Using interface engineering,a highly efficient catalyst with a shell@core structure was successfully synthesized by growing an amorphous material composed of Ni,Mo,and P on Cu nanowires(Ni-MoP@CuNWs).This catalyst onl...Using interface engineering,a highly efficient catalyst with a shell@core structure was successfully synthesized by growing an amorphous material composed of Ni,Mo,and P on Cu nanowires(Ni-MoP@CuNWs).This catalyst only requires an overpotential of 35 mV to reach a current density of 10 mA cm^(-2).The exceptional hydrogen evolution reaction(HER)activity is attributed to the unique amorphous rod-like nature of NiMoP@CuNWs,which possesses a special hydrophilic feature,en-hances mass transfer,promotes effective contact between the electrode and electrolyte solution,and exposes more active sites during the catalytic process.Density functional theory revealed that the introduction of Mo weakens the binding strength of the Ni site on the catalyst surface with the H atom and promotes the desorption process of the H_(2)product significantly.Owing to its facile syn-thesis,low cost,and high catalytic performance,this electrocatalyst is a promising option for com-mercial applications as a water electrolysis catalyst.展开更多
Developing stable and efficient nonprecious-metal-based oxygen evolution catalysts in the neutral electrolyte is a challenging but essential goal for various electrochemical systems.Particularly,cobalt-based spinels h...Developing stable and efficient nonprecious-metal-based oxygen evolution catalysts in the neutral electrolyte is a challenging but essential goal for various electrochemical systems.Particularly,cobalt-based spinels have drawn a considerable amount of attention but most of them operate in alkali solutions.However,the frequently studied Co-Fe spinel system never exhibits appreciable stability in nonbasic conditions,not to mention attract further investigation on its key structural motif and transition states for activity loss.Herein,we report exceptional stable Co-Fe spinel oxygen evolution catalysts(~30%Fe is optimal)in a neutral electrolyte,owing to its unique metal ion arrangements in the crystal lattice.The introduced iron content enters both the octahedral and tetrahedral sites of the spinel as Fe^(2+)and Fe^(3+)(with Co ions having mixed distribution as well).Combining density functional theory calculations,we find that the introduction of Fe to Co_(3)O_(4)lowers the covalency of metal-oxygen bonds and can help suppress the oxidation of Co^(2+/3+)and 0^(2-).It implies that the Co-Fe spinel will have minor surface reconstruction and less lattice oxygen loss during the oxygen evolution reaction process in comparison with Co_(3)O_(4)and hence show much better stability.These findings suggest that there is still much chance for the spinel structures,especially using reasonable sublattices engineering via multimetal doping to develop advanced oxygen evolution catalysts.展开更多
Electrocatalytic water splitting for hydrogen production is hampered by the sluggish oxygen evolution reaction(OER)and large power consumption and replacing the OER with thermodynamically favourable reactions can impr...Electrocatalytic water splitting for hydrogen production is hampered by the sluggish oxygen evolution reaction(OER)and large power consumption and replacing the OER with thermodynamically favourable reactions can improve the energy conversion efficiency.Since iron corrodes easily and even self-corrodes to form magnetic iron oxide species and generate corrosion currents,a novel strategy to integrate the hydrogen evolution reaction(HER)with waste Fe upgrading reaction(FUR)is proposed and demonstrated for energy-efficient hydrogen production in neutral media.The heterostructured MoSe_(2)/MoO_(2) grown on carbon cloth(MSM/CC)shows superior HER performance to that of commercial Pt/C at high current densities.By replacing conventional OER with FUR,the potential required to afford the anodic current density of 10 m A cm^(-2)decreases by 95%.The HER/FUR overall reaction shows an ultralow voltage of 0.68 V for 10 m A cm^(-2)with a power equivalent of 2.69 k Wh per m^(3)H_(2).Additionally,the Fe species formed at the anode extract the Rhodamine B(Rh B)pollutant by flocculation and also produce nanosized magnetic powder and beneficiated Rh B for value-adding applications.This work demonstrates both energy-saving hydrogen production and pollutant recycling without carbon emission by a single system and reveals a new direction to integrate hydrogen production with environmental recovery to achieve carbon neutrality.展开更多
Currently,more than 86%of global energy consumption is still mainly dependent on traditional fossil fuels,which causes resource scarcity and even emission of high amounts of carbon dioxide(CO_(2)),resulting in a sever...Currently,more than 86%of global energy consumption is still mainly dependent on traditional fossil fuels,which causes resource scarcity and even emission of high amounts of carbon dioxide(CO_(2)),resulting in a severe“Greenhouse effect.”Considering this situation,the concept of“carbon neutrality”has been put forward by 125 countries one after another.To achieve the goals of“carbon neutrality,”two main strategies to reduce CO_(2) emissions and develop sustainable clean energy can be adopted.Notably,these are crucial for the synthesis of advanced single-atom catalysts(SACs)for energyrelated applications.In this review,we highlight unique SACs for conversion of CO_(2) into high-efficiency carbon energy,for example,through photocatalytic,electrocatalytic,and thermal catalytic hydrogenation technologies,to convert CO_(2) into hydrocarbon fuels(CO,CH_(4),HCOOH,CH_(3)OH,and multicarbon[C_(2+)]products).In addition,we introduce advanced energy conversion technologies and devices to replace traditional polluting fossil fuels,such as photocatalytic and electrocatalytic water splitting to produce hydrogen energy and a high-efficiency oxygen reduction reaction(ORR)for fuel cells.Impressively,several representative examples of SACs(including d-,ds-,p-,and f-blocks)for CO_(2) conversion,water splitting to H2,and ORR are discussed to describe synthesis methods,characterization,and corresponding catalytic activity.Finally,this review concludes with a description of the challenges and outlooks for future applications of SACs in contributing toward carbon neutrality.展开更多
It is significant for the rational construction of the high–efficient bifunctional electrocatalysts for in–depth understandings of how to improve the electron transfer and ion/oxygen transport in catalyzing oxygen r...It is significant for the rational construction of the high–efficient bifunctional electrocatalysts for in–depth understandings of how to improve the electron transfer and ion/oxygen transport in catalyzing oxygen reduction reaction and oxygen evolution reaction(ORR and OER),but still full of vital challenges.Herein,we synthesize the novel“three–in–one”catalyst that engineers core–shell Mott–Schottky Co_(9)S_(8)/Co heterostructure on the defective reduced graphene oxide(Co_(9)S_(8)/Co–rGO).The Co_(9)S_(8)/Co–rGO catalyst exhibits abundant Mott–Schottky heterogeneous–interfaces,the well–defined core–shell nanostructure as well as the defective carbon architecture,which provide the multiple guarantees for enhancing the electron transfer and ion/oxygen transport,thus boosting the catalytic ORR and OER activities in neutral electrolyte.As expected,the integrated core–shell Mott–Schottky Co_(9)S_(8)/Co–rGO catalyst delivers the most robust and efficient rechargeable ZABs performance in neutral solution electrolytes accompanied with a power density of 59.5 mW cm^(-2) and superior cycling stability at 5 mA cm^(-2) over 200 h.This work not only emphasizes the rational designing of the high–efficient bifunctional oxygen catalysts from the fundamental understanding of accelerating the electron transfer and ion/oxygen transport,but also sheds light on the practical application prospects in more friendly environmentally neutral rechargeable ZABs.展开更多
Cobalt-based phosphate/phosphonates are a class of promising water oxidation catalysts at neutralpH.Herein,we reported a facile hydrothermal synthesis of various nanostructured cobalt phe-nylphosphonates.It is found t...Cobalt-based phosphate/phosphonates are a class of promising water oxidation catalysts at neutralpH.Herein,we reported a facile hydrothermal synthesis of various nanostructured cobalt phe-nylphosphonates.It is found that the number of hydroxyl group of structure-directing reagent iscrucial for the construction of 3D hierarchical structures including hierarchical nanosheet flow-er-like assemblies and nanothorn microsphere.These samples were characterized by scanningelectron microscopy,transmission electron microscopy,X-ray diffraction,infrared,and X-ray pho-toelectron spectroscopy techniques.They can act as highly efficient electrocatalysts for the oxygenevolution reaction at neutral pH.Among these,hierarchical cobalt phenylphosphonate nanothornflowers present excellent performance,affording a current density of 1 mA cm^-2 required a smalloverpotential of 393 mV.This work offers a new clue to develop high-performance metal phospho-nate/phosphate catalysts toward electrochemical water oxidation.展开更多
Hydrogen evolution reaction(HER)in neutral medium suffers from slow kinetics as compared to that in alkaline or acidic conditions,owing to larger Ohmic loss and low proton concentration.Here we report that a self-supp...Hydrogen evolution reaction(HER)in neutral medium suffers from slow kinetics as compared to that in alkaline or acidic conditions,owing to larger Ohmic loss and low proton concentration.Here we report that a self-supported nanoporous Au-SnO_(x)(NP Au-SnO_(x))catalyst with gradient tin oxide surface could significantly enhance HER activity in neutral buffer solution(0.2 M PBS).The NP Au-SnO_(x)catalyst exhibits a low onset overpotential of 38 mV and a small Tafel slope of 79 mV dec^(−1).The current density of 10 mA cm^(−2)is manifested at an overpotential as low as 148 mV,representing the comparable performance of Pt/C catalyst.This high catalytic activity can retain at least 10 hours without any detectable decay.The superior HER activity is proposed to originate from the gradient SnO_(x)structure and metal/oxide interfaces in nanoporous ligaments.Furthermore,the X-ray photoelectron spectroscopy reveals that the gradient oxide in the ligament is remarkably stable during long-term reaction.展开更多
Grounded ship faces up exceptionally different stability forces unlike in her normal operating condition. This critical situation must be corrected as soon as can minimize hull stress, the risk of pollution and stabil...Grounded ship faces up exceptionally different stability forces unlike in her normal operating condition. This critical situation must be corrected as soon as can minimize hull stress, the risk of pollution and stability failure. Re-floating the ship need full understanding of the impact of ground reaction （R） on the ship buoyancy and stability. Re-floating the ship has different phases and there are several immediate actions that should be taken by ship＇s crew; one of these phases is re-calculation of ship stability conditions. In this paper, a guide to understanding the effect of the ground reaction （R）, determines the amount of ground pressure and its location. With consideration of the seabed form whether symmetric of asymmetric. Calculating the magnitude of the ground reaction （R） using different applicable methods, explaining the effect of using weight to re-float the ship by her own means, focusing on GM calculation after grounding.展开更多
文摘Using interface engineering,a highly efficient catalyst with a shell@core structure was successfully synthesized by growing an amorphous material composed of Ni,Mo,and P on Cu nanowires(Ni-MoP@CuNWs).This catalyst only requires an overpotential of 35 mV to reach a current density of 10 mA cm^(-2).The exceptional hydrogen evolution reaction(HER)activity is attributed to the unique amorphous rod-like nature of NiMoP@CuNWs,which possesses a special hydrophilic feature,en-hances mass transfer,promotes effective contact between the electrode and electrolyte solution,and exposes more active sites during the catalytic process.Density functional theory revealed that the introduction of Mo weakens the binding strength of the Ni site on the catalyst surface with the H atom and promotes the desorption process of the H_(2)product significantly.Owing to its facile syn-thesis,low cost,and high catalytic performance,this electrocatalyst is a promising option for com-mercial applications as a water electrolysis catalyst.
基金the financial support by the National Natural Science Foundation of China(NSFC,grant nos.21905288 and 51904288)Zhejiang Provincial Natural Science Foundation(LZ21B030001)+3 种基金K.C.Wong Education Foundation(GJTD-2019-13)Ningbo major special projects of the Plan“Science and Technology Innovation 2025”(grant nos.2018B10056 and 2019B10046)Ningbo 3315 ProgramYongjiang Talent Introduction Program(no.2021A-115-G)
文摘Developing stable and efficient nonprecious-metal-based oxygen evolution catalysts in the neutral electrolyte is a challenging but essential goal for various electrochemical systems.Particularly,cobalt-based spinels have drawn a considerable amount of attention but most of them operate in alkali solutions.However,the frequently studied Co-Fe spinel system never exhibits appreciable stability in nonbasic conditions,not to mention attract further investigation on its key structural motif and transition states for activity loss.Herein,we report exceptional stable Co-Fe spinel oxygen evolution catalysts(~30%Fe is optimal)in a neutral electrolyte,owing to its unique metal ion arrangements in the crystal lattice.The introduced iron content enters both the octahedral and tetrahedral sites of the spinel as Fe^(2+)and Fe^(3+)(with Co ions having mixed distribution as well).Combining density functional theory calculations,we find that the introduction of Fe to Co_(3)O_(4)lowers the covalency of metal-oxygen bonds and can help suppress the oxidation of Co^(2+/3+)and 0^(2-).It implies that the Co-Fe spinel will have minor surface reconstruction and less lattice oxygen loss during the oxygen evolution reaction process in comparison with Co_(3)O_(4)and hence show much better stability.These findings suggest that there is still much chance for the spinel structures,especially using reasonable sublattices engineering via multimetal doping to develop advanced oxygen evolution catalysts.
基金financially supported by the Key Research and Development Program of Hubei Province (2021BAA208)the National Natural Science Foundation of China (52002294,51974208 and U2003130)+3 种基金the Young Top-notch Talent Cultivation Program of Hubei ProvinceKnowledge Innovation Program of Wuhan-Shuguang Project (2022010801020364)the City University of Hong Kong Strategic Research Grant (SRG) (7005505)the City University of Hong Kong Donation Research Grant (DONRMG 9229021)。
文摘Electrocatalytic water splitting for hydrogen production is hampered by the sluggish oxygen evolution reaction(OER)and large power consumption and replacing the OER with thermodynamically favourable reactions can improve the energy conversion efficiency.Since iron corrodes easily and even self-corrodes to form magnetic iron oxide species and generate corrosion currents,a novel strategy to integrate the hydrogen evolution reaction(HER)with waste Fe upgrading reaction(FUR)is proposed and demonstrated for energy-efficient hydrogen production in neutral media.The heterostructured MoSe_(2)/MoO_(2) grown on carbon cloth(MSM/CC)shows superior HER performance to that of commercial Pt/C at high current densities.By replacing conventional OER with FUR,the potential required to afford the anodic current density of 10 m A cm^(-2)decreases by 95%.The HER/FUR overall reaction shows an ultralow voltage of 0.68 V for 10 m A cm^(-2)with a power equivalent of 2.69 k Wh per m^(3)H_(2).Additionally,the Fe species formed at the anode extract the Rhodamine B(Rh B)pollutant by flocculation and also produce nanosized magnetic powder and beneficiated Rh B for value-adding applications.This work demonstrates both energy-saving hydrogen production and pollutant recycling without carbon emission by a single system and reveals a new direction to integrate hydrogen production with environmental recovery to achieve carbon neutrality.
基金National Key R&D Program of China,Grant/Award Number:2018YFA0702003National Natural Science Foundation of China,Grant/Award Numbers:21890383,21871159Science and Technology Key Project of Guangdong Province of China,Grant/Award Number:2020B010188002。
文摘Currently,more than 86%of global energy consumption is still mainly dependent on traditional fossil fuels,which causes resource scarcity and even emission of high amounts of carbon dioxide(CO_(2)),resulting in a severe“Greenhouse effect.”Considering this situation,the concept of“carbon neutrality”has been put forward by 125 countries one after another.To achieve the goals of“carbon neutrality,”two main strategies to reduce CO_(2) emissions and develop sustainable clean energy can be adopted.Notably,these are crucial for the synthesis of advanced single-atom catalysts(SACs)for energyrelated applications.In this review,we highlight unique SACs for conversion of CO_(2) into high-efficiency carbon energy,for example,through photocatalytic,electrocatalytic,and thermal catalytic hydrogenation technologies,to convert CO_(2) into hydrocarbon fuels(CO,CH_(4),HCOOH,CH_(3)OH,and multicarbon[C_(2+)]products).In addition,we introduce advanced energy conversion technologies and devices to replace traditional polluting fossil fuels,such as photocatalytic and electrocatalytic water splitting to produce hydrogen energy and a high-efficiency oxygen reduction reaction(ORR)for fuel cells.Impressively,several representative examples of SACs(including d-,ds-,p-,and f-blocks)for CO_(2) conversion,water splitting to H2,and ORR are discussed to describe synthesis methods,characterization,and corresponding catalytic activity.Finally,this review concludes with a description of the challenges and outlooks for future applications of SACs in contributing toward carbon neutrality.
基金financially supported by the National Natural Science Foundation of China (21775142)the Sino–German Center for Research Promotion (Grants GZ 1351)+1 种基金the Natural Science Foundation of Shandong Province (ZR2020ZD10)the Research Funds for the Central Universities (202061031)。
文摘It is significant for the rational construction of the high–efficient bifunctional electrocatalysts for in–depth understandings of how to improve the electron transfer and ion/oxygen transport in catalyzing oxygen reduction reaction and oxygen evolution reaction(ORR and OER),but still full of vital challenges.Herein,we synthesize the novel“three–in–one”catalyst that engineers core–shell Mott–Schottky Co_(9)S_(8)/Co heterostructure on the defective reduced graphene oxide(Co_(9)S_(8)/Co–rGO).The Co_(9)S_(8)/Co–rGO catalyst exhibits abundant Mott–Schottky heterogeneous–interfaces,the well–defined core–shell nanostructure as well as the defective carbon architecture,which provide the multiple guarantees for enhancing the electron transfer and ion/oxygen transport,thus boosting the catalytic ORR and OER activities in neutral electrolyte.As expected,the integrated core–shell Mott–Schottky Co_(9)S_(8)/Co–rGO catalyst delivers the most robust and efficient rechargeable ZABs performance in neutral solution electrolytes accompanied with a power density of 59.5 mW cm^(-2) and superior cycling stability at 5 mA cm^(-2) over 200 h.This work not only emphasizes the rational designing of the high–efficient bifunctional oxygen catalysts from the fundamental understanding of accelerating the electron transfer and ion/oxygen transport,but also sheds light on the practical application prospects in more friendly environmentally neutral rechargeable ZABs.
文摘Cobalt-based phosphate/phosphonates are a class of promising water oxidation catalysts at neutralpH.Herein,we reported a facile hydrothermal synthesis of various nanostructured cobalt phe-nylphosphonates.It is found that the number of hydroxyl group of structure-directing reagent iscrucial for the construction of 3D hierarchical structures including hierarchical nanosheet flow-er-like assemblies and nanothorn microsphere.These samples were characterized by scanningelectron microscopy,transmission electron microscopy,X-ray diffraction,infrared,and X-ray pho-toelectron spectroscopy techniques.They can act as highly efficient electrocatalysts for the oxygenevolution reaction at neutral pH.Among these,hierarchical cobalt phenylphosphonate nanothornflowers present excellent performance,affording a current density of 1 mA cm^-2 required a smalloverpotential of 393 mV.This work offers a new clue to develop high-performance metal phospho-nate/phosphate catalysts toward electrochemical water oxidation.
基金financial support from the National Natural Science Foundation of China(51771078,91545131 and 51371084)China Postdoctoral Science Foundation(No.2017M612455).
文摘Hydrogen evolution reaction(HER)in neutral medium suffers from slow kinetics as compared to that in alkaline or acidic conditions,owing to larger Ohmic loss and low proton concentration.Here we report that a self-supported nanoporous Au-SnO_(x)(NP Au-SnO_(x))catalyst with gradient tin oxide surface could significantly enhance HER activity in neutral buffer solution(0.2 M PBS).The NP Au-SnO_(x)catalyst exhibits a low onset overpotential of 38 mV and a small Tafel slope of 79 mV dec^(−1).The current density of 10 mA cm^(−2)is manifested at an overpotential as low as 148 mV,representing the comparable performance of Pt/C catalyst.This high catalytic activity can retain at least 10 hours without any detectable decay.The superior HER activity is proposed to originate from the gradient SnO_(x)structure and metal/oxide interfaces in nanoporous ligaments.Furthermore,the X-ray photoelectron spectroscopy reveals that the gradient oxide in the ligament is remarkably stable during long-term reaction.
文摘Grounded ship faces up exceptionally different stability forces unlike in her normal operating condition. This critical situation must be corrected as soon as can minimize hull stress, the risk of pollution and stability failure. Re-floating the ship need full understanding of the impact of ground reaction （R） on the ship buoyancy and stability. Re-floating the ship has different phases and there are several immediate actions that should be taken by ship＇s crew; one of these phases is re-calculation of ship stability conditions. In this paper, a guide to understanding the effect of the ground reaction （R）, determines the amount of ground pressure and its location. With consideration of the seabed form whether symmetric of asymmetric. Calculating the magnitude of the ground reaction （R） using different applicable methods, explaining the effect of using weight to re-float the ship by her own means, focusing on GM calculation after grounding.
