Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)technology,which enables carbon capture storage and resource utilization by reducing CO_(2) to valuable chemicals or fuels,has become a global research hotspot in re...Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)technology,which enables carbon capture storage and resource utilization by reducing CO_(2) to valuable chemicals or fuels,has become a global research hotspot in recent decades.Among the many products of CO_(2)RR(carbon monoxide,acids,aldehydes and alcohols,olefins,etc.),alcohols(methanol,ethanol,propanol,etc.)have a higher market value and energy density,but it is also more difficult to produce.Copper is known to be effective in catalyzing CO_(2) to high valueadded alcohols,but with poor selectivity.The progress of Cu-based catalysts for the selective generation of alcohols,including copper oxides,bimetals,single atoms and composites is reviewed.Meanwhile,to improve Cu-based catalyst activity and modulate product selectivity,the modulation strategies are straighten out,including morphological regulation,crystalline surface,oxidation state,as well as elemental doping and defect engineering.Based on the research progress of electrocatalytic CO_(2) reduction for alcohol production on Cu-based materials,the reaction pathways and the key intermediates of the electrocatalytic CO_(2)RR to methanol,ethanol and propanol are summarized.Finally,the problems of traditional electrocatalytic CO_(2)RR are introduced,and the future applications of machine learning and theoretical calculations are prospected.An in-depth discussion and a comprehensive review of the reaction mechanism,catalyst types and regulation strategies were carried out with a view to promoting the development of electrocatalytic CO_(2)RR to alcohols.展开更多
The interfacial reaction behavior of Al and Ti_3AlC_(2)at different pouring temperatures and its effect on the microstructure and mechanical properties of the composites were investigated.The results show that the add...The interfacial reaction behavior of Al and Ti_3AlC_(2)at different pouring temperatures and its effect on the microstructure and mechanical properties of the composites were investigated.The results show that the addition of3.0 wt.%Ti_3AlC_(2)refines the average grain size ofα(Al)in the composite by 50.1%compared to Al6061 alloy.Morphological analyses indicate that an in-situ Al_(3Ti)transition layer of-180 nm in thickness is generated around the edge of Ti_3AlC_(2)at 720℃,forming a well-bonded Al-Al_(3Ti)interface.At this processing temperature,the ultimate tensile strength of A16061-3.0 wt.%Ti_3AlC_(2)composite is 199.2 MPa,an improvement of 41.5%over the Al6061 matrix.Mechanism analyses further elucidate that 720℃is favourable for forming the nano-sized transition layer at the Ti_3AlC_(2)edges.And,the thermal mismatch strengthening plays a dominant role in this state,with a strengthening contribution of about 74.8%.展开更多
Ni^(2+)/Cu^(2+)/SO_(4)^(2-)/polyvinyl alcohol precursor fibers with uniform diameters were prepared through electrospinning.Nickel-based composite nanoalloys containing Ni,Cu,and S were prepared through heat treatment...Ni^(2+)/Cu^(2+)/SO_(4)^(2-)/polyvinyl alcohol precursor fibers with uniform diameters were prepared through electrospinning.Nickel-based composite nanoalloys containing Ni,Cu,and S were prepared through heat treatment in an Ar atmosphere.The experimental results show that the main components of the prepared nanoalloys are NiCu,Ni_(3)S_(2),Ni,and C.The nanoalloys exhibit fine grain sizes about 200-500 nm,which can increase with increasing heat treatment temperature.Electrochemical test results show that the nickel sulfidemodified NiCu nanoalloy composites exhibit excellent oxygen evolution reaction properties,and the oxygen evolution reaction properties gradually improve with the increasing heat treatment temperature.The sample prepared at 1 000℃ for 40 min show a low overpotential of 423 mV and a small Tafel slope of 134 mV·dec^(-1) at a current density of 10 mA·cm^(-2).展开更多
A ternary system of PTFE/Al/Bi_(2)O_(3)is constructed by incorporating PTFE-based reactive material and thermite for enhancing the energy release of the PTFE-based reactive material.The effects of Bi_(2)O_(3)in the PT...A ternary system of PTFE/Al/Bi_(2)O_(3)is constructed by incorporating PTFE-based reactive material and thermite for enhancing the energy release of the PTFE-based reactive material.The effects of Bi_(2)O_(3)in the PTFE/Al/Bi_(2)O_(3)on both mechanical properties and the energy release were investigated through various tests such as thermogravimetry-differential scanning calorimetry,adiabatic oxygen bomb test and split Hopkinson pressure bar test.The microstructure observed through scanning electron microscope and Xray diffraction results are used to analyze the ignition and reaction mechanism of PTFE/Al/Bi_(2)O_(3).The results indicate that the PTFE/Al/Bi_(2)O_(3)are capable of triggering the exothermic reaction of molten PTFE/Bi_(2)O_(3)and Al/Bi_(2)O_(3)over the PTFE/Al reactive materials,thereby promoting reactions.The excessive aluminum in the ternary system is beneficial for increasing energy release.The ignition of shock-induced chemical reactions in PTFE/Al/Bi_(2)O_(3)is closely related to the material fracture.The dominant mechanism for hot-spot generation under Split Hopkinson Pressure Bar test is the frictional temperature rise at the microcrack after failure.展开更多
The reduction of molecular nitrogen(N_(2))to ammonia(NH_(3))under mild conditions is one of the most promising studies in the energy field due to the important role of NH_(3)in modern industry,production,and life.The ...The reduction of molecular nitrogen(N_(2))to ammonia(NH_(3))under mild conditions is one of the most promising studies in the energy field due to the important role of NH_(3)in modern industry,production,and life.The photocatalytic reduction of N_(2)is expected to achieve clean and sustainable NH_(3)production by using clean solar energy.To date,the new photocatalysts for photocatalytic reduction of N_(2)to NH_(3)at room temperature and atmospheric pressure have not been fully developed.The major challenge is to achieve high light-absorption efficiency,conversion efficiency,and stability of photocatalysts.Herein,the methods for measuring produced NH_(3)are compared,and the problems related to possible NH_(3)pollution in photocatalytic systems are mentioned to provide accurate ideas for measuring photocatalytic efficiency.The recent progress of nitrogen reduction reaction(NRR)photocatalysts at ambient temperature and pressure is summarized by introducing charge transfer,migration,and separation in photocatalytic NRR,which provides a guidance for the selection of future photocatalyst.More importantly,we introduce the latest research strategies of photocatalysts in detail,which can guide the preparation and design of photocatalysts with high NRR activity.展开更多
Water electrolysis is considered as one most promising technique for hydrogen production.The high efficiency electrocatalyst is the key to accelerating the sluggish kinetics of the hydrogen evolution reaction(HER) in ...Water electrolysis is considered as one most promising technique for hydrogen production.The high efficiency electrocatalyst is the key to accelerating the sluggish kinetics of the hydrogen evolution reaction(HER) in alkaline media.In this work,an efficient HER electrocatalyst with hetero-interfacial metal-metal oxide structure was constructed through a redox solid phase reaction(SPR) strategy.During the annealing process under Ar atmosphere,RuO_(2) and WS_(2)in RuO_(2)/WS_(2)precursor were converted to Ru nanoparticles(NPs) and WO3in situ,where tiny Ru NPs and oxygen vacancies were uniformly distributed onto the newly formed WO3nanosheets.Different characterization techniques were adopted to confirm the successful formation of Ru/WO_(3)electrocatalyst(RWOC).The optimized RWOC sample annealed at 400℃ exhibited the low overpotential value of 13 mV at a current density of 10 mA cm^(-2)and strong durability under the alkaline condition.Density functional theoretical calculations further revealed that the promoted adsorption/desorption rate of reaction intermediates and the accelerated kinetics of HER process were deduced to the synergistic effect between Ru and WO_(3)in electrocatalyst.This work provides a feasible method to fabricate highly efficient HER electrocatalysts.展开更多
Transition metal-nitrogen-carbon materials(M-N-Cs),particularly Fe-N-Cs,have been found to be electroactive for accelerating oxygen reduction reaction(ORR)kinetics.Although substantial efforts have been devoted to des...Transition metal-nitrogen-carbon materials(M-N-Cs),particularly Fe-N-Cs,have been found to be electroactive for accelerating oxygen reduction reaction(ORR)kinetics.Although substantial efforts have been devoted to design Fe-N-Cs with increased active species content,surface area,and electronic conductivity,their performance is still far from satisfactory.Hitherto,there is limited research about regulation on the electronic spin states of Fe centers for Fe-N-Cs electrocatalysts to improve their catalytic performance.Here,we introduce Ti_(3)C_(2) MXene with sulfur terminals to regulate the electronic configuration of FeN_(4) species and dramatically enhance catalytic activity toward ORR.The MXene with sulfur terminals induce the spin-state transition of FeN_(4) species and Fe 3d electron delocalization with d band center upshift,enabling the Fe(II)ions to bind oxygen in the end-on adsorption mode favorable to initiate the reduction of oxygen and boosting oxygen-containing groups adsorption on FeN_(4) species and ORR kinetics.The resulting FeN_(4)-Ti_(3)C_(2)Sx exhibits comparable catalytic performance to those of commercial Pt-C.The developed wearable ZABs using FeN_(4)-Ti_(3)C_(2)Sx also exhibit fast kinetics and excellent stability.This study confirms that regulation of the electronic structure of active species via coupling with their support can be a major contributor to enhance their catalytic activity.展开更多
Electrocatalyst designs based on oxophilic foreign atoms are considered a promising approach for developing efficient pH-universal hydrogen evolution reaction(HER)electrocatalysts by overcoming the sluggish alkaline H...Electrocatalyst designs based on oxophilic foreign atoms are considered a promising approach for developing efficient pH-universal hydrogen evolution reaction(HER)electrocatalysts by overcoming the sluggish alkaline HER kinetics.Here,we design ternary transition metals-based nickel telluride(Mo WNi Te)catalysts consisting of high valence non-3d Mo and W metals and oxophilic Te as a first demonstration of non-precious heterogeneous electrocatalysts following the bifunctional mechanism.The Mo WNi Te showed excellent HER catalytic performance with overpotentials of 72,125,and 182 mV to reach the current densities of 10,100,and 1000 mA cm^(-2),respectively,and the corresponding Tafel slope of 47,52,and 58 mV dec-1in alkaline media,which is much superior to commercial Pt/C.Additionally,the HER performance of Mo WNi Te is well maintained up to 3000 h at the current density of 100 mA cm^(-2).It is further demonstrated that the Mo WNi Te exhibits remarkable HER activities with an overpotential of 45 mV(31 mV)and Tafel slope of 60 mV dec-1(34 mV dec-1)at 10 mA cm^(-2)in neutral(acid)media.The superior HER performance of Mo WNi Te is attributed to the electronic structure modulation,inducing highly active low valence states by the incorporation of high valence non-3d transition metals.It is also attributed to the oxophilic effect of Te,accelerating water dissociation kinetics through a bifunctional catalytic mechanism in alkaline media.Density functional theory calculations further reveal that such synergistic effects lead to reduced free energy for an efficient water dissociation process,resulting in remarkable HER catalytic performances within universal pH environments.展开更多
Nickel-rich transition-metal oxides are widely regarded as promising cathode materials for high-energydensity lithium-ion batteries for emerging electric vehicles. However, achieving high energy density in Ni-rich cat...Nickel-rich transition-metal oxides are widely regarded as promising cathode materials for high-energydensity lithium-ion batteries for emerging electric vehicles. However, achieving high energy density in Ni-rich cathodes is accompanied by substantial safety and cycle-life obstacles. The major issues of Ni-rich cathodes at high working potentials are originated from the unstable cathode-electrolyte interface, while the underlying mechanism of parasitic reactions towards surface reconstructions of cathode materials is not well understood. In this work, we controlled the Li_(2)CO_(3) impurity content on LiNi_(0.83)Mn_(0.1)Co_(0.07)O_(2) cathodes using air, tank-air, and O_(2) synthesis environments. Home-built high-precision leakage current and on-line electrochemical mass spectroscopy experiments verify that Li_(2)CO_(3) impurity is a significant promoter of parasitic reactions on Ni-rich cathodes. The rate of parasitic reactions is strongly correlated to Li_(2)CO_(3) content and severe performance deterioration of Ni83 cathodes.The post-mortem characterizations via high-resolution transition electron microscope and X-ray photoelectron spectroscopy depth profiles reveal that parasitic reactions promote more Ni reduction and O deficiency and even rock-salt phase transformation at the surface of cathode materials. Our observation suggests that surface reconstructions have a strong affiliation to parasitic reactions that create chemically acidic environment to etch away the lattice oxygen and offer the electrical charge to reduce the valence state of transition metal. Thus, this study advances our understanding on surface reconstructions of Nirich cathodes and prepares us for searching for rational strategies.展开更多
Water splitting is important to the conversion and storage of renewable energy,but slow kinetics of the oxygen evolution reaction(OER)greatly limits its utility.Here,under visible light illumination,the p-n WO_(3)/SnS...Water splitting is important to the conversion and storage of renewable energy,but slow kinetics of the oxygen evolution reaction(OER)greatly limits its utility.Here,under visible light illumination,the p-n WO_(3)/SnSe_(2)(WS)heterojunction significantly activates OER catalysis of CoFe-layered double hydroxide(CF)/carbon nanotubes(CNTs).Specifically,the catalyst achieves an overpotential of 224 mV at 10 mA cm^(-2)and a small Tafel slope of 47 mV dec^(-1),superior to RuO_(2)and most previously reported transition metal-based OER catalysts.The p-n WS heterojunction shows strong light absorption to produce photogenerated carriers.The photogenerated holes are trapped by CF to suppresses the charge recombination and facilitate charge transfer,which accelerates OER kinetics and boost the activity for the OER.This work highlights the possibility of using heterojunctions to activate OER catalysis and advances the design of energy-efficient catalysts for water oxidation systems using solar energy.展开更多
Developing high efficient Pd-based electrocatalysts for oxygen reduction reaction(ORR) is still challenging for alkaline membrane fuel cell,since the strong oxygen adsorption energy and easy agglomerative intrinsic pr...Developing high efficient Pd-based electrocatalysts for oxygen reduction reaction(ORR) is still challenging for alkaline membrane fuel cell,since the strong oxygen adsorption energy and easy agglomerative intrinsic properties. In order to simultaneously solve these problems, Pd/Co_(3)O_(4)–N–C multidimensional materials with porous structures is designed as the ORR catalysts. In details, the ZIF-67 with polyhedral structure was firstly synthesized and then annealed at high-temperature to prepare the N-doped Co_(3)O_(4)carbon-based material, which was used to homogeneously confine Pd nanoparticles and obtained the Pd/Co_(3)O_(4)–N–C series catalysts. The formation of Co–N and C–N bond could provide efficient active sites for ORR. Simultaneously, the strong electronic interaction in the interface between the Pd and N-doped Co_(3)O_(4)could disperse and avoid the agglomeration of Pd nanoparticles and ensure the exposure of active sites, which is crucial to lower the energy barrier toward ORR and substantially enhance the ORR kinetics. Hence, the Pd/Co_(3)O_(4)–N–C nanocompounds exhibited excellent ORR catalytic performance, ideal Pd mass activity, and durability in 0.1 mol L-1KOH solution compared with Co_(3)O_(4)–N–C and Pd/C. The scalable synthesis method, relatively low cost, and excellent electrochemical ORR performance indicated that the obtained Pd/Co_(3)O_(4)–N–C electrocatalyst had the potential for application on fuel cells.展开更多
The mechanism of decomposition of calcium inosilicate(CaSiO_3) synthesized through chemical deposition method using analytical reagent NaSiO_3·9H_2O and CaCl_2 during the alkali fusion process using NaOH was inve...The mechanism of decomposition of calcium inosilicate(CaSiO_3) synthesized through chemical deposition method using analytical reagent NaSiO_3·9H_2O and CaCl_2 during the alkali fusion process using NaOH was investigated by Raman spectroscopy in situ,X-ray diffraction and Fourier transform infrared spectrometer(FTIR).The results show that the tetrahedral silica chains within CaSiO_3 are gradually disrupted and transformed into nesosilicate with the isolated SiO_4 tetrahedra at the beginning of the alkali fusion process.The three intermediates including Ca_2SiO_4,Na_2CaSiO_4 and Na_2SiO_3 appear simultaneously in the decomposition of CaSiO_3,while the final products are Ca(OH)_2 and Na_4SiO_4.It can be concluded that there exist two reaction pathways in the alkali fusion process of CaSiO_3:one is ion exchange,the other is in the main form of the framework structure change of silicate.The reaction pathway is led by silicate structure transformation in the alkali fusion process.展开更多
基金supported by the Fundamental Research Funds for the Central Universities (FRF-EYIT-23-07)。
文摘Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)technology,which enables carbon capture storage and resource utilization by reducing CO_(2) to valuable chemicals or fuels,has become a global research hotspot in recent decades.Among the many products of CO_(2)RR(carbon monoxide,acids,aldehydes and alcohols,olefins,etc.),alcohols(methanol,ethanol,propanol,etc.)have a higher market value and energy density,but it is also more difficult to produce.Copper is known to be effective in catalyzing CO_(2) to high valueadded alcohols,but with poor selectivity.The progress of Cu-based catalysts for the selective generation of alcohols,including copper oxides,bimetals,single atoms and composites is reviewed.Meanwhile,to improve Cu-based catalyst activity and modulate product selectivity,the modulation strategies are straighten out,including morphological regulation,crystalline surface,oxidation state,as well as elemental doping and defect engineering.Based on the research progress of electrocatalytic CO_(2) reduction for alcohol production on Cu-based materials,the reaction pathways and the key intermediates of the electrocatalytic CO_(2)RR to methanol,ethanol and propanol are summarized.Finally,the problems of traditional electrocatalytic CO_(2)RR are introduced,and the future applications of machine learning and theoretical calculations are prospected.An in-depth discussion and a comprehensive review of the reaction mechanism,catalyst types and regulation strategies were carried out with a view to promoting the development of electrocatalytic CO_(2)RR to alcohols.
基金financially supported by the National Natural Science Foundation of China(No.51965040)Science and Technology Project of Jiangxi Provincial Department of Transportation,China(No.2022H0048)。
文摘The interfacial reaction behavior of Al and Ti_3AlC_(2)at different pouring temperatures and its effect on the microstructure and mechanical properties of the composites were investigated.The results show that the addition of3.0 wt.%Ti_3AlC_(2)refines the average grain size ofα(Al)in the composite by 50.1%compared to Al6061 alloy.Morphological analyses indicate that an in-situ Al_(3Ti)transition layer of-180 nm in thickness is generated around the edge of Ti_3AlC_(2)at 720℃,forming a well-bonded Al-Al_(3Ti)interface.At this processing temperature,the ultimate tensile strength of A16061-3.0 wt.%Ti_3AlC_(2)composite is 199.2 MPa,an improvement of 41.5%over the Al6061 matrix.Mechanism analyses further elucidate that 720℃is favourable for forming the nano-sized transition layer at the Ti_3AlC_(2)edges.And,the thermal mismatch strengthening plays a dominant role in this state,with a strengthening contribution of about 74.8%.
基金Funded by the Doctoral Fund of Chengdu University(No.2081919131)the Sichuan Science and Technology Program(No.2023YFG0229)。
文摘Ni^(2+)/Cu^(2+)/SO_(4)^(2-)/polyvinyl alcohol precursor fibers with uniform diameters were prepared through electrospinning.Nickel-based composite nanoalloys containing Ni,Cu,and S were prepared through heat treatment in an Ar atmosphere.The experimental results show that the main components of the prepared nanoalloys are NiCu,Ni_(3)S_(2),Ni,and C.The nanoalloys exhibit fine grain sizes about 200-500 nm,which can increase with increasing heat treatment temperature.Electrochemical test results show that the nickel sulfidemodified NiCu nanoalloy composites exhibit excellent oxygen evolution reaction properties,and the oxygen evolution reaction properties gradually improve with the increasing heat treatment temperature.The sample prepared at 1 000℃ for 40 min show a low overpotential of 423 mV and a small Tafel slope of 134 mV·dec^(-1) at a current density of 10 mA·cm^(-2).
基金the National Natural Science Foundation of China (Grant No.12002045)State Key Laboratory of Explosion Science and Technology,Beijing Institute of Technology (Grant No.QNKT22-09)。
文摘A ternary system of PTFE/Al/Bi_(2)O_(3)is constructed by incorporating PTFE-based reactive material and thermite for enhancing the energy release of the PTFE-based reactive material.The effects of Bi_(2)O_(3)in the PTFE/Al/Bi_(2)O_(3)on both mechanical properties and the energy release were investigated through various tests such as thermogravimetry-differential scanning calorimetry,adiabatic oxygen bomb test and split Hopkinson pressure bar test.The microstructure observed through scanning electron microscope and Xray diffraction results are used to analyze the ignition and reaction mechanism of PTFE/Al/Bi_(2)O_(3).The results indicate that the PTFE/Al/Bi_(2)O_(3)are capable of triggering the exothermic reaction of molten PTFE/Bi_(2)O_(3)and Al/Bi_(2)O_(3)over the PTFE/Al reactive materials,thereby promoting reactions.The excessive aluminum in the ternary system is beneficial for increasing energy release.The ignition of shock-induced chemical reactions in PTFE/Al/Bi_(2)O_(3)is closely related to the material fracture.The dominant mechanism for hot-spot generation under Split Hopkinson Pressure Bar test is the frictional temperature rise at the microcrack after failure.
基金Taishan Scholars Program of Shandong Province,Grant/Award Number:tsqn201812068Higher School Youth Innovation Team of Shandong Province,Grant/Award Number:2019KJA013+1 种基金The Opening Fund of State Key Laboratory of Heavy Oil Processing,Grant/Award Number:SKLOP202002006National Natural Science Foundation of China,Grant/Award Number:51872173。
文摘The reduction of molecular nitrogen(N_(2))to ammonia(NH_(3))under mild conditions is one of the most promising studies in the energy field due to the important role of NH_(3)in modern industry,production,and life.The photocatalytic reduction of N_(2)is expected to achieve clean and sustainable NH_(3)production by using clean solar energy.To date,the new photocatalysts for photocatalytic reduction of N_(2)to NH_(3)at room temperature and atmospheric pressure have not been fully developed.The major challenge is to achieve high light-absorption efficiency,conversion efficiency,and stability of photocatalysts.Herein,the methods for measuring produced NH_(3)are compared,and the problems related to possible NH_(3)pollution in photocatalytic systems are mentioned to provide accurate ideas for measuring photocatalytic efficiency.The recent progress of nitrogen reduction reaction(NRR)photocatalysts at ambient temperature and pressure is summarized by introducing charge transfer,migration,and separation in photocatalytic NRR,which provides a guidance for the selection of future photocatalyst.More importantly,we introduce the latest research strategies of photocatalysts in detail,which can guide the preparation and design of photocatalysts with high NRR activity.
基金supported by the grants from the Research Grants Council of the Hong Kong Special Administrative Region,China (Project No. 16205721)Guangdong Basic and Applied Basic Research Foundation (Project No.2021A1515011815)Poly U Start-up Fund (Project No. 1-BDC4)。
文摘Water electrolysis is considered as one most promising technique for hydrogen production.The high efficiency electrocatalyst is the key to accelerating the sluggish kinetics of the hydrogen evolution reaction(HER) in alkaline media.In this work,an efficient HER electrocatalyst with hetero-interfacial metal-metal oxide structure was constructed through a redox solid phase reaction(SPR) strategy.During the annealing process under Ar atmosphere,RuO_(2) and WS_(2)in RuO_(2)/WS_(2)precursor were converted to Ru nanoparticles(NPs) and WO3in situ,where tiny Ru NPs and oxygen vacancies were uniformly distributed onto the newly formed WO3nanosheets.Different characterization techniques were adopted to confirm the successful formation of Ru/WO_(3)electrocatalyst(RWOC).The optimized RWOC sample annealed at 400℃ exhibited the low overpotential value of 13 mV at a current density of 10 mA cm^(-2)and strong durability under the alkaline condition.Density functional theoretical calculations further revealed that the promoted adsorption/desorption rate of reaction intermediates and the accelerated kinetics of HER process were deduced to the synergistic effect between Ru and WO_(3)in electrocatalyst.This work provides a feasible method to fabricate highly efficient HER electrocatalysts.
基金supported by a Grant of the Innovation and Technology Commission of Hong Kong(Project number:ITS/461/18)City University of Hong Kong(Project number:9678179).
文摘Transition metal-nitrogen-carbon materials(M-N-Cs),particularly Fe-N-Cs,have been found to be electroactive for accelerating oxygen reduction reaction(ORR)kinetics.Although substantial efforts have been devoted to design Fe-N-Cs with increased active species content,surface area,and electronic conductivity,their performance is still far from satisfactory.Hitherto,there is limited research about regulation on the electronic spin states of Fe centers for Fe-N-Cs electrocatalysts to improve their catalytic performance.Here,we introduce Ti_(3)C_(2) MXene with sulfur terminals to regulate the electronic configuration of FeN_(4) species and dramatically enhance catalytic activity toward ORR.The MXene with sulfur terminals induce the spin-state transition of FeN_(4) species and Fe 3d electron delocalization with d band center upshift,enabling the Fe(II)ions to bind oxygen in the end-on adsorption mode favorable to initiate the reduction of oxygen and boosting oxygen-containing groups adsorption on FeN_(4) species and ORR kinetics.The resulting FeN_(4)-Ti_(3)C_(2)Sx exhibits comparable catalytic performance to those of commercial Pt-C.The developed wearable ZABs using FeN_(4)-Ti_(3)C_(2)Sx also exhibit fast kinetics and excellent stability.This study confirms that regulation of the electronic structure of active species via coupling with their support can be a major contributor to enhance their catalytic activity.
基金supported through the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(2022M3H4A1A04096478)the support from the Supercomputing Center of Wuhan University。
文摘Electrocatalyst designs based on oxophilic foreign atoms are considered a promising approach for developing efficient pH-universal hydrogen evolution reaction(HER)electrocatalysts by overcoming the sluggish alkaline HER kinetics.Here,we design ternary transition metals-based nickel telluride(Mo WNi Te)catalysts consisting of high valence non-3d Mo and W metals and oxophilic Te as a first demonstration of non-precious heterogeneous electrocatalysts following the bifunctional mechanism.The Mo WNi Te showed excellent HER catalytic performance with overpotentials of 72,125,and 182 mV to reach the current densities of 10,100,and 1000 mA cm^(-2),respectively,and the corresponding Tafel slope of 47,52,and 58 mV dec-1in alkaline media,which is much superior to commercial Pt/C.Additionally,the HER performance of Mo WNi Te is well maintained up to 3000 h at the current density of 100 mA cm^(-2).It is further demonstrated that the Mo WNi Te exhibits remarkable HER activities with an overpotential of 45 mV(31 mV)and Tafel slope of 60 mV dec-1(34 mV dec-1)at 10 mA cm^(-2)in neutral(acid)media.The superior HER performance of Mo WNi Te is attributed to the electronic structure modulation,inducing highly active low valence states by the incorporation of high valence non-3d transition metals.It is also attributed to the oxophilic effect of Te,accelerating water dissociation kinetics through a bifunctional catalytic mechanism in alkaline media.Density functional theory calculations further reveal that such synergistic effects lead to reduced free energy for an efficient water dissociation process,resulting in remarkable HER catalytic performances within universal pH environments.
基金supported by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Advanced Manufacturing Officesupported by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Advanced Manufacturing Office, under Contract No. DE-SC0012704+1 种基金supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract DE-AC02-06CH11357supported by the Vehicle Technologies Office of the U.S. Department of Energy。
文摘Nickel-rich transition-metal oxides are widely regarded as promising cathode materials for high-energydensity lithium-ion batteries for emerging electric vehicles. However, achieving high energy density in Ni-rich cathodes is accompanied by substantial safety and cycle-life obstacles. The major issues of Ni-rich cathodes at high working potentials are originated from the unstable cathode-electrolyte interface, while the underlying mechanism of parasitic reactions towards surface reconstructions of cathode materials is not well understood. In this work, we controlled the Li_(2)CO_(3) impurity content on LiNi_(0.83)Mn_(0.1)Co_(0.07)O_(2) cathodes using air, tank-air, and O_(2) synthesis environments. Home-built high-precision leakage current and on-line electrochemical mass spectroscopy experiments verify that Li_(2)CO_(3) impurity is a significant promoter of parasitic reactions on Ni-rich cathodes. The rate of parasitic reactions is strongly correlated to Li_(2)CO_(3) content and severe performance deterioration of Ni83 cathodes.The post-mortem characterizations via high-resolution transition electron microscope and X-ray photoelectron spectroscopy depth profiles reveal that parasitic reactions promote more Ni reduction and O deficiency and even rock-salt phase transformation at the surface of cathode materials. Our observation suggests that surface reconstructions have a strong affiliation to parasitic reactions that create chemically acidic environment to etch away the lattice oxygen and offer the electrical charge to reduce the valence state of transition metal. Thus, this study advances our understanding on surface reconstructions of Nirich cathodes and prepares us for searching for rational strategies.
基金the National Natural Science Foundation of China(No.41807213)the Hydrogeo-logical Survey Project of Huangshui River(No.DD20190331).
文摘Water splitting is important to the conversion and storage of renewable energy,but slow kinetics of the oxygen evolution reaction(OER)greatly limits its utility.Here,under visible light illumination,the p-n WO_(3)/SnSe_(2)(WS)heterojunction significantly activates OER catalysis of CoFe-layered double hydroxide(CF)/carbon nanotubes(CNTs).Specifically,the catalyst achieves an overpotential of 224 mV at 10 mA cm^(-2)and a small Tafel slope of 47 mV dec^(-1),superior to RuO_(2)and most previously reported transition metal-based OER catalysts.The p-n WS heterojunction shows strong light absorption to produce photogenerated carriers.The photogenerated holes are trapped by CF to suppresses the charge recombination and facilitate charge transfer,which accelerates OER kinetics and boost the activity for the OER.This work highlights the possibility of using heterojunctions to activate OER catalysis and advances the design of energy-efficient catalysts for water oxidation systems using solar energy.
基金funded by National Natural Science Foundation of China (21975129)Natural Science Foundation of Jiangsu Province (BK20190759)+1 种基金Nanjing Forestry UniversityPostgraduate Research & Practice Innovation Program of Jiangsu Province (SJCX21_0337)。
文摘Developing high efficient Pd-based electrocatalysts for oxygen reduction reaction(ORR) is still challenging for alkaline membrane fuel cell,since the strong oxygen adsorption energy and easy agglomerative intrinsic properties. In order to simultaneously solve these problems, Pd/Co_(3)O_(4)–N–C multidimensional materials with porous structures is designed as the ORR catalysts. In details, the ZIF-67 with polyhedral structure was firstly synthesized and then annealed at high-temperature to prepare the N-doped Co_(3)O_(4)carbon-based material, which was used to homogeneously confine Pd nanoparticles and obtained the Pd/Co_(3)O_(4)–N–C series catalysts. The formation of Co–N and C–N bond could provide efficient active sites for ORR. Simultaneously, the strong electronic interaction in the interface between the Pd and N-doped Co_(3)O_(4)could disperse and avoid the agglomeration of Pd nanoparticles and ensure the exposure of active sites, which is crucial to lower the energy barrier toward ORR and substantially enhance the ORR kinetics. Hence, the Pd/Co_(3)O_(4)–N–C nanocompounds exhibited excellent ORR catalytic performance, ideal Pd mass activity, and durability in 0.1 mol L-1KOH solution compared with Co_(3)O_(4)–N–C and Pd/C. The scalable synthesis method, relatively low cost, and excellent electrochemical ORR performance indicated that the obtained Pd/Co_(3)O_(4)–N–C electrocatalyst had the potential for application on fuel cells.
基金Project(20112120120003)supported by the Science and Technology Projects of Ministry of Education of ChinaProject(L2014120)supported by the Educational Commission of Liaoning Province,China
文摘The mechanism of decomposition of calcium inosilicate(CaSiO_3) synthesized through chemical deposition method using analytical reagent NaSiO_3·9H_2O and CaCl_2 during the alkali fusion process using NaOH was investigated by Raman spectroscopy in situ,X-ray diffraction and Fourier transform infrared spectrometer(FTIR).The results show that the tetrahedral silica chains within CaSiO_3 are gradually disrupted and transformed into nesosilicate with the isolated SiO_4 tetrahedra at the beginning of the alkali fusion process.The three intermediates including Ca_2SiO_4,Na_2CaSiO_4 and Na_2SiO_3 appear simultaneously in the decomposition of CaSiO_3,while the final products are Ca(OH)_2 and Na_4SiO_4.It can be concluded that there exist two reaction pathways in the alkali fusion process of CaSiO_3:one is ion exchange,the other is in the main form of the framework structure change of silicate.The reaction pathway is led by silicate structure transformation in the alkali fusion process.
