Fe-N-doped carbon materials(Fe-N-C)are promising candidates for oxygen reduction reaction(ORR)relative to Pt-based catalysts in proton exchange membrane fuel cells(PEMFCs).However,the intrinsic contributions of Fe-N_(...Fe-N-doped carbon materials(Fe-N-C)are promising candidates for oxygen reduction reaction(ORR)relative to Pt-based catalysts in proton exchange membrane fuel cells(PEMFCs).However,the intrinsic contributions of Fe-N_(4)moiety with different chemical/spin states(e.g.D1,D2,D3)to ORR are unclear since various states coexist inevitably.In the present work,Fe-N-C core-shell nanocatalyst with single lowspin Fe(Ⅱ)-N_(4)species(D1)is synthesized and identified with ex-situ ultralow temperature Mossbauer spectroscopy(T=1.6 K)that could essentially differentiate various Fe-N_(4)states and invisible Fe-O species.By quantifying with CO-pulse chemisorption,site density and turnover frequency of Fe-N-C catalysts reach 2.4×10^(-9)site g^(-1)and 23 e site~(-1)s^(-1)during the ORR,respectively.Half-wave potential(0.915V_(RHE))of the Fe-N-C catalyst is more positive(approximately 54 mV)than that of Pt/C.Moreover,we observe that the performance of PEMFCs on Fe-N-C almost achieves the 2025 target of the US Department of Energy by demonstrating a current density of 1.037 A cm^(-2)combined with the peak power density of 0,685 W cm^(-2),suggesting the critical role of Fe(Ⅱ)-N_(4)site(D1).After 500 h of running,PEMFCs still deliver a power density of 1.26 W cm^(-2)at 1.0 bar H_(2)-O_(2),An unexpected rate-determining step is figured out by isotopic labelling experiment and theoretical calculation.This work not only offers valuable insights regarding the intrinsic contribution of Fe-N_(4)with a single spin state to alkaline/acidic ORR,but also provides great opportunities for developing high-performance stable PEMFCs.展开更多
Metal-free carbon,as the most representative heterogeneous metal-free catalysts,have received considerable interests in electro-and thermo-catalytic reac-tions due to their impressive performance and sustainability.Ov...Metal-free carbon,as the most representative heterogeneous metal-free catalysts,have received considerable interests in electro-and thermo-catalytic reac-tions due to their impressive performance and sustainability.Over the past decade,well-designed carbon catalysts with tunable structures and heteroatom groups coupled with various characterization techniques have proposed numerous reaction mechanisms.However,active sites,key intermediate species,precise structure-activity relationships and dynamic evolution processes of carbon catalysts are still rife with controversies due to the monotony and limitation of used experimental methods.In this Review,we sum-marize the extensive efforts on model catalysts since the 2000s,particularly in the past decade,to overcome the influences of material and structure limitations in metal-free carbon catalysis.Using both nanomolecule model and bulk model,the real contribution of each alien species,defect and edge configuration to a series of fundamentally important reactions,such as thermocatalytic reactions,electrocatalytic reactions,were systematically studied.Combined with in situ techniques,isotope labeling and size control,the detailed reaction mechanisms,the precise 2D structure-activity relationships and the rate-determining steps were revealed at a molecular level.Furthermore,the outlook of model carbon catalysis has also been proposed in this work.展开更多
The carbon-based metal-free materials as catalysts(named as carbocatalysts) have been attracting tremendous attentions in electric-,solar-and thermal-driven reactions nowadays.Compared to electrocatalysis and photocat...The carbon-based metal-free materials as catalysts(named as carbocatalysts) have been attracting tremendous attentions in electric-,solar-and thermal-driven reactions nowadays.Compared to electrocatalysis and photocatalysis,the thermal-driven catalysis(thermocatalysis) including liquid phase and gas phase reactions involves wider scope and is relatively easy to realize practical large-scale applications.Over the past several years,some striking achievements on the design of new carbon-based metal-free materials with well-defined structures and heteroatom groups as well as the revelation of new reaction mechanisms and active sites in thermocatalysis have been obtained.However,comparative discussions regarding these recent achievements have been rarely highlighted.In this review,we systematically summarize and discuss six kinds of carbocatalysts and their applications in thermocatalysis.These materials include typical oxygen-attached carbon,surface modified carbon(graft with certain organic compounds),mono-doped carbon,co-doped carbon,carbon nitride and materials with carbon as dopant.Some new reaction processes as well as the related reaction mechanisms,active sites and intermediates are reviewed critically.Moreover,an outlook on the in-depth investigation of the metalfree carbocatalysis in the future is provided.展开更多
Phytoplankton growth rates and mortality rates were experimentally examined at 21 stations during the 2017 spring intermonsoon(April to early May)in the northern and central South China Sea(SCS)using the dilution tech...Phytoplankton growth rates and mortality rates were experimentally examined at 21 stations during the 2017 spring intermonsoon(April to early May)in the northern and central South China Sea(SCS)using the dilution technique,with emphasis on a comparison between the northern and central SCS areas which had different environmental factors.There had been higher temperature but lower nutrients and chlorophyll a concentrations in the central SCS than those in the northern SCS.The mean rates of phytoplankton growth(μ0)and microzooplankton grazing(m)were(0.88±0.33)d–1 and(0.55±0.22)d–1 in the central SCS,and both higher than those in the northern SCS with the values ofμ0((0.81±0.16)d–1)and m((0.30±0.09)d–1),respectively.Phytoplankton growth and microzooplankton grazing rates were significantly coupled in both areas.The microzooplankton grazing impact(m/μ0)on phytoplankton was also higher in the central SCS(0.63±0.12)than that in the northern SCS(0.37±0.06).The microzooplankton abundance was significantly correlated with temperature in the surface.Temperature might more effectively promote the microzooplankton grazing rate than phytoplankton growth rate,which might contribute to higher m and m/μ0 in the central SCS.Compared with temperature,nutrients mainly affected the growth rate of phytoplankton.In the nutrient enrichment treatment,the phytoplankton growth rate(μn)was higher thanμ0 in the central SCS,suggesting phytoplankton growth in the central SCS was nutrient limited.The ratio ofμ0/μn was significantly correlated with nutrients concentrations in the both areas,indicating the limitation of nutrients was related to the concentrations of background nutrients in the study stations.展开更多
Using micro-level data from 2009-2015 and the difference-in-difference method,this paper empirically examines the impact of the Belt and Road Initiative(BRI)on the quality of food imported by Chinese enterprises from ...Using micro-level data from 2009-2015 and the difference-in-difference method,this paper empirically examines the impact of the Belt and Road Initiative(BRI)on the quality of food imported by Chinese enterprises from BRI countries.Our baseline results show that the BRI significantly improved the quality of food imported from these countries.Further investigation reveals that trade patterns,ownership types,import regions,transportation methods,and product quality show significant heterogeneous effects in influencing the quality of imported food.A mechanism analysis indicates that the BRI improves the quality of imported food through three main channels:import trade environment enhancement,competition effect,and consumption upgrading,with the competition effect having the largest impact compared with the other two channels.Our findings suggest that China should not only improve the infrastructure in BRI countries but also use the BRI as an opportunity to enhance the level of cooperation with BRI countries and maintain stability and sustainability in cooperation with them.展开更多
This paper explores the impact of spatial externalities in shaping China's economic geography by establishing a theoretical framework that contains regional productivity,trade barriers and local amenities to captu...This paper explores the impact of spatial externalities in shaping China's economic geography by establishing a theoretical framework that contains regional productivity,trade barriers and local amenities to capture spatial externalities between different regions over time.Combining provincial data on bilateral trade flows with observed information about economic geography during the period 1998-2013,we estimate the distribution and marginal contribution of each explanatory.factor.Empirical results suggest that regional labor density and wage are positively related to exogenous productivity and amenities,and negatively related to trade barriers.Meanwhile,variation in the marginal contribution of exogenous productivity and amenities and trade barriers reflects the regional temporal-spatial features in China's recent marketization process.Therefore,the Chinese government should place more emphasis on absorbing advanced technologies and reducing inter-regional market barriers to promote balanced regional development and improve the eficiency of China s spatial resource allocation.展开更多
基金financial support from the“Hundred Talents Program”of the Chinese Academy of Sciencesthe“Young Talents Training Program”of the Shanghai Branch of the Chinese Academy of Sciences+3 种基金the financial support from the Xiamen City Natural Science Foundation of China(3502Z20227085,3502Z20227256)the National Science Youth Foundation of China(22202205)the Fujian Provincial Natural Science Foundation of China(2022J01502)Open Source Foundation of State Key Laboratory of Structural Chemistry。
文摘Fe-N-doped carbon materials(Fe-N-C)are promising candidates for oxygen reduction reaction(ORR)relative to Pt-based catalysts in proton exchange membrane fuel cells(PEMFCs).However,the intrinsic contributions of Fe-N_(4)moiety with different chemical/spin states(e.g.D1,D2,D3)to ORR are unclear since various states coexist inevitably.In the present work,Fe-N-C core-shell nanocatalyst with single lowspin Fe(Ⅱ)-N_(4)species(D1)is synthesized and identified with ex-situ ultralow temperature Mossbauer spectroscopy(T=1.6 K)that could essentially differentiate various Fe-N_(4)states and invisible Fe-O species.By quantifying with CO-pulse chemisorption,site density and turnover frequency of Fe-N-C catalysts reach 2.4×10^(-9)site g^(-1)and 23 e site~(-1)s^(-1)during the ORR,respectively.Half-wave potential(0.915V_(RHE))of the Fe-N-C catalyst is more positive(approximately 54 mV)than that of Pt/C.Moreover,we observe that the performance of PEMFCs on Fe-N-C almost achieves the 2025 target of the US Department of Energy by demonstrating a current density of 1.037 A cm^(-2)combined with the peak power density of 0,685 W cm^(-2),suggesting the critical role of Fe(Ⅱ)-N_(4)site(D1).After 500 h of running,PEMFCs still deliver a power density of 1.26 W cm^(-2)at 1.0 bar H_(2)-O_(2),An unexpected rate-determining step is figured out by isotopic labelling experiment and theoretical calculation.This work not only offers valuable insights regarding the intrinsic contribution of Fe-N_(4)with a single spin state to alkaline/acidic ORR,but also provides great opportunities for developing high-performance stable PEMFCs.
基金We are grateful for financial support from the“Hundred Talents Program”of the Chinese Academy of Sciences and the“Young Talents Training Program”of the Shanghai Branch of the Chinese Academy of Sciences.We acknowledge the financial support from the National Science Youth Foundation of China(22202205)Xiamen City Natural Science Foundation of China(3502Z20227256)Fujian Provincial Natural Science Foundation of China(2022J01502).
文摘Metal-free carbon,as the most representative heterogeneous metal-free catalysts,have received considerable interests in electro-and thermo-catalytic reac-tions due to their impressive performance and sustainability.Over the past decade,well-designed carbon catalysts with tunable structures and heteroatom groups coupled with various characterization techniques have proposed numerous reaction mechanisms.However,active sites,key intermediate species,precise structure-activity relationships and dynamic evolution processes of carbon catalysts are still rife with controversies due to the monotony and limitation of used experimental methods.In this Review,we sum-marize the extensive efforts on model catalysts since the 2000s,particularly in the past decade,to overcome the influences of material and structure limitations in metal-free carbon catalysis.Using both nanomolecule model and bulk model,the real contribution of each alien species,defect and edge configuration to a series of fundamentally important reactions,such as thermocatalytic reactions,electrocatalytic reactions,were systematically studied.Combined with in situ techniques,isotope labeling and size control,the detailed reaction mechanisms,the precise 2D structure-activity relationships and the rate-determining steps were revealed at a molecular level.Furthermore,the outlook of model carbon catalysis has also been proposed in this work.
基金supported by the Award Program for Fujian Minjiang Scholar Professorship,the National Natural Science Foundation of China(21571035)Chemical Engineering&Technology of Zhejiang Province First-Class Discipline(Taizhou University),Zhejiang Provincial Natural Science Foundation of China(LQ20B060001)Taizhou science and technology planning project(1902gy20)。
文摘The carbon-based metal-free materials as catalysts(named as carbocatalysts) have been attracting tremendous attentions in electric-,solar-and thermal-driven reactions nowadays.Compared to electrocatalysis and photocatalysis,the thermal-driven catalysis(thermocatalysis) including liquid phase and gas phase reactions involves wider scope and is relatively easy to realize practical large-scale applications.Over the past several years,some striking achievements on the design of new carbon-based metal-free materials with well-defined structures and heteroatom groups as well as the revelation of new reaction mechanisms and active sites in thermocatalysis have been obtained.However,comparative discussions regarding these recent achievements have been rarely highlighted.In this review,we systematically summarize and discuss six kinds of carbocatalysts and their applications in thermocatalysis.These materials include typical oxygen-attached carbon,surface modified carbon(graft with certain organic compounds),mono-doped carbon,co-doped carbon,carbon nitride and materials with carbon as dopant.Some new reaction processes as well as the related reaction mechanisms,active sites and intermediates are reviewed critically.Moreover,an outlook on the in-depth investigation of the metalfree carbocatalysis in the future is provided.
基金The National Key Research and Development Program of China under contract No.2019YFC1407805the National Natural Science Foundation of China under contract Nos 41876134 and 41676112+2 种基金the University Innovation Team Training Program for Tianjin under contract No.TD12-5003the Tianjin 131 Innovation Team Program under contract No.20180314the Changjiang Scholar Program of Chinese Ministry of Education to Jun Sun under contract No.T2014253。
文摘Phytoplankton growth rates and mortality rates were experimentally examined at 21 stations during the 2017 spring intermonsoon(April to early May)in the northern and central South China Sea(SCS)using the dilution technique,with emphasis on a comparison between the northern and central SCS areas which had different environmental factors.There had been higher temperature but lower nutrients and chlorophyll a concentrations in the central SCS than those in the northern SCS.The mean rates of phytoplankton growth(μ0)and microzooplankton grazing(m)were(0.88±0.33)d–1 and(0.55±0.22)d–1 in the central SCS,and both higher than those in the northern SCS with the values ofμ0((0.81±0.16)d–1)and m((0.30±0.09)d–1),respectively.Phytoplankton growth and microzooplankton grazing rates were significantly coupled in both areas.The microzooplankton grazing impact(m/μ0)on phytoplankton was also higher in the central SCS(0.63±0.12)than that in the northern SCS(0.37±0.06).The microzooplankton abundance was significantly correlated with temperature in the surface.Temperature might more effectively promote the microzooplankton grazing rate than phytoplankton growth rate,which might contribute to higher m and m/μ0 in the central SCS.Compared with temperature,nutrients mainly affected the growth rate of phytoplankton.In the nutrient enrichment treatment,the phytoplankton growth rate(μn)was higher thanμ0 in the central SCS,suggesting phytoplankton growth in the central SCS was nutrient limited.The ratio ofμ0/μn was significantly correlated with nutrients concentrations in the both areas,indicating the limitation of nutrients was related to the concentrations of background nutrients in the study stations.
基金supported by the National Natural Science Foundation of China(Nos.71673251,71873120,and 7217030190)the Characteristic Innovation Project of Colleges and Universities in Guangdong Province of China(No.2021WTSCX329).
文摘Using micro-level data from 2009-2015 and the difference-in-difference method,this paper empirically examines the impact of the Belt and Road Initiative(BRI)on the quality of food imported by Chinese enterprises from BRI countries.Our baseline results show that the BRI significantly improved the quality of food imported from these countries.Further investigation reveals that trade patterns,ownership types,import regions,transportation methods,and product quality show significant heterogeneous effects in influencing the quality of imported food.A mechanism analysis indicates that the BRI improves the quality of imported food through three main channels:import trade environment enhancement,competition effect,and consumption upgrading,with the competition effect having the largest impact compared with the other two channels.Our findings suggest that China should not only improve the infrastructure in BRI countries but also use the BRI as an opportunity to enhance the level of cooperation with BRI countries and maintain stability and sustainability in cooperation with them.
基金The authors are grateful for support from the National Natural Science Foundation of China(No.71573269 and No.71873120)the China National Social Science Foundation(No.16BJY119)the Priority Academic Program Development of Jiangsu Higher Education Institutions and Zhejiang Province Natural Science Foundation(No.LY 18G030004).
文摘This paper explores the impact of spatial externalities in shaping China's economic geography by establishing a theoretical framework that contains regional productivity,trade barriers and local amenities to capture spatial externalities between different regions over time.Combining provincial data on bilateral trade flows with observed information about economic geography during the period 1998-2013,we estimate the distribution and marginal contribution of each explanatory.factor.Empirical results suggest that regional labor density and wage are positively related to exogenous productivity and amenities,and negatively related to trade barriers.Meanwhile,variation in the marginal contribution of exogenous productivity and amenities and trade barriers reflects the regional temporal-spatial features in China's recent marketization process.Therefore,the Chinese government should place more emphasis on absorbing advanced technologies and reducing inter-regional market barriers to promote balanced regional development and improve the eficiency of China s spatial resource allocation.
