Molybdenum carbide has shown great potential in various hydrogenation reactions,and serves as a primary active species for synthesis of ethanol from dimethyl oxalate hydrogenation process which is a crucial step in th...Molybdenum carbide has shown great potential in various hydrogenation reactions,and serves as a primary active species for synthesis of ethanol from dimethyl oxalate hydrogenation process which is a crucial step in the efficient utilization of coal resources.In this study,a molybdenum carbide catalyst with a three-dimensional mesh-like hollow structure and lattice defects was carefully designed.The MoO_(3)precursor with abundant oxygen vacancies and defects was prepared by flame spray pyrolysis,and a structural modifier,Cu,was introduced by sputtering.The Cu deposited by sputtering affected the carburization and phase evolution processes.A three-dimensional mesh-like hollow structure composed of defective molybdenum carbide is formed,with theβ-Mo_(2)C exhibiting lattice distortions and defects.This defectiveβ-Mo_(2)C exhibits high reactivity,and facilitates the C=O hydrogenation process,showing a high reactivity of 83.1%yield in the hydrogenation of dimethyl oxalate.This work provides a new approach to the design and application of molybdenum carbide catalysts.展开更多
The synergy of single atoms(SAs)and nanoparticles(NPs)has demonstrated great potential in promoting the electrocatalytic carbon dioxide reduction reaction(CO_(2)RR);however,the rationalization of the SAs/NPs proportio...The synergy of single atoms(SAs)and nanoparticles(NPs)has demonstrated great potential in promoting the electrocatalytic carbon dioxide reduction reaction(CO_(2)RR);however,the rationalization of the SAs/NPs proportion remains one challenge for the catalyst design.Herein,a Ni2+-loaded porous poly(ionic liquids)(PIL)precursor synthesized through the free radical self-polymerization of the ionic liquid monomer,1-allyl-3-vinylimidazolium chloride,was pyrolyzed to prepare the Ni,N co-doped carbon materials,in which the proportion of Ni SAs and NPs could be facilely modulated by controlling the annealing temperature.The catalyst Ni-NC-1000 with a moderate proportion of Ni SAs and NPs exhibited high efficiency in the electrocatalytic conversion of CO_(2)into CO.Operando Ni K-edge X-ray absorption near-edge structure(XANES)spectra and theoretical calculations were conducted to gain insight into the synergy of Ni SAs and NPs.The charge transfer from Ni NPs to the surrounding carbon layer and then to the Ni SAs resulted in the electron-enriched Ni SAs active sites.In the electroreduction of CO_(2),the coexistence of Ni SAs and NPs strengthened the CO_(2)activation and the affinity towards the key intermediate of*COOH,lowering the free energy for the potential-determining*CO_(2)→*COOH step,and therefore promoted the catalysis efficiency.展开更多
Regulating the location of the metal promoters plays a vital role in catalyst structure and its catalytic behavior during CO_(2)hydrogenation to higher alcohols.Herein,we selected the metal promoters with a precipitat...Regulating the location of the metal promoters plays a vital role in catalyst structure and its catalytic behavior during CO_(2)hydrogenation to higher alcohols.Herein,we selected the metal promoters with a precipitation pH similar to that of Cu^(2+)or Fe^(3+)to prepare a series of CuFe-based catalysts.Characterization results show that doping Al or Cr promoter,located with the Fe phase,suppressed the excessive carburization of the Fe phase and maintained an optimal proportion between Fe_(3)O_(4) and amorphous iron carbide(FeC_(x)),thus exhibiting superior catalytic activity and stability.In contrast,doping Zn or In promoter,located with the Cu phase,underwent a deeper carburization and formed more crys-talline FeC_(x),showing an inferior performance.The CuFeCr catalyst achieved the highest space-time yield of 330 mg g_(cat)^(-1)h^(-1)for higher alcohols among these catalysts.This study provides a novel strategy for opti-mizing the structure of the active phases for CO_(2)hydrogenation.展开更多
Fe-N-C catalysts are promising substitutes for precious-metal platinum in acidic oxygen reduction reactions(ORR),yet their moderate intrinsic activity and susceptibility to reactive oxygen species(ROS)-induced degrada...Fe-N-C catalysts are promising substitutes for precious-metal platinum in acidic oxygen reduction reactions(ORR),yet their moderate intrinsic activity and susceptibility to reactive oxygen species(ROS)-induced degradation hinder practical implementation.Herein,we fabricate a Ru-Fe dual-site catalyst(RuFe-N-C)through a two-step pyrolysis strategy.Structural characterization reveals atomic-scale proximity between Ru single atoms and Fe-N_(4) moieties,exhibiting a projected distance of~1.7Å.This configuration induces Fe–N bond elongation accompanied by 2.5%lattice distortion.The optimized RuFe-N-C catalyst exhibits high ORR performance,with a half-wave potential(E_(1/2))of 0.840 V and peak power density(P_(max))of 938 mW cm^(-2) under 150 kPa absolute H_(2)-O_(2).These metrics signify substantial enhancements relative to conventional Fe-N-C benchmarks(+21 mV in E_(1/2) and+42%in P_(max)).Moreover,the catalyst maintains outstanding stability,showing merely 17 mV E_(1/2) decay after 10000 accelerated durability test(ADT)cycles.Experimental analyses reveal a bifunctional mechanism:(1)Adjacent Ru sites substantially enhance the intrinsic ORR activity of Fe-N_(4) moieties,delivering a notable turnover frequency(TOF=17.86 e site^(-1) s^(-1) at 0.85 V vs.RHE)that exceeds state-of-the-art Fe-N-C benchmarks by 1-2 orders of magnitude(<1 e site^(-1) s^(-1));(2)Ru centers function as electron relays that facilitate ROS scavenging,thus suppressing degradation.This work establishes a paradigm for engineering bimetallic single-atom catalysts through synergistic electronic modulation to concurrently enhance activity and stability.展开更多
The exchange of inorganic nutrients at the coastal sediment-water interface(SWI)plays a crucial role in regulating the nutrient budget in overlying water.The related studies mainly focus on the mid-to high-latitude re...The exchange of inorganic nutrients at the coastal sediment-water interface(SWI)plays a crucial role in regulating the nutrient budget in overlying water.The related studies mainly focus on the mid-to high-latitude regions,leaving a significant gap in the quantitative assessment of nutrient exchange and environmental controls at the SWI in lowlatitude coastal regions.We quantitatively assess the exchange of inorganic nutrients at the SWI in three tropical bays(Dongzhai Harbor,Xiaohai Lagoon,Qinglan Harbor).Sediments act as a source of ammonium,phosphate,and silicate,but for nitrate,sediments can be both a source and sink,although with substantial spatial and temporal variations in their fluxes.Labile organic matter is a critical regulator for the fluxes of inorganic nutrients at the SWI.The sedimentary nutrients input with high N/P molar ratio will alter the nutrient stoichiometry to mitigate the nitrogen limitation in coastal waters.However,the internal sediment release in these tropical bays plays a relative weak role in contributing to the nutrient addition in comparison with the other external nutrient sources including riverine input,submarine groundwater discharge,and atmospheric deposition.According to the global compilation on SWI nutrient fluxes,we propose that water column primary production and external inputs to interpret the variation in exchange and fluxes of nutrients at the SWI in different ecosystems.Such a conceptual understanding of these chain biogeochemical processes involving external nutrient input,primary production,particulate organic matter settling,and the accumulation and release of inorganic nutrients in sediments will be helpful for the scientific-based pollution prevent and control in coastal waters.展开更多
Prescribed burning is commonly used to maintain forest ecosystem functions and reduce the risk of future wildfires.Although many studies have investigated the response of microbial community to wildfires in forest eco...Prescribed burning is commonly used to maintain forest ecosystem functions and reduce the risk of future wildfires.Although many studies have investigated the response of microbial community to wildfires in forest ecosystems,the effects of prescribed burnings on soil microbial community structure are less studied.It is also unclear that how post-fire soil physiochemical properties changes affected soil microbial communities.Here,we studied the impacts of prescribed burning on soil microbiome in three typical temperate forests of northern China by collecting soil physicochemical and high-throughput sequencing for 16S rRNA and 18S rRNA was applied to analyze the diversity and community composition of soil microbes(bacteria and fungi).Compared with pre-fire condition,prescribed burning significantly decreased Chaol index and altered soil bacterial communities(P<0.05),whereas it had no significant effect on fungal diversity and community structure of the(P>0.05).Planctomycetes and Actinobacteria made the greatest contributions to the bacterial community dissimilarity between the pre-fire and post-fire conditions.The main variables influencing the post-fire soil microbial community structure are soil pH,available phosphorus,total nitrogen,and the ratio of soil total carbon to soil total nitrogen,which could account for 73.5% of the variation in the microbial community structure in these stands.Our findings demonstrated a great discrepancy in the responses of bacteria and fungi to prescribed burning.Prescribed burning altered the soil microbial structure by modifying the physicochemical properties.Our results pointed that it is essential to evaluate the impact of prescribed burnings on forest ecosystem functions.These findings provide an important baseline for assessing post-fire microbial recovery in the region and offer critical guidance for restoration efforts.展开更多
Objective: To investigate the effects of different delivery modes on perinatal pelvic floor muscle strength, PG, ACTH and CRP of high-risk pregnant women. Methods: 380 high-risk pregnant women who gave birth in our ho...Objective: To investigate the effects of different delivery modes on perinatal pelvic floor muscle strength, PG, ACTH and CRP of high-risk pregnant women. Methods: 380 high-risk pregnant women who gave birth in our hospital from March 2021 to February 2022 were selected as subjects, including 100 vaginal natural delivery, 156 forceps assisted delivery and 124 cesarean section. Pelvic floor pressure, PG, ACTH, CRP, IL-6, TNF-α and IL-4, IL-10 levels were evaluated and compared. The perinatal occurrence of pelvic floor functional disease (PFD) in high-risk pregnant women in each group was analyzed and evaluated. Results: There were statistical differences in the amount of postpartum blood loss (P 0.0001, F = 99.01), postpartum blood loss 24 h (P = 0.0004, F = 19.54) and hospital stay (P 0.0001, F = 70.81) among the three groups of high-risk women in natural vaginal delivery, forceps delivery and cesarean section. In addition, there were 72, 134 and 70 cases of abnormal pelvic floor fatigue in natural vaginal delivery, forceps assisted delivery and cesarean section (P 0.0001, χ<sup>2</sup> = 30.16). There were 36, 79 and 21 cases of muscle injury, respectively (P 0.0001, χ<sup>2</sup> = 34.16). There were 49, 98 and 43 cases of dysmuscular contraction, respectively (P 0.0001, χ<sup>2</sup> = 21.94). There were 65, 120 and 41 cases with vaginal dynamic pressure 80 cm H<sub>2</sub>O (P 0.0001, χ<sup>2</sup> = 56.86), respectively. The.展开更多
文摘Molybdenum carbide has shown great potential in various hydrogenation reactions,and serves as a primary active species for synthesis of ethanol from dimethyl oxalate hydrogenation process which is a crucial step in the efficient utilization of coal resources.In this study,a molybdenum carbide catalyst with a three-dimensional mesh-like hollow structure and lattice defects was carefully designed.The MoO_(3)precursor with abundant oxygen vacancies and defects was prepared by flame spray pyrolysis,and a structural modifier,Cu,was introduced by sputtering.The Cu deposited by sputtering affected the carburization and phase evolution processes.A three-dimensional mesh-like hollow structure composed of defective molybdenum carbide is formed,with theβ-Mo_(2)C exhibiting lattice distortions and defects.This defectiveβ-Mo_(2)C exhibits high reactivity,and facilitates the C=O hydrogenation process,showing a high reactivity of 83.1%yield in the hydrogenation of dimethyl oxalate.This work provides a new approach to the design and application of molybdenum carbide catalysts.
基金National Natural Science Foundation of China(grants 22072065,22178162,and 22222806)Distinguished Youth Foundation of Jiangsu Province(grant BK20220053)Six talent peaks project in Jiangsu Province(grant JNHB-035)。
文摘The synergy of single atoms(SAs)and nanoparticles(NPs)has demonstrated great potential in promoting the electrocatalytic carbon dioxide reduction reaction(CO_(2)RR);however,the rationalization of the SAs/NPs proportion remains one challenge for the catalyst design.Herein,a Ni2+-loaded porous poly(ionic liquids)(PIL)precursor synthesized through the free radical self-polymerization of the ionic liquid monomer,1-allyl-3-vinylimidazolium chloride,was pyrolyzed to prepare the Ni,N co-doped carbon materials,in which the proportion of Ni SAs and NPs could be facilely modulated by controlling the annealing temperature.The catalyst Ni-NC-1000 with a moderate proportion of Ni SAs and NPs exhibited high efficiency in the electrocatalytic conversion of CO_(2)into CO.Operando Ni K-edge X-ray absorption near-edge structure(XANES)spectra and theoretical calculations were conducted to gain insight into the synergy of Ni SAs and NPs.The charge transfer from Ni NPs to the surrounding carbon layer and then to the Ni SAs resulted in the electron-enriched Ni SAs active sites.In the electroreduction of CO_(2),the coexistence of Ni SAs and NPs strengthened the CO_(2)activation and the affinity towards the key intermediate of*COOH,lowering the free energy for the potential-determining*CO_(2)→*COOH step,and therefore promoted the catalysis efficiency.
基金financially supported by the National Key R&D Program of China (2023YFB4104501)the National Natural Science Foundation of China (22372165)+2 种基金the Liaoning Binhai Laboratory (LBLA-2024-01)the Grant. YLU-DNL Fund (2023001)DICP (Grant: DICP I202457)
文摘Regulating the location of the metal promoters plays a vital role in catalyst structure and its catalytic behavior during CO_(2)hydrogenation to higher alcohols.Herein,we selected the metal promoters with a precipitation pH similar to that of Cu^(2+)or Fe^(3+)to prepare a series of CuFe-based catalysts.Characterization results show that doping Al or Cr promoter,located with the Fe phase,suppressed the excessive carburization of the Fe phase and maintained an optimal proportion between Fe_(3)O_(4) and amorphous iron carbide(FeC_(x)),thus exhibiting superior catalytic activity and stability.In contrast,doping Zn or In promoter,located with the Cu phase,underwent a deeper carburization and formed more crys-talline FeC_(x),showing an inferior performance.The CuFeCr catalyst achieved the highest space-time yield of 330 mg g_(cat)^(-1)h^(-1)for higher alcohols among these catalysts.This study provides a novel strategy for opti-mizing the structure of the active phases for CO_(2)hydrogenation.
文摘Fe-N-C catalysts are promising substitutes for precious-metal platinum in acidic oxygen reduction reactions(ORR),yet their moderate intrinsic activity and susceptibility to reactive oxygen species(ROS)-induced degradation hinder practical implementation.Herein,we fabricate a Ru-Fe dual-site catalyst(RuFe-N-C)through a two-step pyrolysis strategy.Structural characterization reveals atomic-scale proximity between Ru single atoms and Fe-N_(4) moieties,exhibiting a projected distance of~1.7Å.This configuration induces Fe–N bond elongation accompanied by 2.5%lattice distortion.The optimized RuFe-N-C catalyst exhibits high ORR performance,with a half-wave potential(E_(1/2))of 0.840 V and peak power density(P_(max))of 938 mW cm^(-2) under 150 kPa absolute H_(2)-O_(2).These metrics signify substantial enhancements relative to conventional Fe-N-C benchmarks(+21 mV in E_(1/2) and+42%in P_(max)).Moreover,the catalyst maintains outstanding stability,showing merely 17 mV E_(1/2) decay after 10000 accelerated durability test(ADT)cycles.Experimental analyses reveal a bifunctional mechanism:(1)Adjacent Ru sites substantially enhance the intrinsic ORR activity of Fe-N_(4) moieties,delivering a notable turnover frequency(TOF=17.86 e site^(-1) s^(-1) at 0.85 V vs.RHE)that exceeds state-of-the-art Fe-N-C benchmarks by 1-2 orders of magnitude(<1 e site^(-1) s^(-1));(2)Ru centers function as electron relays that facilitate ROS scavenging,thus suppressing degradation.This work establishes a paradigm for engineering bimetallic single-atom catalysts through synergistic electronic modulation to concurrently enhance activity and stability.
基金The Major Science and Technology Plan of Hainan Province under contract No.ZDKJ2021008the Hainan Provincial Natural Science Foundation of China under contract No.623RC456+1 种基金the Hainan Province Science and Technology Special Fund under contract Nos ZDYF2021SHFZ064 and ZDYF2022SHFZ056the Collaborative Innovation Center of Marine Science and Technology in Hainan University under contract No.XTCX2022HYC19.
文摘The exchange of inorganic nutrients at the coastal sediment-water interface(SWI)plays a crucial role in regulating the nutrient budget in overlying water.The related studies mainly focus on the mid-to high-latitude regions,leaving a significant gap in the quantitative assessment of nutrient exchange and environmental controls at the SWI in lowlatitude coastal regions.We quantitatively assess the exchange of inorganic nutrients at the SWI in three tropical bays(Dongzhai Harbor,Xiaohai Lagoon,Qinglan Harbor).Sediments act as a source of ammonium,phosphate,and silicate,but for nitrate,sediments can be both a source and sink,although with substantial spatial and temporal variations in their fluxes.Labile organic matter is a critical regulator for the fluxes of inorganic nutrients at the SWI.The sedimentary nutrients input with high N/P molar ratio will alter the nutrient stoichiometry to mitigate the nitrogen limitation in coastal waters.However,the internal sediment release in these tropical bays plays a relative weak role in contributing to the nutrient addition in comparison with the other external nutrient sources including riverine input,submarine groundwater discharge,and atmospheric deposition.According to the global compilation on SWI nutrient fluxes,we propose that water column primary production and external inputs to interpret the variation in exchange and fluxes of nutrients at the SWI in different ecosystems.Such a conceptual understanding of these chain biogeochemical processes involving external nutrient input,primary production,particulate organic matter settling,and the accumulation and release of inorganic nutrients in sediments will be helpful for the scientific-based pollution prevent and control in coastal waters.
基金financially supported by the National Natural Science Foundation(No.32471868,No.32001324)Youth Lift Project of China Association for Science and Technology(No.YESS20210370)+1 种基金Fundamental Research Funds for the Central Universities(2572023CT01)We thank the Grassland Bureau and the National Innovation Alliance of Wildland Fire Prevention and Control Technology of China for supporting this research.
文摘Prescribed burning is commonly used to maintain forest ecosystem functions and reduce the risk of future wildfires.Although many studies have investigated the response of microbial community to wildfires in forest ecosystems,the effects of prescribed burnings on soil microbial community structure are less studied.It is also unclear that how post-fire soil physiochemical properties changes affected soil microbial communities.Here,we studied the impacts of prescribed burning on soil microbiome in three typical temperate forests of northern China by collecting soil physicochemical and high-throughput sequencing for 16S rRNA and 18S rRNA was applied to analyze the diversity and community composition of soil microbes(bacteria and fungi).Compared with pre-fire condition,prescribed burning significantly decreased Chaol index and altered soil bacterial communities(P<0.05),whereas it had no significant effect on fungal diversity and community structure of the(P>0.05).Planctomycetes and Actinobacteria made the greatest contributions to the bacterial community dissimilarity between the pre-fire and post-fire conditions.The main variables influencing the post-fire soil microbial community structure are soil pH,available phosphorus,total nitrogen,and the ratio of soil total carbon to soil total nitrogen,which could account for 73.5% of the variation in the microbial community structure in these stands.Our findings demonstrated a great discrepancy in the responses of bacteria and fungi to prescribed burning.Prescribed burning altered the soil microbial structure by modifying the physicochemical properties.Our results pointed that it is essential to evaluate the impact of prescribed burnings on forest ecosystem functions.These findings provide an important baseline for assessing post-fire microbial recovery in the region and offer critical guidance for restoration efforts.
文摘Objective: To investigate the effects of different delivery modes on perinatal pelvic floor muscle strength, PG, ACTH and CRP of high-risk pregnant women. Methods: 380 high-risk pregnant women who gave birth in our hospital from March 2021 to February 2022 were selected as subjects, including 100 vaginal natural delivery, 156 forceps assisted delivery and 124 cesarean section. Pelvic floor pressure, PG, ACTH, CRP, IL-6, TNF-α and IL-4, IL-10 levels were evaluated and compared. The perinatal occurrence of pelvic floor functional disease (PFD) in high-risk pregnant women in each group was analyzed and evaluated. Results: There were statistical differences in the amount of postpartum blood loss (P 0.0001, F = 99.01), postpartum blood loss 24 h (P = 0.0004, F = 19.54) and hospital stay (P 0.0001, F = 70.81) among the three groups of high-risk women in natural vaginal delivery, forceps delivery and cesarean section. In addition, there were 72, 134 and 70 cases of abnormal pelvic floor fatigue in natural vaginal delivery, forceps assisted delivery and cesarean section (P 0.0001, χ<sup>2</sup> = 30.16). There were 36, 79 and 21 cases of muscle injury, respectively (P 0.0001, χ<sup>2</sup> = 34.16). There were 49, 98 and 43 cases of dysmuscular contraction, respectively (P 0.0001, χ<sup>2</sup> = 21.94). There were 65, 120 and 41 cases with vaginal dynamic pressure 80 cm H<sub>2</sub>O (P 0.0001, χ<sup>2</sup> = 56.86), respectively. The.
