The electron configuration of the active sites can be effectively modulated by regulating the inherent nanostructure of the electrocatalysts,thereby enhancing their electrocatalytic performance.To tackle the unexplore...The electron configuration of the active sites can be effectively modulated by regulating the inherent nanostructure of the electrocatalysts,thereby enhancing their electrocatalytic performance.To tackle the unexplored challenge of substantial electrochemical overpotential,surface reconstruction has emerged as a necessary strategy.Focusing on key aspects such as Janus structures,overflow effects,the d-band center displacement hypothesis,and interface coupling related to electrochemical reactions is essential for water electrolysis.Emerging as frontrunners among next-generation electrocatalysts,Mott-Schottky(M-S)catalysts feature a heterojunction formed between a metal and a semiconductor,offering customizable and predictable interfacial synergy.This review offers an in-depth examination of the processes driving the hydrogen and oxygen evolution reactions(HER and OER),highlighting the benefits of employing nanoscale transition metal nitrides,carbides,oxides,and phosphides in M-S heterointerface catalysts.Furthermore,the challenges,limitations,and future prospects of employing M-S heterostructured catalysts for water splitting are thoroughly discussed.展开更多
Plant species diversity is one of the most widely used indicators in ecosystem management.The relation of species diversity with the size of the sample plot has not been fully determined for Oriental beech forests(Fag...Plant species diversity is one of the most widely used indicators in ecosystem management.The relation of species diversity with the size of the sample plot has not been fully determined for Oriental beech forests(Fagus orientalis Lipsky),a widespread species in the Hyrcanian region.Assessing the impacts of plot size on species diversity is fundamental for an ecosystem-based approach to forest management.This study determined the relation of species diversity and plot size by investigating species richness and abundance of both canopy and forest floor.Two hundred and fifty-six sample plots of 625 m^(2) each were layout in a grid pattern across 16 ha.Base plots(25 m×25 m)were integrated in different scales to investigate the effect of plot size on species diversity.The total included nine plots of 0.063,0.125,0.188,0.250,0.375,0.500,0.563,0.750 and 1 ha.Ten biodiversity indices were calculated.The results show that species richness in the different plot sizes was less than the actual value.The estimated value of the Simpson species diversity index was not significantly different from actual values for both canopy and forest floor diversity.The coefficient of variation of this index for the 1-ha sample plot showed the lowest amount across different plot sizes.Inverse Hill species diversity was insignificant difference across different plot sizes with an area greater than 0.500 ha.The modified Hill evenness index for the 1-ha sample size was a correct estimation of the 16-ha for both canopy and forest floor;however,the precision estimation was higher for the canopy layer.All plots greater than 0.250-ha provided an accurate estimation of the Camargo evenness index for forest floor species,but was inaccurate across different plot sizes for the canopy layer.The results indicate that the same plot size did not have the same effect across species diversity measurements.Our results show that correct estimation of species diversity measurements is related to the selection of appropriate indicators and plot size to increase the accuracy of the estimate so that the cost and time of biodiversity management may be reduced.展开更多
Understanding local variation in forest biomass allows for a better evaluation of broad-scale patterns and interpretation of forest ecosystems’role in carbon dynamics.This study focuses on patterns of aboveground tre...Understanding local variation in forest biomass allows for a better evaluation of broad-scale patterns and interpretation of forest ecosystems’role in carbon dynamics.This study focuses on patterns of aboveground tree biomass within a fully censused 20 ha forest plot in a temperate forest of northern Alabama,USA.We evaluated the relationship between biomass and topography using ridge and valley landforms along with digitally derived moisture and solar radiation indices.Every live woody stem over 1 cm diameter at breast height within this plot was mapped,measured,and identified to species in 2019-2022,and diameter data were used along with speciesspecific wood density to map the aboveground biomass at the scale of 20 m×20 m quadrats.The aboveground tree biomass was 211 Mg·ha^(-1).Other than small stream areas that experienced recent natural disturbances,the total stand biomass was not associated with landform or topographic indices.Dominant species,in contrast,had strong associations with topography.American beech(Fagus grandifolia)and yellow-poplar(Liriodendron tulipfera)dominated the valley landform,with 37% and 54% greater biomass in the valley than their plot average,respectively.Three other dominant species,white oak(Quercus alba),southern shagbark hickory(Carya carolinaeseptentrionalis),and white ash(Fraxinus americana),were more abundant on slopes and benches,thus partitioning the site.Of the six dominant species,only sugar maple(Acer saccharum)was not associated with landform.Moreover,both topographic wetness and potential radiation indices were significant predictors of dominant species biomass within each of the landforms.The study highlights the need to consider species when examining forest productivity in a range of site conditions.展开更多
Lithium-oxygen batteries(LOBs)with high energy density are a promising advanced energy storage technology.However,the slow cathodic redox kinetics during cycling causes the discharge products to fail to decompose in t...Lithium-oxygen batteries(LOBs)with high energy density are a promising advanced energy storage technology.However,the slow cathodic redox kinetics during cycling causes the discharge products to fail to decompose in time,resulting in large polarization and battery failure in a short time.Therefore,a self-supporting interconnected nanosheet array network NiCo_(2)O_(4)/MnO_(2)with a Mott-Schottky heterostructure on titanium paper(TP-NCO/MO)is ingeniously designed as an efficient cathode catalyst material for LOBs.This heterostructure can accelerate electron transfer and influence the charge transfer process during adsorption of intermediate by triggering the interface disturbance at the heterogeneous interface,thus accelerating oxygen reduction and oxygen evolution kinetics and regulating product decomposition,which is expected to solve the above problems.The meticulously designed unique structural advantages enable the TP-NCO/MO cathode catalyst to exhibit an astounding ultra-long cycle life of 800 cycles and an extraordinarily low overpotential of 0.73 V.This study utilizes a simple method to cleverly regulate the morphology of the discharge products by constructing a Mott-Schottky heterostructure,providing important reference for the design of efficient catalysts aimed at optimizing the adsorption of reaction intermediates.展开更多
The disparity in the transfer of carriers(electrons/mass)during the reaction in zinc-air batteries(ZABs)results in sluggish kinetics of the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER),along with e...The disparity in the transfer of carriers(electrons/mass)during the reaction in zinc-air batteries(ZABs)results in sluggish kinetics of the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER),along with elevated overpotentials,thereby imposing additional constraints on its utilization.Therefore,the pre-design and target-development of inexpensive,high-performance,and long-term stable bifunctional catalysts are urgently needed.In this work,an apically guiding dual-functional electrocatalyst(Ag-FeN_(x)-N-C)was prepared,in which a hierarchical porous nitrogen-doped carbon with three-dimensional(3D)hollow star-shaped structure is used as a substrate and high-conductivity Ag nanoparticles are coupled with iron nitride(FeN_(x))nanoparticles.Theoretical calculations indicate that the Mott-Schottky heterojunction as an inherent electric field comes from the two-phase bound of Ag and FeN_(x),of which electron accumulation in the FeN_(x)phase region and electron depletion in the Ag phase region promote orientated-guiding charge migration.The effective modulation of local electronic structures felicitously reforms the d-band electron-group distribution,and intellectually tunes the masstransfer reaction energy barriers for both ORR/OER.Additionally,the hollow star-s haped hierarchical porous structure provides an apical region for fast mass transfer.Experimental results show that the halfwave potential for ORR is 0.914 V,and the overpotential for OER is only 327 mV at 10 mA cm^(-2).A rechargeable ZAB with Ag-FeN_(x)-N-C as the air cathode demonstrates long-term cycling performance exceeding 1500 cycles(500 h),with a power density of 180 mW cm^(-2).Moreover,when employing AgFeN_(x)-N-C as the air cathode,flexible ZABs demonstrate a notable open-circuit voltage of 1.42 V and achieve a maximum power density of 65.6 mW cm^(-2).Ag-FeN_(x)-N-C shows guiding electron/mass transfer route and apical reaction microenvironment for the electrocatalyst architecture in the exploration prospects of ZABs.展开更多
Vacancy engineering and Mott-Schottky heterostructure can accelerate charge transfer,regulate adsorption energy of reaction intermediates,and provide additional active sites,which are regarded as valid means for impro...Vacancy engineering and Mott-Schottky heterostructure can accelerate charge transfer,regulate adsorption energy of reaction intermediates,and provide additional active sites,which are regarded as valid means for improving catalytic activity.However,the underlying mechanism of synergistic regulation of interfacial charge transfer and optimization of electrocatalytic activity by combining vacancy and Mott-Schottky junction remains unclear.Herein,the growth of a bifunctional NiCo/NiCoP Mott-Schottky electrode with abundant phosphorus vacancies on foam nickel(NF)has been synthesized through continuous phosphating and reduction processes.The obtained NiCo/NiCoP heterojunctions show remarkable OER and HER activities,and the overpotentials for OER and HER are as low as 117 and 60 mV at 10 mA/cm^(2) in 1 mol/L KOH,respectively.Moreover,as both the cathode and anode of overall water splitting,the voltage of the bifunctional NiCo/NiCoP electrocatalyst is 1.44 V at 10 mA/cm^(2),which are far exceeding the benchmark commercial electrodes.DFT theoretical calculation results confirm that the phosphorus vacancies and build-in electric field can effectively accelerate ion and electron transfer between NiCo alloy and NiCoP semiconductor,tailor the electronic structure of the metal centers and lower the Gibbs free energy of the intermediates.Furthermore,the unique self-supported integrated structure is beneficial to facilitate the exposure of the active site,avoid catalyst shedding,thus improving the activity and structural stability of NiCo/NiCoP.This study provides an avenue for the controllable synthesis and performance optimization of Mott-Schottky electrocatalysts.展开更多
基金supported by the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(2021L574)the Guizhou Provincial Science and Technology Foundation([2024]ZK General 425 and 438)+1 种基金the National Natural Science Foundation of China(22309033)the Academic Young Talent Foundation of Guizhou Normal University([2022]B05 and B06)。
文摘The electron configuration of the active sites can be effectively modulated by regulating the inherent nanostructure of the electrocatalysts,thereby enhancing their electrocatalytic performance.To tackle the unexplored challenge of substantial electrochemical overpotential,surface reconstruction has emerged as a necessary strategy.Focusing on key aspects such as Janus structures,overflow effects,the d-band center displacement hypothesis,and interface coupling related to electrochemical reactions is essential for water electrolysis.Emerging as frontrunners among next-generation electrocatalysts,Mott-Schottky(M-S)catalysts feature a heterojunction formed between a metal and a semiconductor,offering customizable and predictable interfacial synergy.This review offers an in-depth examination of the processes driving the hydrogen and oxygen evolution reactions(HER and OER),highlighting the benefits of employing nanoscale transition metal nitrides,carbides,oxides,and phosphides in M-S heterointerface catalysts.Furthermore,the challenges,limitations,and future prospects of employing M-S heterostructured catalysts for water splitting are thoroughly discussed.
基金funded by Gorgan University of Agricultural Sciences and Natural Resources(grant number 9318124503).
文摘Plant species diversity is one of the most widely used indicators in ecosystem management.The relation of species diversity with the size of the sample plot has not been fully determined for Oriental beech forests(Fagus orientalis Lipsky),a widespread species in the Hyrcanian region.Assessing the impacts of plot size on species diversity is fundamental for an ecosystem-based approach to forest management.This study determined the relation of species diversity and plot size by investigating species richness and abundance of both canopy and forest floor.Two hundred and fifty-six sample plots of 625 m^(2) each were layout in a grid pattern across 16 ha.Base plots(25 m×25 m)were integrated in different scales to investigate the effect of plot size on species diversity.The total included nine plots of 0.063,0.125,0.188,0.250,0.375,0.500,0.563,0.750 and 1 ha.Ten biodiversity indices were calculated.The results show that species richness in the different plot sizes was less than the actual value.The estimated value of the Simpson species diversity index was not significantly different from actual values for both canopy and forest floor diversity.The coefficient of variation of this index for the 1-ha sample plot showed the lowest amount across different plot sizes.Inverse Hill species diversity was insignificant difference across different plot sizes with an area greater than 0.500 ha.The modified Hill evenness index for the 1-ha sample size was a correct estimation of the 16-ha for both canopy and forest floor;however,the precision estimation was higher for the canopy layer.All plots greater than 0.250-ha provided an accurate estimation of the Camargo evenness index for forest floor species,but was inaccurate across different plot sizes for the canopy layer.The results indicate that the same plot size did not have the same effect across species diversity measurements.Our results show that correct estimation of species diversity measurements is related to the selection of appropriate indicators and plot size to increase the accuracy of the estimate so that the cost and time of biodiversity management may be reduced.
基金supported in part by the intramural research program of the US Department of Agriculture,National Institute of Food and Agriculture,Evans-Allen#1024525,and Capacity Building Grant#006531supported in part by the US National Science Foundation RII Track 2 FEC:Leveraging Intelligent Informatics and Smart Data for Improved Understanding of Northern Forest Ecosystem Resiliency(INSPIRES)#1920908by The Lyndhurst Foundation.
文摘Understanding local variation in forest biomass allows for a better evaluation of broad-scale patterns and interpretation of forest ecosystems’role in carbon dynamics.This study focuses on patterns of aboveground tree biomass within a fully censused 20 ha forest plot in a temperate forest of northern Alabama,USA.We evaluated the relationship between biomass and topography using ridge and valley landforms along with digitally derived moisture and solar radiation indices.Every live woody stem over 1 cm diameter at breast height within this plot was mapped,measured,and identified to species in 2019-2022,and diameter data were used along with speciesspecific wood density to map the aboveground biomass at the scale of 20 m×20 m quadrats.The aboveground tree biomass was 211 Mg·ha^(-1).Other than small stream areas that experienced recent natural disturbances,the total stand biomass was not associated with landform or topographic indices.Dominant species,in contrast,had strong associations with topography.American beech(Fagus grandifolia)and yellow-poplar(Liriodendron tulipfera)dominated the valley landform,with 37% and 54% greater biomass in the valley than their plot average,respectively.Three other dominant species,white oak(Quercus alba),southern shagbark hickory(Carya carolinaeseptentrionalis),and white ash(Fraxinus americana),were more abundant on slopes and benches,thus partitioning the site.Of the six dominant species,only sugar maple(Acer saccharum)was not associated with landform.Moreover,both topographic wetness and potential radiation indices were significant predictors of dominant species biomass within each of the landforms.The study highlights the need to consider species when examining forest productivity in a range of site conditions.
基金the financial support from the National Natural Science Foundation of China (grant nos. 51971184 and 51931006)the Natural Science Foundation of Fujian Province of China (no. 2023J01033)+1 种基金the Fundamental Research Funds for the Central Universities of China (Xiamen University: no. 20 720 200 068)the “Double First Class” Foundation of Materials Intelligent Manufacturing Discipline of Xiamen University
文摘Lithium-oxygen batteries(LOBs)with high energy density are a promising advanced energy storage technology.However,the slow cathodic redox kinetics during cycling causes the discharge products to fail to decompose in time,resulting in large polarization and battery failure in a short time.Therefore,a self-supporting interconnected nanosheet array network NiCo_(2)O_(4)/MnO_(2)with a Mott-Schottky heterostructure on titanium paper(TP-NCO/MO)is ingeniously designed as an efficient cathode catalyst material for LOBs.This heterostructure can accelerate electron transfer and influence the charge transfer process during adsorption of intermediate by triggering the interface disturbance at the heterogeneous interface,thus accelerating oxygen reduction and oxygen evolution kinetics and regulating product decomposition,which is expected to solve the above problems.The meticulously designed unique structural advantages enable the TP-NCO/MO cathode catalyst to exhibit an astounding ultra-long cycle life of 800 cycles and an extraordinarily low overpotential of 0.73 V.This study utilizes a simple method to cleverly regulate the morphology of the discharge products by constructing a Mott-Schottky heterostructure,providing important reference for the design of efficient catalysts aimed at optimizing the adsorption of reaction intermediates.
基金the financial support of the National Natural Science Foundation of China(52002079,22378074,22179025 and U20A20340)the Guangdong Basic and Applied Basic Research Foundation(2022A1515140085)+2 种基金the Research Fund Program of Guangdong Provincial Key Laboratory of Fuel Cell Technology(FC202209)the Guangzhou Hongmian Project(HMJH-20200012)the Foshan Introducing Innovative and Entrepreneurial Teams(1920001000108)。
文摘The disparity in the transfer of carriers(electrons/mass)during the reaction in zinc-air batteries(ZABs)results in sluggish kinetics of the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER),along with elevated overpotentials,thereby imposing additional constraints on its utilization.Therefore,the pre-design and target-development of inexpensive,high-performance,and long-term stable bifunctional catalysts are urgently needed.In this work,an apically guiding dual-functional electrocatalyst(Ag-FeN_(x)-N-C)was prepared,in which a hierarchical porous nitrogen-doped carbon with three-dimensional(3D)hollow star-shaped structure is used as a substrate and high-conductivity Ag nanoparticles are coupled with iron nitride(FeN_(x))nanoparticles.Theoretical calculations indicate that the Mott-Schottky heterojunction as an inherent electric field comes from the two-phase bound of Ag and FeN_(x),of which electron accumulation in the FeN_(x)phase region and electron depletion in the Ag phase region promote orientated-guiding charge migration.The effective modulation of local electronic structures felicitously reforms the d-band electron-group distribution,and intellectually tunes the masstransfer reaction energy barriers for both ORR/OER.Additionally,the hollow star-s haped hierarchical porous structure provides an apical region for fast mass transfer.Experimental results show that the halfwave potential for ORR is 0.914 V,and the overpotential for OER is only 327 mV at 10 mA cm^(-2).A rechargeable ZAB with Ag-FeN_(x)-N-C as the air cathode demonstrates long-term cycling performance exceeding 1500 cycles(500 h),with a power density of 180 mW cm^(-2).Moreover,when employing AgFeN_(x)-N-C as the air cathode,flexible ZABs demonstrate a notable open-circuit voltage of 1.42 V and achieve a maximum power density of 65.6 mW cm^(-2).Ag-FeN_(x)-N-C shows guiding electron/mass transfer route and apical reaction microenvironment for the electrocatalyst architecture in the exploration prospects of ZABs.
基金financially supported by the National Natural Science Foundation of China(NSFC,Nos.22269015,22205119)Natural Science Foundation of Inner Mongolia Autonomous Region of China(Nos.2021ZD11,2019BS02015).
文摘Vacancy engineering and Mott-Schottky heterostructure can accelerate charge transfer,regulate adsorption energy of reaction intermediates,and provide additional active sites,which are regarded as valid means for improving catalytic activity.However,the underlying mechanism of synergistic regulation of interfacial charge transfer and optimization of electrocatalytic activity by combining vacancy and Mott-Schottky junction remains unclear.Herein,the growth of a bifunctional NiCo/NiCoP Mott-Schottky electrode with abundant phosphorus vacancies on foam nickel(NF)has been synthesized through continuous phosphating and reduction processes.The obtained NiCo/NiCoP heterojunctions show remarkable OER and HER activities,and the overpotentials for OER and HER are as low as 117 and 60 mV at 10 mA/cm^(2) in 1 mol/L KOH,respectively.Moreover,as both the cathode and anode of overall water splitting,the voltage of the bifunctional NiCo/NiCoP electrocatalyst is 1.44 V at 10 mA/cm^(2),which are far exceeding the benchmark commercial electrodes.DFT theoretical calculation results confirm that the phosphorus vacancies and build-in electric field can effectively accelerate ion and electron transfer between NiCo alloy and NiCoP semiconductor,tailor the electronic structure of the metal centers and lower the Gibbs free energy of the intermediates.Furthermore,the unique self-supported integrated structure is beneficial to facilitate the exposure of the active site,avoid catalyst shedding,thus improving the activity and structural stability of NiCo/NiCoP.This study provides an avenue for the controllable synthesis and performance optimization of Mott-Schottky electrocatalysts.
