The transfer mechanisms. calculating methods and ecological significance of nitrogen transfer between legumes and non-legumes are briefly reviewed. There are three pathways 0f nitrogen transf6r from legumes to neighbo...The transfer mechanisms. calculating methods and ecological significance of nitrogen transfer between legumes and non-legumes are briefly reviewed. There are three pathways 0f nitrogen transf6r from legumes to neighboring non-legumes: (1) the nitrogen pass in soluble form from the donor legume root into the soil solution, move by diffusion or/and mass flow to the receiver root and be taken up by the latter, (2) nitrogen pass into the soil solution as before, be taken up and transported by mycorrhizal hyphae attached to the receiver roots,(3) if mycorrhizal hyphae form connections (bridges) between the two root systems, the nitrogen could pass into the fungus within the donor root and be transported into the receiver root without ever being in the soil solution. The mechanisms of nitrogen transfer between N2-fixing plants and non-N2-fixing plants are reviewed in terms of indirect and direct pathways. The indirect N-transfer process is related to the release of nitrogen from legumes(donor plants), the possible interaction of this nitrogen with soil, the decomposition and mineralization of legumes and tumover of nitrogen, the nitrogen absorbing and competing abilities of the legume and the non-legume (receiver plant). The direCt nitrogen transfer process is generally considered to be related to the nitrogen gradient and physiological imbalance between legumes and non-legumes, and when the donor legume lies in stressful stage (i.e. removal of shoots or attacked by insects), the nitrogen transfer can be improved significantly. Themethods of deterrnining nitrogen transfer (lndirect 15N-isotope. dilution method and direct 15N determination method) are evaluated, and their advantages and shortcomings are shown in this review.展开更多
A study was conducted to determine the effects of elevated CO2 on soil N process at Changbai Mountain in Jilin Province, northeastern China （42°24＂N, 128°06＂E, and 738 m elevation）. A randomized complete...A study was conducted to determine the effects of elevated CO2 on soil N process at Changbai Mountain in Jilin Province, northeastern China （42°24＂N, 128°06＂E, and 738 m elevation）. A randomized complete block design of ambient and elevated CO2 was established in an open-top chamber facility in the spring of 1999. Changpai Scotch pine （Pinus sylvestris var. sylvestriformis seeds were sowed in May, 1999 and CO2 fumigation treatments began after seeds germination. In each year, the exposure started at the end of April and stopped at the end of October. Soil samples were collected in June and August 2006 and in June 2007, and soil nitrifying, denitrifying and N2-fixing enzyme activities were measured. Results show that soil nitrifying enzyme activities （NEA） in the 5-10 cm soil layer were significantly increased at elevated CO2 by 30.3% in June 2006, by 30.9% in August 2006 and by 11.3% in June 2007. Soil denitrifying enzyme activities （DEA） were significantly decreased by elevated CO2 treatment in June 2006 （P 〈 0.012） and August 2006 （P 〈 0.005） samplings in our study; no significant difference was detected in June 2007, and no significant changes in N2-fixing enzyme activity were found. This study suggests that elevated CO2 can alter soil nitrifying enzyme and denitrifying enzyme activities.展开更多
The effects of chromium and tin on survival, growth, carbon fixation, nitrate reduction, ammonia assimilation, and nitrogenase activity of a N_2-fixing cyanobacterium, Anabaena doliolum, and their amelioration by synt...The effects of chromium and tin on survival, growth, carbon fixation, nitrate reduction, ammonia assimilation, and nitrogenase activity of a N_2-fixing cyanobacterium, Anabaena doliolum, and their amelioration by synthetic and natural complexans, viz., EDTA, nitrilotriacetic acid (NTA), pyridine dicarboxylic acid (PDA), and citrate, have been studied. Chromium proved to be much more toxic than tin, as it inhibited growth yield (49%), carbon fixation (53%), and nitrate reductase (79%), glutamine synthetase (30%), and nitrogenase activities (77%) at its sublethal concentration, whereas tin induced less inhibition of growth yield (42%), carbon fixation (50%). and nitrate reductase (66%), glutamine synthetase (32.4%), and nitrogenase activities (70%). Despite its inhibitory effects at 10μml^(-1), EDTA supplementation in metal-spiked medium counteracted the toxicity of chromium and tin more significantly than NTA, PDA, and citrate. When supplemented with LD_(50) of Cr, EDTA protected growth, carbon fixation, NR, GS. and Noase, respectively, by 32.6, 50.0, 33.3. 17.7. and 65.4%. However, EDTA-induced restoration of the above parameters at a sublethal concentration of tin was only 30.2, 50.0,28.1, 27.7, and 61.5%, respectively. Although NTA and citrate at 10/μgml^(-1) each were stimulatory to various processes of test cyanobacterium, they were comparatively less effective than EDTA in the amelioration of metal toxicity. On the basis of these observations, a generalized hierarchical sequence of protective efficiency of synthetic and natural cornplexing ligands may be given as EDTA > NTA > citrate > PDA. It seems plausible that the toxicity of various heavy metals may be regulated by a large array of organic complexing agents of the aquatic environment because they possess various metal binding sites. (c) 1989 Academic Press,lnc.展开更多
为探究稻茬小麦深施肥“一基一追”机艺融合技术的增产增效减排机制,2021—2024年在长江下游南通稻茬麦区开展大田试验。试验采用缓释掺混肥料(SRF,N∶P_(2)O_(5)∶K_(2)O=26∶12∶12)和普通尿素(U,46%N),结合自主研发的2BFGK-12(6)260...为探究稻茬小麦深施肥“一基一追”机艺融合技术的增产增效减排机制,2021—2024年在长江下游南通稻茬麦区开展大田试验。试验采用缓释掺混肥料(SRF,N∶P_(2)O_(5)∶K_(2)O=26∶12∶12)和普通尿素(U,46%N),结合自主研发的2BFGK-12(6)260全秸秆茬地洁区旋耕智能施肥播种机和3ZF-4(200)中耕追肥机,设置7种施肥模式(30 cm+15 cm宽窄行种植):以尿素4次分施(N 240 kg hm^(-2),基肥∶分蘖肥∶拔节肥∶孕穗肥=5∶1∶2∶2,窄行基施,追肥全田撒施)为对照(CK);减氮15%(N 204 kg hm^(-2))条件下设置6种处理:M_(1)(100%SRF窄行基施);M_(2)(60%SRF窄行基施+40%U拔节期窄行撒施);M_(3)(60%SRF窄行基施+40%U返青期宽行条施);M_(4)(60%SRF窄行基施+40%SRF返青期窄行撒施);M_(5)(60%SRF窄行基施+40%SRF返青期宽行条施);M_(4+5)(60%SRF窄行基施+20%SRF返青期宽行条施+20%SRF返青期窄行撒施)。研究比较不同施肥模式对小麦产量效益、根系形态生理、氮素利用效率及N_(2)O排放的影响。结果表明,与CK相比,M_(2)~M_(5)处理提高了小麦产量(4.0%~19.0%)和经济效益(13.7%~35.7%),其中M_(4)和M_(5)处理表现最优,分别增产14.1%和19.0%,经济效益提升34.5%和35.7%。这些处理明显改善了根系特性(根干重密度增加9.7%~111.8%,根系活力和氧化力分别提高6.8%~52.0%和4.2%~44.2%),降低N_(2)O累积排放量22.6%~34.5%,提高0~20 cm土层硝态氮含量11.2%~40.0%。在氮素利用方面,M_(2)~M_(5)处理均提高了籽粒氮素积累量、花后氮素积累量及其对籽粒氮素的贡献率,氮肥利用效率指标(包括偏生产力、农学效率和表观利用率)分别显著提升了22.4%~40.0%、29.7%~74.3%和9.41~18.77个百分点。值得注意的是,M_(4)和M_(5)处理表现出最优的综合效益:N_(2)O累积排放量降幅最大(分别达27.0%和34.5%),氮肥表观利用率2季均维持在43.0%以上(均值分别为43.5%和46.8%),同时在生育后期保持较高的根系活性和耕层无机氮含量。相比之下,M_(1)处理虽然实现了最大的N_(2)O减排效果(降幅35.9%),但导致减产10.4%和经济效益下降10.8%,且氮肥利用效率呈现不稳定的年际变化特征。而优化处理M_(4+5)进一步改善了根系形态生理特性,并提高氮肥表观利用率和籽粒氮素积累量。综上,减氮15%条件下(N 204 kg hm^(-2)),缓混肥2次施用处理(M_(4)和M_(5))能实现产量、经济效益、氮肥利用效率和N_(2)O减排的协同提高,并以追肥深施处理(M_(5))效应更强。本研究为稻茬小麦缓释肥减氮优化高效应用提供重要理论依据。展开更多
As one of the major volatile components in extraterrestrial materials,nitrogen(N_(2))isotopes serve not only as tracers for the formation and evolution of the solar system,but also play a critical role in assessing pl...As one of the major volatile components in extraterrestrial materials,nitrogen(N_(2))isotopes serve not only as tracers for the formation and evolution of the solar system,but also play a critical role in assessing planetary habitability and the search for extraterrestrial life.The integrated measurement of N_(2)and argon(Ar)isotopes by using noble gas mass spectrometry represents a state-of-the-art technique for such investigations.To support the growing demands of planetary science research in China,we have developed a high-efficiency,high-precision method for the integrated analysis of N_(2)and Ar isotopes.This was achieved by enhancing gas extraction and purification systems and integrating them with a static noble gas mass spectrometer.This method enables integrated N_(2)-Ar isotope measurements on submilligram samples,significantly improving sample utilization and reducing the impact of sample heterogeneity on volatile analysis.The system integrates CO_(2)laser heating,a modular two-stage Zr-Al getter pump,and a CuO furnace-based purification process,effectively reducing background levels(N_(2)blank as low as 0.35×10^(−6)cubic centimeters at standard temperature and pressure[ccSTP]).Analytical precision is ensured through calibration with atmospheric air and CO corrections.To validate the reliability of the method,we performed N_(2)-Ar isotope analyses on the Allende carbonaceous chondrite,one of the most extensively studied meteorites internationally.The measured N_(2)concentrations range from 19.2 to 29.8 ppm,withδ15N values between−44.8‰and−33.0‰.Concentrations of 40Ar,36Ar,and 38Ar are(12.5-21.1)×10^(−6)ccSTP/g,(90.9-150.3)×10^(−9)ccSTP/g,and(19.2-30.7)×10^(−9)ccSTP/g,respectively.These values correspond to cosmic-ray exposure ages of 4.5-5.7 Ma,consistent with previous reports.Step-heating experiments further reveal distinct release patterns of N and Ar isotopes,as well as their associations with specific mineral phases in the meteorite.In summary,the combined N_(2)-Ar isotopic system offers significant advantages for tracing volatile sources in extraterrestrial materials and will provide essential analytical support for upcoming Chinese planetary missions,such as Tianwen-2.展开更多
Photocatalytic oxygen reduction provides a sustainable method for on-site hydrogen peroxide(H_(2)O_(2))synthesis.However,most photocatalysts suffer from moderate kinetics due to sluggish electron transfer and ineffici...Photocatalytic oxygen reduction provides a sustainable method for on-site hydrogen peroxide(H_(2)O_(2))synthesis.However,most photocatalysts suffer from moderate kinetics due to sluggish electron transfer and inefficient oxygen adsorption and activation.Herein,sodium(Na)and potassium(K)are co-incorporated into graphitic carbon nitride(g-C_(3)N_(4))via a stepwise co-doping strategy combining sodium chloride-induced and molten salt-assisted polymerization.Experimental results and density functional theory calculations demonstrate that the synergistic interaction between intralayer Na+ions and interlayer K^(+)ions facilitates charge carrier separation and migration both within and between g-C_(3)N_(4)layers.Additionally,multiple heteroatom sites enhance surface charge polarization and introduce cyano groups,which synergistically promote oxygen molecule(O_(2))adsorption and elevate local proton coverage.Simultaneously,the energy barrier for H_(2)O_(2)desorption on the optimal photocatalyst(5Na/3.3K-CN)is lowered,thus improving H_(2)O_(2)production efficiency.Eventually,5Na/3.3K-CN exhibits an impressive H_(2)O_(2)yield of 2541.6μmol·g^(-1)·h^(-1) in an artificial reactor,which is 10.6 times higher than that of pure g-C_(3)N_(4)(240.2μmol·g^(-1)·h^(-1)).Under natural sunlight outdoors,5Na/3.3K-CN still maintains ultrahigh H_(2)O_(2)photosynthesis efficiency,achieving an H_(2)O_(2)photosynthesis rate of 2068.7μmol·g^(-1)·h^(-1).This work introduces a straightforward method to simultaneously optimize charge transfer and O_(2)activation for boosting H_(2)O_(2)photosynthesis,offering valuable insights toward the real-world deployment of g-C_(3)N_(4)-based photocatalysts in environmental protection and energy conversion.展开更多
While thermal air exfoliation is widely used to prepare graphitic carbon nitride(g-C_(3)N_(4))nanosheets,the effects of calcination conditions and atmosphere on their electronic structure and photocatalytic CO_(2)redu...While thermal air exfoliation is widely used to prepare graphitic carbon nitride(g-C_(3)N_(4))nanosheets,the effects of calcination conditions and atmosphere on their electronic structure and photocatalytic CO_(2)reduction reaction(CO_(2)RR)performance remain systematically unexplored.We prepared g-C_(3)N_(4)nanosheets with varying thickness and defects by controlling exfoliation parameters.The obtained nanosheets calcined longest in air exhibited highest CO_(2)RR activity,twice that of bulk g-C_(3)N_(4).The comprehensive analysis of structural characterizations indicates the thickness of g-C_(3)N_(4)nanosheets became thinner,and the defects increased as the calcination time increased.The N vacancies(N_(v))and O-doping caused by N_(2) and O_(2)from air,respectively,enable valence band elevation(N_(v))and conduction band depression(O-doping)that collectively redistribute the electronic structure.Nitrogen/oxygen dual-defects generated impurity levels,reduced the work function and band gap of g-C_(3)N_(4)nanosheets,and served as shallow traps for photogenerated e^(-).The results of in-situ spectroscopy indicate these increased effective e^(-)are enriched around of N atoms to react with the adsorbed CO_(2).During the CO_(2)reduction process,the N_(v) promoted the formation of*COOH,and this dual-defect co-promoted the*CO desorption,resulting in the improved CO_(2)RR activity.These results comprehensively analyze the regulatory effect of thermal air calcination on the electronic structure of g-C_(3)N_(4),providing valuable insights for designing g-C_(3)N_(4)nanosheets based photocatalysts for CO_(2)RR.展开更多
Achieving heterogeneous photocatalytic activation of sp^(3)C-H bonds and carboxylation of CO_(2)to produce arylacetic acids and alkyl carboxylic acids with increased carbon chains is a highly significant and demanding...Achieving heterogeneous photocatalytic activation of sp^(3)C-H bonds and carboxylation of CO_(2)to produce arylacetic acids and alkyl carboxylic acids with increased carbon chains is a highly significant and demanding research endeavor.In this work,a new method for synthesizing redox centers spatially separated Z-scheme CdS@graphitic carbon nitride(g-C_(3)N_(4))was developed,aiming to achieve photocatalytic benzylic and aliphatic sp^(3)C-H activation as well as CO_(2)carboxylation without sacrificial agent.Notably,both benzylic and aliphatic sp^(3)C-H activation together with CO_(2)carboxylation were achieved in heterogeneous photocatalytic system,resulting in the production of carboxylic acids with increased carbon chains under mild conditions.Various methylbenzene derivatives and cycloalkanes were employed to synthesize carbon-chain increased acids via a process involving K_(3)PO_(4)-assisted photogenerated holes activation for benzyl radical generation,photoinduced CO_(2)reduction,as well as solvent-assisted chemoselective carboxylation.Various characterizations and density functional theory(DFT)results revealed that Z-scheme CdS@g-C_(3)N_(4)not just significantly enhanced separation of charges and accumulation of photoinduced electrons on g-C_(3)N_(4)but also facilitated adsorption along with activation of CO_(2).This research provided novel heterogeneous photocatalytic approach to produce carbon chains increased carboxylic acids via sp^(3)C-H activation and CO_(2)carboxylation.展开更多
文摘The transfer mechanisms. calculating methods and ecological significance of nitrogen transfer between legumes and non-legumes are briefly reviewed. There are three pathways 0f nitrogen transf6r from legumes to neighboring non-legumes: (1) the nitrogen pass in soluble form from the donor legume root into the soil solution, move by diffusion or/and mass flow to the receiver root and be taken up by the latter, (2) nitrogen pass into the soil solution as before, be taken up and transported by mycorrhizal hyphae attached to the receiver roots,(3) if mycorrhizal hyphae form connections (bridges) between the two root systems, the nitrogen could pass into the fungus within the donor root and be transported into the receiver root without ever being in the soil solution. The mechanisms of nitrogen transfer between N2-fixing plants and non-N2-fixing plants are reviewed in terms of indirect and direct pathways. The indirect N-transfer process is related to the release of nitrogen from legumes(donor plants), the possible interaction of this nitrogen with soil, the decomposition and mineralization of legumes and tumover of nitrogen, the nitrogen absorbing and competing abilities of the legume and the non-legume (receiver plant). The direCt nitrogen transfer process is generally considered to be related to the nitrogen gradient and physiological imbalance between legumes and non-legumes, and when the donor legume lies in stressful stage (i.e. removal of shoots or attacked by insects), the nitrogen transfer can be improved significantly. Themethods of deterrnining nitrogen transfer (lndirect 15N-isotope. dilution method and direct 15N determination method) are evaluated, and their advantages and shortcomings are shown in this review.
基金supported by the National Natural Science Foundation of China (No.90411020)Major State Basic Research Development Program of China (973 Program)(2002CB412502).
文摘A study was conducted to determine the effects of elevated CO2 on soil N process at Changbai Mountain in Jilin Province, northeastern China （42°24＂N, 128°06＂E, and 738 m elevation）. A randomized complete block design of ambient and elevated CO2 was established in an open-top chamber facility in the spring of 1999. Changpai Scotch pine （Pinus sylvestris var. sylvestriformis seeds were sowed in May, 1999 and CO2 fumigation treatments began after seeds germination. In each year, the exposure started at the end of April and stopped at the end of October. Soil samples were collected in June and August 2006 and in June 2007, and soil nitrifying, denitrifying and N2-fixing enzyme activities were measured. Results show that soil nitrifying enzyme activities （NEA） in the 5-10 cm soil layer were significantly increased at elevated CO2 by 30.3% in June 2006, by 30.9% in August 2006 and by 11.3% in June 2007. Soil denitrifying enzyme activities （DEA） were significantly decreased by elevated CO2 treatment in June 2006 （P 〈 0.012） and August 2006 （P 〈 0.005） samplings in our study; no significant difference was detected in June 2007, and no significant changes in N2-fixing enzyme activity were found. This study suggests that elevated CO2 can alter soil nitrifying enzyme and denitrifying enzyme activities.
文摘The effects of chromium and tin on survival, growth, carbon fixation, nitrate reduction, ammonia assimilation, and nitrogenase activity of a N_2-fixing cyanobacterium, Anabaena doliolum, and their amelioration by synthetic and natural complexans, viz., EDTA, nitrilotriacetic acid (NTA), pyridine dicarboxylic acid (PDA), and citrate, have been studied. Chromium proved to be much more toxic than tin, as it inhibited growth yield (49%), carbon fixation (53%), and nitrate reductase (79%), glutamine synthetase (30%), and nitrogenase activities (77%) at its sublethal concentration, whereas tin induced less inhibition of growth yield (42%), carbon fixation (50%). and nitrate reductase (66%), glutamine synthetase (32.4%), and nitrogenase activities (70%). Despite its inhibitory effects at 10μml^(-1), EDTA supplementation in metal-spiked medium counteracted the toxicity of chromium and tin more significantly than NTA, PDA, and citrate. When supplemented with LD_(50) of Cr, EDTA protected growth, carbon fixation, NR, GS. and Noase, respectively, by 32.6, 50.0, 33.3. 17.7. and 65.4%. However, EDTA-induced restoration of the above parameters at a sublethal concentration of tin was only 30.2, 50.0,28.1, 27.7, and 61.5%, respectively. Although NTA and citrate at 10/μgml^(-1) each were stimulatory to various processes of test cyanobacterium, they were comparatively less effective than EDTA in the amelioration of metal toxicity. On the basis of these observations, a generalized hierarchical sequence of protective efficiency of synthetic and natural cornplexing ligands may be given as EDTA > NTA > citrate > PDA. It seems plausible that the toxicity of various heavy metals may be regulated by a large array of organic complexing agents of the aquatic environment because they possess various metal binding sites. (c) 1989 Academic Press,lnc.
文摘为探究稻茬小麦深施肥“一基一追”机艺融合技术的增产增效减排机制,2021—2024年在长江下游南通稻茬麦区开展大田试验。试验采用缓释掺混肥料(SRF,N∶P_(2)O_(5)∶K_(2)O=26∶12∶12)和普通尿素(U,46%N),结合自主研发的2BFGK-12(6)260全秸秆茬地洁区旋耕智能施肥播种机和3ZF-4(200)中耕追肥机,设置7种施肥模式(30 cm+15 cm宽窄行种植):以尿素4次分施(N 240 kg hm^(-2),基肥∶分蘖肥∶拔节肥∶孕穗肥=5∶1∶2∶2,窄行基施,追肥全田撒施)为对照(CK);减氮15%(N 204 kg hm^(-2))条件下设置6种处理:M_(1)(100%SRF窄行基施);M_(2)(60%SRF窄行基施+40%U拔节期窄行撒施);M_(3)(60%SRF窄行基施+40%U返青期宽行条施);M_(4)(60%SRF窄行基施+40%SRF返青期窄行撒施);M_(5)(60%SRF窄行基施+40%SRF返青期宽行条施);M_(4+5)(60%SRF窄行基施+20%SRF返青期宽行条施+20%SRF返青期窄行撒施)。研究比较不同施肥模式对小麦产量效益、根系形态生理、氮素利用效率及N_(2)O排放的影响。结果表明,与CK相比,M_(2)~M_(5)处理提高了小麦产量(4.0%~19.0%)和经济效益(13.7%~35.7%),其中M_(4)和M_(5)处理表现最优,分别增产14.1%和19.0%,经济效益提升34.5%和35.7%。这些处理明显改善了根系特性(根干重密度增加9.7%~111.8%,根系活力和氧化力分别提高6.8%~52.0%和4.2%~44.2%),降低N_(2)O累积排放量22.6%~34.5%,提高0~20 cm土层硝态氮含量11.2%~40.0%。在氮素利用方面,M_(2)~M_(5)处理均提高了籽粒氮素积累量、花后氮素积累量及其对籽粒氮素的贡献率,氮肥利用效率指标(包括偏生产力、农学效率和表观利用率)分别显著提升了22.4%~40.0%、29.7%~74.3%和9.41~18.77个百分点。值得注意的是,M_(4)和M_(5)处理表现出最优的综合效益:N_(2)O累积排放量降幅最大(分别达27.0%和34.5%),氮肥表观利用率2季均维持在43.0%以上(均值分别为43.5%和46.8%),同时在生育后期保持较高的根系活性和耕层无机氮含量。相比之下,M_(1)处理虽然实现了最大的N_(2)O减排效果(降幅35.9%),但导致减产10.4%和经济效益下降10.8%,且氮肥利用效率呈现不稳定的年际变化特征。而优化处理M_(4+5)进一步改善了根系形态生理特性,并提高氮肥表观利用率和籽粒氮素积累量。综上,减氮15%条件下(N 204 kg hm^(-2)),缓混肥2次施用处理(M_(4)和M_(5))能实现产量、经济效益、氮肥利用效率和N_(2)O减排的协同提高,并以追肥深施处理(M_(5))效应更强。本研究为稻茬小麦缓释肥减氮优化高效应用提供重要理论依据。
基金supported by the Bureau of Frontier Sciences and Basic Research,Chinese Academy of Sciences(Grant No.QYJ-2025-0103)the National Natural Science Foundation of China(Grant Nos.42441834,42241105,42441825,and 42203048)the Key Research Program of the Institute of Geology and Geophysics,Chinese Academy of Sciences(Grant No.IGGCAS-202401).
文摘As one of the major volatile components in extraterrestrial materials,nitrogen(N_(2))isotopes serve not only as tracers for the formation and evolution of the solar system,but also play a critical role in assessing planetary habitability and the search for extraterrestrial life.The integrated measurement of N_(2)and argon(Ar)isotopes by using noble gas mass spectrometry represents a state-of-the-art technique for such investigations.To support the growing demands of planetary science research in China,we have developed a high-efficiency,high-precision method for the integrated analysis of N_(2)and Ar isotopes.This was achieved by enhancing gas extraction and purification systems and integrating them with a static noble gas mass spectrometer.This method enables integrated N_(2)-Ar isotope measurements on submilligram samples,significantly improving sample utilization and reducing the impact of sample heterogeneity on volatile analysis.The system integrates CO_(2)laser heating,a modular two-stage Zr-Al getter pump,and a CuO furnace-based purification process,effectively reducing background levels(N_(2)blank as low as 0.35×10^(−6)cubic centimeters at standard temperature and pressure[ccSTP]).Analytical precision is ensured through calibration with atmospheric air and CO corrections.To validate the reliability of the method,we performed N_(2)-Ar isotope analyses on the Allende carbonaceous chondrite,one of the most extensively studied meteorites internationally.The measured N_(2)concentrations range from 19.2 to 29.8 ppm,withδ15N values between−44.8‰and−33.0‰.Concentrations of 40Ar,36Ar,and 38Ar are(12.5-21.1)×10^(−6)ccSTP/g,(90.9-150.3)×10^(−9)ccSTP/g,and(19.2-30.7)×10^(−9)ccSTP/g,respectively.These values correspond to cosmic-ray exposure ages of 4.5-5.7 Ma,consistent with previous reports.Step-heating experiments further reveal distinct release patterns of N and Ar isotopes,as well as their associations with specific mineral phases in the meteorite.In summary,the combined N_(2)-Ar isotopic system offers significant advantages for tracing volatile sources in extraterrestrial materials and will provide essential analytical support for upcoming Chinese planetary missions,such as Tianwen-2.
基金supported by the Program for New Century Talents in University(No.NCET-11-0951)from the Ministry of Education of ChinaKey Laboratory Project Fund of CAS(No.2005DP173065-2016-04).
文摘Photocatalytic oxygen reduction provides a sustainable method for on-site hydrogen peroxide(H_(2)O_(2))synthesis.However,most photocatalysts suffer from moderate kinetics due to sluggish electron transfer and inefficient oxygen adsorption and activation.Herein,sodium(Na)and potassium(K)are co-incorporated into graphitic carbon nitride(g-C_(3)N_(4))via a stepwise co-doping strategy combining sodium chloride-induced and molten salt-assisted polymerization.Experimental results and density functional theory calculations demonstrate that the synergistic interaction between intralayer Na+ions and interlayer K^(+)ions facilitates charge carrier separation and migration both within and between g-C_(3)N_(4)layers.Additionally,multiple heteroatom sites enhance surface charge polarization and introduce cyano groups,which synergistically promote oxygen molecule(O_(2))adsorption and elevate local proton coverage.Simultaneously,the energy barrier for H_(2)O_(2)desorption on the optimal photocatalyst(5Na/3.3K-CN)is lowered,thus improving H_(2)O_(2)production efficiency.Eventually,5Na/3.3K-CN exhibits an impressive H_(2)O_(2)yield of 2541.6μmol·g^(-1)·h^(-1) in an artificial reactor,which is 10.6 times higher than that of pure g-C_(3)N_(4)(240.2μmol·g^(-1)·h^(-1)).Under natural sunlight outdoors,5Na/3.3K-CN still maintains ultrahigh H_(2)O_(2)photosynthesis efficiency,achieving an H_(2)O_(2)photosynthesis rate of 2068.7μmol·g^(-1)·h^(-1).This work introduces a straightforward method to simultaneously optimize charge transfer and O_(2)activation for boosting H_(2)O_(2)photosynthesis,offering valuable insights toward the real-world deployment of g-C_(3)N_(4)-based photocatalysts in environmental protection and energy conversion.
基金supported by the National Natural Science Foundation of China(Nos.62004143 and 22502150)the Key Project of Scientific Research Plan of Hubei Provincial Department of Education(No.D20241501)+5 种基金the China Postdoctoral Science Foundation(No.2024M762505)the Postdoctoral Fellowship Program(Grade C)(No.GZC20250787)the China Postdoctoral Science Foundation-Hubei Joint Support Program(No.2025T032HB)the Scientific Research Fund Project of Wuhan Institute of Technology(Nos.K2024053,K2025102,and 25QD010)the Open Fund of the Guangdong Provincial Key Laboratory of Electronic Functional Materials and Devices(No.EFMD2024006Z)the Innovation Project of Engineering Research Center of Phosphorus Resources Development and Utilization of Ministry of Education(No.LCX202404).
文摘While thermal air exfoliation is widely used to prepare graphitic carbon nitride(g-C_(3)N_(4))nanosheets,the effects of calcination conditions and atmosphere on their electronic structure and photocatalytic CO_(2)reduction reaction(CO_(2)RR)performance remain systematically unexplored.We prepared g-C_(3)N_(4)nanosheets with varying thickness and defects by controlling exfoliation parameters.The obtained nanosheets calcined longest in air exhibited highest CO_(2)RR activity,twice that of bulk g-C_(3)N_(4).The comprehensive analysis of structural characterizations indicates the thickness of g-C_(3)N_(4)nanosheets became thinner,and the defects increased as the calcination time increased.The N vacancies(N_(v))and O-doping caused by N_(2) and O_(2)from air,respectively,enable valence band elevation(N_(v))and conduction band depression(O-doping)that collectively redistribute the electronic structure.Nitrogen/oxygen dual-defects generated impurity levels,reduced the work function and band gap of g-C_(3)N_(4)nanosheets,and served as shallow traps for photogenerated e^(-).The results of in-situ spectroscopy indicate these increased effective e^(-)are enriched around of N atoms to react with the adsorbed CO_(2).During the CO_(2)reduction process,the N_(v) promoted the formation of*COOH,and this dual-defect co-promoted the*CO desorption,resulting in the improved CO_(2)RR activity.These results comprehensively analyze the regulatory effect of thermal air calcination on the electronic structure of g-C_(3)N_(4),providing valuable insights for designing g-C_(3)N_(4)nanosheets based photocatalysts for CO_(2)RR.
基金financially supported by Natural Science Foundation Project of CQ(No.CSTB2023NSCQ-LZX0067)Science and Technology Research Program of Chongqing Municipal Education Commission(No.KJZD-K202200804)+1 种基金Venture&Innovation Support Program for Chongqing Overseas Returnees(No.cx2020113)National Natural Science Foundation of China(No.21201184).
文摘Achieving heterogeneous photocatalytic activation of sp^(3)C-H bonds and carboxylation of CO_(2)to produce arylacetic acids and alkyl carboxylic acids with increased carbon chains is a highly significant and demanding research endeavor.In this work,a new method for synthesizing redox centers spatially separated Z-scheme CdS@graphitic carbon nitride(g-C_(3)N_(4))was developed,aiming to achieve photocatalytic benzylic and aliphatic sp^(3)C-H activation as well as CO_(2)carboxylation without sacrificial agent.Notably,both benzylic and aliphatic sp^(3)C-H activation together with CO_(2)carboxylation were achieved in heterogeneous photocatalytic system,resulting in the production of carboxylic acids with increased carbon chains under mild conditions.Various methylbenzene derivatives and cycloalkanes were employed to synthesize carbon-chain increased acids via a process involving K_(3)PO_(4)-assisted photogenerated holes activation for benzyl radical generation,photoinduced CO_(2)reduction,as well as solvent-assisted chemoselective carboxylation.Various characterizations and density functional theory(DFT)results revealed that Z-scheme CdS@g-C_(3)N_(4)not just significantly enhanced separation of charges and accumulation of photoinduced electrons on g-C_(3)N_(4)but also facilitated adsorption along with activation of CO_(2).This research provided novel heterogeneous photocatalytic approach to produce carbon chains increased carboxylic acids via sp^(3)C-H activation and CO_(2)carboxylation.
