired to overwhelm high energy barriers for anodic oxygen evolution reaction processes.Herein,a heterostructure of cobalt-iron oxide/black phosphorus nanosheets is in-situ synthesized via a facile and novel three-electrode electrolysis method.Bulky black phosphorus is exfoliated into its nanosheets at the cathode while the CoFe oxide is derived directly from the metal wire anode during the electrolysis process.This heterostructure exhibits excellent electrocatalytic oxygen evolution reaction(OER)performance,and the overpotential at 10 mA·cm^(−2)is 51 mV lower than that of the commercial RuO_(2)catalyst.Its superior OER performance stems from the favorable adsorption behavior and an enlarged electrochemical active surface area of the catalyst.To reveal the origin of excellent OER performance from the point of adsorption strength of OH*,methanol oxidation reaction(MOR)test is applied under the identified OER operating conditions.Further introduction of light illumination enhances the OER activity of this heterostructure.The overpotential drops down to 280 mV,benefiting from pronounced photochemical response of black phosphorus nanosheets and iron oxide inside the heterostructure.This work develops a new electrochemical method to construct high performance and light-sensitive heterostructures from black phosphorus nanosheets for the OER.
基金This work was supported by Shanxi Province Science Foundation(General Program:20210302124446)Basic Research Project from Institute of Coal Chemistry,CAS(SCJC-HN-2022-17)+1 种基金FoundationofStateKeyLaboratoryof Coal Conversion(2022BWZ006)Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering(Grant Number:2022-K71).
文摘Optimizing the structure of an electrocatalyst is critical to achieve its outstand-ing performance as well as to establish relationships between its composition and its performance.In this work,a series of mesoporous RhPt electrocatalysts(RhPt-MPS)with different compositions are designed and synthesized toward the ethanol oxidation reaction(EOR).The mesoporous structure of RhPt-MPS exposes abundant surface sites and channels for mass transfer of ethanol,and thus boosts the catalytic EOR performance.It has been confirmed that Rh not only reduces the oxidation potential of EOR,but also effectively facilitates the breakage of C-C bond.Stemming from structural and compositional advantages of the RhPt 0.6-MPS electrocatalyst,it exhibits the highest activity(2846.0 mA mg^(–1))for the EOR when compared with other RhPt-MPS,Rh-MPS,and Pt-MPS electrocatalysts.It also delivers excellent stability and high selectivity than other electrocatalysts.
基金the National Natural Science Foundation of China，NSFC Research Fund for International Young Scientists，the Fundamental Research Funds for the Central Universities
文摘The present work is focused on developing a novel biomaterial platform to achieve enhanced direct electron transfer （DET） of hemoprotein and higher biosensor performance on vertically aligned carbon hybrid TiO2 nanotubes （C-TiO2 NTs）. Using a simple surfactant-assisted method, controllable hybridization of TiO2 NTs with conductive amorphous carbon species is realized. The obtained C-TiO2 NTs is ingeniously chosen to serve as an ideal ＂vessel＂ for protein immobilization and biosensor applications. Results show that the appropriate hybridization of C into TiO2 NTs leads to a much better conductivity of TiO2 NTs without destroying their preponderant tubular structures or damaging their excellent biocompatibility and hydrophilicity. When used in loading proteins, the C-TiO2 NTs can be used as a super vessel for rapid and substantive immobilization of hemoglobin （Hb）, with a large surface electroactive Hb coverage （I＊） of 3.3 × 10 9 mol·cm^-2. Enhanced DET of Hb is commendably observed on the constructed Hb/C-TiO2 NTs biosensor with a couple of well-defined redox peaks in a fast electron transfer process. The biosensor further exhibits fast response, high sensitivity and stability for the amperometric biosensing of H202 with the detection limit as low as 3.1 × 10^-8 mol/L.
基金This work was financially supported by the National Natural Science Foundation of China(Grant No.21571119)the Applied Basic Research Project of Shanxi Province(Grant Nos.201901D211393 and 201901D211398)+5 种基金the Natural Science Foundation of Shanxi Province(Grant No.20210302124473)the Scientific and Technological Innovation Programs of Higher Education Institution in Shanxi(Grant No.2019L0466)the Graduate Education Innovation Project of Shanxi Province(Grant No.2021Y480)the China postdoctoral Science Foundation(Grant No.2021M691366)the Graduate Education Innovation Project of Shanxi Normal University(Grant No.2021XSY038)the 1331 Engineering of Shanxi Province.
文摘Developing high-activity and low-cost catalysts is the key to eliminate the limitation of sluggish anodic oxygen evolution reaction(OER)during electrocatalytic overall water splitting.Herein,Ni‒Fe/black phosphorous(BP)composites are synthesized using a simple three-electrode system,where exfoliation of bulky BP and synthesis of NiFe composites are simultaneously achieved.Under light illumination,the optimized Ni‒Fe/BP composite exhibits excellent photoelectrocatalytic OER performance(e.g.,the overpotential is 58 mV lower than a commercial RuO_(2) electrocatalyst at a current density of 10 mA·cm^(-2)).The electron transfer on this composite is proved to follow a Ni‒BP‒Fe pathway.The electronic structure of this Ni‒Fe/BP composite is effectively regulated,leading to optimized adsorption strength of the intermediate OH*and improved intrinsic activity for the OER.Together with active sites on the support,this Ni‒Fe/BP composite possesses abundant electrochemical active sites and a bug surface area for the OER.The introduction of light further accelerates the electrocatalytic OER.This work provides a novel and facile method to synthesize high-performance metal/BP composites as well as the approaches to reveal their OER mechanisms.
基金supported by the Shanxi Province Science Foundation(20210302124446 and 202102070301018)the Basic Research Project from Institute of Coal Chemistry,CAS(SCJC-HN-2022-17).
文摘CONSPECTUS:Hydrogen generation from electrocatalytic water splitting is widely regarded as an important energy conversion process based on its high compatibility with clean and renewable energy sources.It thus has the potential to help society achieve cleanness and sustainability.For the long-term production of highly purified hydrogen for industrial applications,it is preferred for the hydrogen evolution reaction(HER)to occur under mild working conditions or in alkaline media.However,such practical reaction efficiencies are hindered by additional water dissociation and multistep electron transfer.This stems from the sluggish kinetics of the HER in alkaline media,where the reaction rate is 2 to 3 orders of magnitude lower than in acidic media.Up to now,Pt has been extensively accepted as the symbolic catalyst for HER thanks to its appropriate hydrogen adsorption capability.Unfortunately,its activity is not acceptable due to its poor efficiency for water dissociation in alkaline solutions.In this regard,advanced catalysts that have both high catalytic activity for water dissociation and an appropriate hydrogen adsorption capacity are highly desired.Among the reported Pt-free catalysts for alkaline HER,Rh-based electrocatalysts exhibit obviously enhanced performances.It has been experimentally and theoretically confirmed that the Rh catalyst is located near the top of the Trasatti volcano plot for the HER,indicating its suitable adsorption energy of H*to facilitate the HER.In addition,the Rh catalyst possesses stronger competence for water dissociation than the Pt catalyst,which is a prerequisite for highly effective alkaline HER.In this context,a series of experiments with Rh-based electrocatalysts toward the alkaline HER have been actualized over the past decades.These proposed Rhbased catalysts have displayed impressive performances and promising prospects for hydrogen production.To realize the industrial application of hydrogen generation,Rh-based catalysts still require development,such as with the conceptual design of the catalysts and corresponding advanced synthesis methods.In short,further improvement of the catalytic performances of Rh-based catalysts depends on the development of various regulation strategies.In this Account,we highlight the recent progress and achievements of the regulation strategies for Rh-based catalysts and the corresponding enhancement principle for alkaline HER.We start with an introduction and comparison of the different mechanisms in acidic versus alkaline HER processes,emphasizing the principles of designing highly efficient catalysts toward alkaline HER.On the basis of previously reported studies,we conduct an in-depth discussion about the regulation strategies for Rh-based electrocatalysts and the performance optimization toward alkaline HER.This part is divided into three sections:structural engineering(e.g.,size,alloy,and morphology regulation),surface engineering(e.g.,element doping,facet controlling,and compound constructing),and interface engineering(e.g.,Rh/compound and Rh/carbon interfaces).The effective electronic modulation of Rhbased catalysts in these strategies is also outlined.At the end of this Account,some insights regarding the current challenges of Rhbased catalysts for alkaline HER and future research directions in this exciting field are provided.
基金the China Scholarship Council(CSC)for the financial support(No.202008420219)X.D.thanks the CSC for the financial support(No.202106250006)N.Y.thanks the financial support from the Deutsche Forschungsgemeinschaft(DFG,German Research Foundation)under the Project No.457444676.
文摘CONSPECTUS:Diamond composite(DC)refers to a system which consists of diamond(Dia)and other components.Various interactions between diamond and other components exist.The first DC,Dia/β-silicon carbide(β-SiC)composite,was grown in 1992 by means of chemical vapor deposition(CVD)technique.
基金supported by the National Key Research and Development Program of China(2022YFE0138900)National Natural Science Foundation of China(21972017)+2 种基金the Fundamental Research Funds for the Central Universities(2232022D-18,CUSF-DH-T-2023061)Shanghai Sailing Program(22YF1400700)the Chenguang Program of Shanghai Education Development Foundation and Shanghai Municipal Education Commission(22CGA37).
文摘Highly electrocatalytic and durable Co-Nx-C frameworks containing carbon nanofibers(CNFs)/carbon nitrides(CNs)are vital materials for rechargeable zinc-air batteries(RZABs).However,the existing Co-Nx-C frameworks experience severe agglomeration during synthesis and limited active site accessibility/mechanical robustness.In this work,a photo-enhanced bifunctional catalyst with a type II p-n heterojunction(g-C_(3)N_(4)-Co@CNT/Co-N_(4)/C@CNF)is achieved through a combined“electrospinning+calcination+ball milling”approach.The composite integrates graphitic carbon nitride(g-C_(3)N_(4))nanosheets with dual active Co sites(nanoparticles and Co-N_(4)single atoms)anchored on conductive carbon nanofibers.This architecture enables efficient charge separation,enhanced light absorption,and accelerated oxygen redox kinetics.DFT calculations reveal that g-C_(3)N_(4)modulates the electronic structure and lowers the reaction free-energy barriers,leading the d-band center closer to the Fermi level.Under light irradiation,the g-C_(3)N_(4)-Co@CNT/Co-N_(4)/C@CNF exhibits outstanding ORR/OER catalytic performance,with a small overpotential gap of 0.684 V(E_(1/2)=0.930 V,E_(j:10)=1.614 V).In practical application:1)light-enhanced liquid ZABs with g-C_(3)N_(4)-Co@CNT/Co-N_(4)/C@CNF photoactive catalysts manifest a peak power density of 310 mW cm^(-2)and a long cycle life exceeding 1100 h.2)Light-enhanced flexible ZABs also can reach a peak power density of 96 mW cm^(-2)and tolerate a wide range of bending angles(0°-180°-0°)during harsh operation.This work offers a new platform for designing efficient photo-electrocatalysts and advancing next-generation solar-electrochemical energy conversion systems.
