In this study,the nitrogen removal performance of partial denitrificaiton/anammox(PDA)process was investigated by using an UASB reactor.High total nitrogen(TN)removal efficiency(91.97%)was achieved at an influent nitr...In this study,the nitrogen removal performance of partial denitrificaiton/anammox(PDA)process was investigated by using an UASB reactor.High total nitrogen(TN)removal efficiency(91.97%)was achieved at an influent nitrogen loading rate of 0.64 kg/(m3·d).Anammox bacteria did execute the function of converting nitrate to nitrite in PDA system according to ^(15)N isotope labeling experiments and the contribution was approximately 36.3%.Candidatus_Brocadia,Candidatus_Kuenenia and Thauera were functional strains for anammox and denitrification process,respectively.Thauera and Candidatus_Brocadia were more important for TN removal at high loading rates(0.64 kg/(m3·d)).This result can provide a theoretical and technical foundation for the application of the PDA process.展开更多
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
Recent advances in utilizing ^(17)O isotopic labeling methods for solid-state nuclear magnetic resonance(NMR)investigations of metal oxides for lithium-ion batteries have yielded extensive insights into their structur...Recent advances in utilizing ^(17)O isotopic labeling methods for solid-state nuclear magnetic resonance(NMR)investigations of metal oxides for lithium-ion batteries have yielded extensive insights into their structural and dynamic details.Herein,we commence with a brief introduction to recent research on lithium-ion battery oxide materials studied using ^(17)O solid-state NMR spectroscopy.Then we delve into a review of ^(17)O isotopic labeling methods for tagging oxygen sites in both the bulk and surfaces of metal oxides.At last,the unresolved problems and the future research directions for advancing the ^(17)O labeling technique are discussed.展开更多
Electrochemical nitrogen reduction reaction (eNRR) is an alternative promising manner for sustainable N2 fixation with low-emission. The major challenge for developing an efficient electrocatalyst is the cleaving of t...Electrochemical nitrogen reduction reaction (eNRR) is an alternative promising manner for sustainable N2 fixation with low-emission. The major challenge for developing an efficient electrocatalyst is the cleaving of the stable Ntriple bondN triple bonds. Herein, we design a new MoS_(2) with in-plane defect cluster through a bottom-up approach for the first time, where the defect cluster is composed of three adjacent S vacancies. The well-defined in-plane defect clusters could contribute to the strong chemical adsorption and activation towards inert nitrogen, achieving an excellent eNRR performance with an ammonia yield rate of 43.4 ± 3 μg h^(−1) mgcat.^(−1) and a Faradaic efficiency of 16.8 ± 2% at −0.3 V (vs. RHE). The performance is much higher than that of MoS_(2) with the edge defect. Isotopic labeling confirms that N atoms of produced NH4+ originate from N2. Furthermore, the in-plane defect clusters realized the alternate hydrogenation of nitrogen in a side-on way to synthesize ammonia. This work provides a prospecting strategy for fine-tuning in-plane defects in a catalyst, and also promotes the progress of eNRR.展开更多
Fast pyrolysis of biomass will produce various furan derivatives, among which 5-hydroxymethyl furfural（5-HMF） and furfural（FF） are usually the two most important compounds derived from holocellulose. In this study...Fast pyrolysis of biomass will produce various furan derivatives, among which 5-hydroxymethyl furfural（5-HMF） and furfural（FF） are usually the two most important compounds derived from holocellulose. In this study, density functional theory（DFT） calculations are utilized to reveal the formation mechanisms and pathways of 5-HMF and FF from two hexose units of holocellulose, i.e., glucose and mannose. In addition, fast pyrolysis experiments of glucose and mannose are conducted to substantiate the computational results, and the orientation of 5-HMF and FF is determined by 13C-labeled glucoses. Experimental results indicate that C1 provides the aldehyde group in both 5-HMF and FF, and FF is mainly derived from C1 to C5 segment. According to the computational results, glucose and mannose have similar reaction pathways to form 5-HMF and FF with d-fructose（DF） and 3-deoxy-glucosone（3-DG） as the key intermediates. 5-HMF and FF are formed via competing pathways. The formation of 5-HMF is more competitive than that of FF, leading to higher yield of 5-HMF than FF from both hexoses. In addition, compared with glucose,mannose can form 5-HMF and FF via extra pathways because of the epimerization at C2 position. Therefore, mannose pyrolysis results in higher yields of 5-HMF and FF than glucose pyrolysis.展开更多
Ectomycorrhizal(EM)networks provide a variety of services to plants and ecosystems include nutrient uptake and transfer,seedling survival,internal cycling of nutrients,plant competition,and so on.To deeply their struc...Ectomycorrhizal(EM)networks provide a variety of services to plants and ecosystems include nutrient uptake and transfer,seedling survival,internal cycling of nutrients,plant competition,and so on.To deeply their structure and function in ecosystems,we investigated the spatial patterns and nitrogen(N)transfer of EM networks usingN labelling technique in a Mongolian scotch pine(Pinus sylvestris var.mongolica Litv.)plantation in Northeastern China.In August 2011,four plots(20 × 20 m)were set up in the plantation.125 ml 5 at.%0.15 mol/LNHNOsolution was injected into soil at the center of each plot.Before and 2,6,30 and 215 days after theN application,needles(current year)of each pine were sampled along four 12 m sampling lines.Needle total N andN concentrations were analyzed.We observed needle N andN concentrations increased significantly over time afterN application,up to 31 and0.42%,respectively.There was no correlation between needle N concentration andN/N ratio(R2=0.40,n=5,P=0.156),while excess needle N concentration and excess needleN/N ratio were positively correlated across different time intervals(R~2=0.89,n=4,P\0.05),but deceased with time interval lengthening.NeedleN/N ratio increased with time,but it was not correlated with distance.NeedleN/N ratio was negative with distance before and 6th day and 30th day,positive with distance at 2nd day,but the trend was considerably weaker,their slop were close to zero.These results demonstrated that EM networks were ubiquitous and uniformly distributed in the Mongolian scotch pine plantation and a random network.We found N transfer efficiency was very high,absorbed N by EM network was transferred as wide as possible,we observed N uptake of plant had strong bias forN andN,namely N fractionation.Understanding the structure and function of EM networks in ecosystems may lead to a deeper understanding of ecological stability and evolution,and thus provide new theoretical approaches to improve conservation practices for the management of the Earth’s ecosystems.展开更多
基金supported by the Natural Science Foundation of Shandong Province (ZR2019MEE038)the Fundamental Research Funds for the Central Universities (19CX02038A)the Key R&D Program of Shandong Province (Major Scientific and Technological Innovation Project 2019JZZY020502)
文摘In this study,the nitrogen removal performance of partial denitrificaiton/anammox(PDA)process was investigated by using an UASB reactor.High total nitrogen(TN)removal efficiency(91.97%)was achieved at an influent nitrogen loading rate of 0.64 kg/(m3·d).Anammox bacteria did execute the function of converting nitrate to nitrite in PDA system according to ^(15)N isotope labeling experiments and the contribution was approximately 36.3%.Candidatus_Brocadia,Candidatus_Kuenenia and Thauera were functional strains for anammox and denitrification process,respectively.Thauera and Candidatus_Brocadia were more important for TN removal at high loading rates(0.64 kg/(m3·d)).This result can provide a theoretical and technical foundation for the application of the PDA process.
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supported by National Key R&D Program of China(2021YFA1502803)the National Natural Science Foundation of China(NSFC)(21972066,91745202)+3 种基金NSFC-Royal Society Joint Program(21661130149)L.P.thanks the Royal Society and Newton Fund for a Royal Society-Newton Advanced Fellowshipsupported by the Research Funds for the Frontiers Science Centre for Critical Earth Material Cycling,Nanjing Universitya Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘Recent advances in utilizing ^(17)O isotopic labeling methods for solid-state nuclear magnetic resonance(NMR)investigations of metal oxides for lithium-ion batteries have yielded extensive insights into their structural and dynamic details.Herein,we commence with a brief introduction to recent research on lithium-ion battery oxide materials studied using ^(17)O solid-state NMR spectroscopy.Then we delve into a review of ^(17)O isotopic labeling methods for tagging oxygen sites in both the bulk and surfaces of metal oxides.At last,the unresolved problems and the future research directions for advancing the ^(17)O labeling technique are discussed.
基金This work was supported by the National Natural Science Foundation of China(22078063,21825801).
文摘Electrochemical nitrogen reduction reaction (eNRR) is an alternative promising manner for sustainable N2 fixation with low-emission. The major challenge for developing an efficient electrocatalyst is the cleaving of the stable Ntriple bondN triple bonds. Herein, we design a new MoS_(2) with in-plane defect cluster through a bottom-up approach for the first time, where the defect cluster is composed of three adjacent S vacancies. The well-defined in-plane defect clusters could contribute to the strong chemical adsorption and activation towards inert nitrogen, achieving an excellent eNRR performance with an ammonia yield rate of 43.4 ± 3 μg h^(−1) mgcat.^(−1) and a Faradaic efficiency of 16.8 ± 2% at −0.3 V (vs. RHE). The performance is much higher than that of MoS_(2) with the edge defect. Isotopic labeling confirms that N atoms of produced NH4+ originate from N2. Furthermore, the in-plane defect clusters realized the alternate hydrogenation of nitrogen in a side-on way to synthesize ammonia. This work provides a prospecting strategy for fine-tuning in-plane defects in a catalyst, and also promotes the progress of eNRR.
基金financial support from the National Natural Science Foundation of China (51576064, 51676193)Beijing Nova Program (Z171100001117064)+2 种基金Beijing Natural Science Foundation (3172030)the Foundation of Stake Key Laboratory of Coal Combustion (FSKLCCA1706)the Fundamental Research Funds for the Central Universities (2017MS071, 2016YQ05)
文摘Fast pyrolysis of biomass will produce various furan derivatives, among which 5-hydroxymethyl furfural（5-HMF） and furfural（FF） are usually the two most important compounds derived from holocellulose. In this study, density functional theory（DFT） calculations are utilized to reveal the formation mechanisms and pathways of 5-HMF and FF from two hexose units of holocellulose, i.e., glucose and mannose. In addition, fast pyrolysis experiments of glucose and mannose are conducted to substantiate the computational results, and the orientation of 5-HMF and FF is determined by 13C-labeled glucoses. Experimental results indicate that C1 provides the aldehyde group in both 5-HMF and FF, and FF is mainly derived from C1 to C5 segment. According to the computational results, glucose and mannose have similar reaction pathways to form 5-HMF and FF with d-fructose（DF） and 3-deoxy-glucosone（3-DG） as the key intermediates. 5-HMF and FF are formed via competing pathways. The formation of 5-HMF is more competitive than that of FF, leading to higher yield of 5-HMF than FF from both hexoses. In addition, compared with glucose,mannose can form 5-HMF and FF via extra pathways because of the epimerization at C2 position. Therefore, mannose pyrolysis results in higher yields of 5-HMF and FF than glucose pyrolysis.
基金supported by National Natural Science Foundation of China(30830024)
文摘Ectomycorrhizal(EM)networks provide a variety of services to plants and ecosystems include nutrient uptake and transfer,seedling survival,internal cycling of nutrients,plant competition,and so on.To deeply their structure and function in ecosystems,we investigated the spatial patterns and nitrogen(N)transfer of EM networks usingN labelling technique in a Mongolian scotch pine(Pinus sylvestris var.mongolica Litv.)plantation in Northeastern China.In August 2011,four plots(20 × 20 m)were set up in the plantation.125 ml 5 at.%0.15 mol/LNHNOsolution was injected into soil at the center of each plot.Before and 2,6,30 and 215 days after theN application,needles(current year)of each pine were sampled along four 12 m sampling lines.Needle total N andN concentrations were analyzed.We observed needle N andN concentrations increased significantly over time afterN application,up to 31 and0.42%,respectively.There was no correlation between needle N concentration andN/N ratio(R2=0.40,n=5,P=0.156),while excess needle N concentration and excess needleN/N ratio were positively correlated across different time intervals(R~2=0.89,n=4,P\0.05),but deceased with time interval lengthening.NeedleN/N ratio increased with time,but it was not correlated with distance.NeedleN/N ratio was negative with distance before and 6th day and 30th day,positive with distance at 2nd day,but the trend was considerably weaker,their slop were close to zero.These results demonstrated that EM networks were ubiquitous and uniformly distributed in the Mongolian scotch pine plantation and a random network.We found N transfer efficiency was very high,absorbed N by EM network was transferred as wide as possible,we observed N uptake of plant had strong bias forN andN,namely N fractionation.Understanding the structure and function of EM networks in ecosystems may lead to a deeper understanding of ecological stability and evolution,and thus provide new theoretical approaches to improve conservation practices for the management of the Earth’s ecosystems.
