Designing catalysts with high catalytic activity and stability is the key to achieve the commercial application of MgH_(2).Herein,the sulfur doped Ti_(3)C_(2)(S-Ti_(3)C_(2))was successfully prepared by heat treatment ...Designing catalysts with high catalytic activity and stability is the key to achieve the commercial application of MgH_(2).Herein,the sulfur doped Ti_(3)C_(2)(S-Ti_(3)C_(2))was successfully prepared by heat treatment of Ti_(3)C_(2)MXene under Ar/H_(2)S atmosphere to facilitate the hydrogen release and uptake from MgH_(2).The S-Ti_(3)C_(2)exhibited pleasant catalytic effect on the hydriding/dehydriding kinetics and cyclic stability of MgH_(2).The addition of 5 wt%S-Ti_(3)C_(2)into MgH_(2)resulted in a reduction of 114℃in the starting dehydriding temperature compared to pure MgH_(2).MgH_(2)+5 wt%S-Ti_(3)C_(2)sample could quickly release 6.6 wt%hydrogen in 17 min at 220℃,and 6.8 wt%H_(2)was absorbed in 25 min at 200℃.Cyclic testing revealed that MgH_(2)+5 wt%S-Ti_(3)C_(2)system achieved a reversible hydrogen capacity of 6.5 wt%.Characterization analysis demonstrated that Ti-species(Ti0,Ti^(2+),Ti-S,and Ti^(3+))as active species significantly lowered the dehydrogenation temperature and promoted the re-/dehydrogenation kinetics of MgH_(2),and sulfur doping can effectively improve the stability of Ti0 and Ti^(3+),contributing to the improvement of cyclic stability of MgH_(2).This study provides strategy for the construction of catalysts for hydrogen storage materials.展开更多
Ammonia borane(AB)is an excellent candidate for the chemical storage of hydrogen.However,its practical utilization for hydrogen production is hindered by the need for expensive noble-metal-based catalysts.Herein,we re...Ammonia borane(AB)is an excellent candidate for the chemical storage of hydrogen.However,its practical utilization for hydrogen production is hindered by the need for expensive noble-metal-based catalysts.Herein,we report Co-Co3O4 nanoparticles(NPs)facilely deposited on carbon dots(CDs)as a highly efficient,robust,and noble-metal-free catalyst for the hydrolysis of AB.The incorporation of the multiinterfaces between Co,Co3O4 NPs,and CDs endows this hybrid material with excellent catalytic activity(rB=6816 mLH2 min^-1 gCo^-1)exceeding that of previous non-noble-metal NP systems and even that of some noble-metal NP systems.A further mechanistic study suggests that these interfacial interactions can affect the electronic structures of interfacial atoms and provide abundant adsorption sites for AB and water molecules,resulting in a low energy barrier for the activation of reactive molecules and thus substantial improvement of the catalytic rate.展开更多
Ammonia borane(NH_(3)BH_(3),AB) is promising for chemical hydrogen sto rage;however,current systems for rapid hydrogen production are limited by the expensive noble metal catalysts required for AB hydrolysis.Here we r...Ammonia borane(NH_(3)BH_(3),AB) is promising for chemical hydrogen sto rage;however,current systems for rapid hydrogen production are limited by the expensive noble metal catalysts required for AB hydrolysis.Here we report the design and synthesis of a highly efficient and robust non-noble-metal catalyst for the hydrolysis of AB at 298 K(TOF=89.56 molH_(2) min^(-1) molCo^(-1)).Experiments and density functional theory calculations were performed to explore the catalyst’s hybrid nanoparticle heterostructure and its catalytic mechanism.The catalyst comprised nitrogen-doped carbon dots confining CoO and CoP,and exhibited strong interface-induced synergistic catalysis for AB hydrolysis that effectively decreased the energy barriers for the dissociation of both AB and water molecules.The co-doping of N and P introduced numerous defects,and further regulated the reactivity of the carbon layers.The heterogeneous interface design technique presented here provides a new strategy for developing efficient and inexpensive non-noblemetal catalysts that may be applicable in other fields related to energy catalysis.展开更多
Ammonia borane(AB) can be catalytically hydrolyzed to provide hydrogen at room temperature due to its high potentaial for hydrogen storage. Non-precious metal heterogeneous catalysts have broad application in the fiel...Ammonia borane(AB) can be catalytically hydrolyzed to provide hydrogen at room temperature due to its high potentaial for hydrogen storage. Non-precious metal heterogeneous catalysts have broad application in the field of energy catalysis. In this article, catalysts precursor is obtained from Co-Ti-resorcinol-formaldehyde resin by sol–gel method. Co/TiO_(2)@N-C(CTC) catalyst is prepared by calcining the precursor under high temperature conditions in nitrogen atmosphere. Co-CoO_x/TiO_(2)@N-C(COTC) is generated by the controllable oxidation reaction of CTC. The catalyst can effectively promote the release of hydrogen during the hydrolytic dehydrogenation of AB. High hydrogen generation at a specific rate of 5905 m L min^(-1) g_(Co)^(-1) is achieved at room temperature. The catalyst retains its 85% initial catalytic activity even for its fifth time use in AB hydrolysis. The synergistic effect among Co, Co_(3)O_(4) and TiO_(2) promotes the rate limiting step with dissociation and activation of water molecules by reducing its activation energy. The applied method in this study promotes the development of non-precious metals in catalysis for utilization in clean energy sources.展开更多
Disease in clams frequently occurred over the last decade and has become a serious threat to the clam aquaculture industry and natural stocks.Mass clam mortality events were reported to be associated with the presence...Disease in clams frequently occurred over the last decade and has become a serious threat to the clam aquaculture industry and natural stocks.Mass clam mortality events were reported to be associated with the presence of opportunistic pathogen vibrio.However,the complexity of infection that occurs in the natural environment remains poorly understood.In this study,we smulated a natural disease outbreak by vibrio immersion infection to study the diversity and dynamics of microbiota in the digestive tract of clam Meretrix petechialis during the infection process.Dramatic changes in operational taxonomic unit richness and phylum composition of the bacterial communities were observed during pathogen invasion.In addition,we investigated the potential relationship between microbiota dynamics and host status during disease progression.Results reveal that,at the end stage of vibrio infection,interindividual variation in the digestive tract microbiota increased,as did the diff erence in individual health status.The moribund clams displayed signs of microbial community shifts to low diversity,and the microbial community was characterized by mass proliferation of a few operational taxonomic units.展开更多
The defect-free structure of Mo-based materials is a“double-edged sword”,which endows the material with excellent stability,but limits its chemical versatility and application in electrochemical hydrogen evolution r...The defect-free structure of Mo-based materials is a“double-edged sword”,which endows the material with excellent stability,but limits its chemical versatility and application in electrochemical hydrogen evolution reaction(HER).Carbon doping engineering is an attractive strategy to effectively improve the performance of Mo-based catalyst and maintain their stability.Herein,we report a cross-linked porous carbon-doped MoO_(2)(C–MoO_(2))-based catalyst Ru/C–MoO_(2) for electrochemical HER,which is prepared by the convenient redox solid-phase reaction(SPR)of porous RuO_(2)/Mo_(2)C composite precursor.Theoretical studies reveal that due to the presence of carbon atoms,the electronic structure of C–MoO_(2) has been properly adjusted,and the loaded small Ru nanoparticles provide a fast water dissociation rate and moderate H adsorption strength.In electrochemical studies under a pH-universal environment,Ru/C–MoO_(2) electrocatalyst exhibits a low overpotential at a current density of 10 mA cm^(-2) and has a low Tafel slope.Meanwhile,Ru/C-MoO_(2) has excellent stability for more than 100 h at an initial current density of 100 mA cm^(-2).展开更多
Boron hydrides release an abundant amount of hydrogen in the presence of a suitable catalyst.Accelerating bimolecular activation kinetics is the key to designing cost-effective catalysts for borohydride hydrolysis.In ...Boron hydrides release an abundant amount of hydrogen in the presence of a suitable catalyst.Accelerating bimolecular activation kinetics is the key to designing cost-effective catalysts for borohydride hydrolysis.In this study,the bimolecular activation of a polar O-Co-P site demonstrated superior hydrogen-generation kinetics(turnover frequency,TOF=37 min−1,298 K)and low activation energy(41.0 kJ mol^(−1))close to that of noble-metal-based catalysts.Through a combination of experiments and theoretical calculations,it was revealed that the activated dangling oxygen atom in the Co–O precursor effectively replaced via surface-phosphorization because of strong electronic interactions between the dangling oxygen and P atoms.This substitution modulated the local coordination environment and electronegativity around the surface Co sites and formed a new polar O-Co-P active site for optimizing the activation kinetics of ammonia borane and water.This strategy based on bimolecular activation may create new avenues in the field of catalysis.展开更多
Metal nanoparticles and metal oxides promisingly provide different catalytic active sites at their interfaces.Constructing high-density interfaces is essential to maximize synergies.Herein,a Cu-Co_(3)O_(4) nanoparticl...Metal nanoparticles and metal oxides promisingly provide different catalytic active sites at their interfaces.Constructing high-density interfaces is essential to maximize synergies.Herein,a Cu-Co_(3)O_(4) nanoparticles interfacial structure produced via pyrolysis and moderate oxidation from metal-organic frameworks has been designed to boost the intrinsic activity.The Cu-Co_(3)O_(4) nanoparticles composites exhibit a turnover frequency of 57.5 min−1 for ammonia borane hydrolysis,far higher than those of monometallic Cu and Co_(3)O_(4) nanoparticles,showing the synergistic effect of Cu and Co_(3)O_(4) nanoparticles at their interface.Density functional theory calculations and in situ Raman spectroscopy reveal the catalytic mechanism of dual active sites,in which Co_(3)O_(4) nanoparticles at Cu-Co_(3)O_(4) interface efficiently bind and activate water molecules and Cu nanoparticles easily activate NH3BH3 molecules.This study opens up a new pathway for achieving high-efficiency noble metal-free catalysts for hydrogen generation and other heterogeneous catalysis.展开更多
Two-dimensional(2D)metal-organic frameworks(MOFs)have emerged as promising photosensitizers in photodynamic therapy in recent years.In comparison to bulk MOFs,constructing 2D MOFs can increase the presence of active s...Two-dimensional(2D)metal-organic frameworks(MOFs)have emerged as promising photosensitizers in photodynamic therapy in recent years.In comparison to bulk MOFs,constructing 2D MOFs can increase the presence of active sites through increasing the surface area ratio.Herein,we report a simple solventmediated synthesis method for preparation of 2D porphyrin-based MOF(In-TCPP)nanosheets without the addition of any surfactants as an efficient photosensitizer for enhancing photodynamic antibacterial therapy.The accurate regulation of the morphology and size of 2D In-TCPP nanosheets can be achieved by varying the ratio of water to N,N-dimethylformamide solvent with the appropriate assistance of pyridine.The optimal synthesized 2D In-TCPP nanosheets exhibit a diameter of 70–120 nm and a thickness of 21.5–27.4 nm.Promisingly,2D In-TCPP nanosheets produce a higher amount of ^(1)O_(2) when exposed to660 nm laser compared to the In-TCPP bulk,indicating that the smaller nanosheets possess more active sites for reactive oxygen species generation and can greatly improve the antibacterial photodynamic therapeutic effect.Both the in vitro and in vivo results prove that the In-TCPP nanosheets can be used as a photosensitizer for efficient photodynamic antibacterial therapy to kill S.aureus and promote wound healing.展开更多
The design of high-performance catalysts is the key to the efficient utilization of hydrogen energy.In this work,a PdCu nanoalloy was successfully anchored on TiO_(2)encapsulated with carbon to construct a catalyst.Ou...The design of high-performance catalysts is the key to the efficient utilization of hydrogen energy.In this work,a PdCu nanoalloy was successfully anchored on TiO_(2)encapsulated with carbon to construct a catalyst.Outstanding kinetics of the hydrolysis of ammonia borane(turnover frequency of 279 mol·min^(-1·)mol_(Pd)^(-1))ranking the third place among Pd-based catalysts was achieved in the absence of alkali.Both experimental research and theoretical calculations reveal a lower activation energy of the B-H bond on the PdCu nanoalloy catalyst than that on pristine Pd and a lower activation energy of the O-H bond than that on pristine Cu.The redistribution of d electron and the shift of the d-band center play a critical role in increasing the electron density of Pd and improving the catalytic performances of Pd_(0.1)Cu_(0.9)/TiO_(2)-porous carbon(Pd_(0.1)Cu_(0.9)/T-PC).This work provides novel insights into highly dual-active alloys and sheds light on the mechanism of dual-active sites in promoting borohydride hydrolysis.展开更多
Magnesium hydride(MgH_(2))is considered as an ideal hydrogen storage material with excellent hydrogen capacity,but the slow kinetics impedes its application.Herein,an efficient additive of V2C MXene-anchored PrF_(3) n...Magnesium hydride(MgH_(2))is considered as an ideal hydrogen storage material with excellent hydrogen capacity,but the slow kinetics impedes its application.Herein,an efficient additive of V2C MXene-anchored PrF_(3) nanoparticles(PrF_(3)/V_(2)C)was synthesized,which presents excellent catalytic effect in improving the reversibility and stability of hydrogen storage in MgH_(2).The initial dehydrogenation temperature of the 5 wt.% PrF_(3)/V_(2)C-containing MgH_(2)(182℃) is 105℃ lower than that of pure MgH_(2),and 6.5 wt.%hydrogen is rapidly released from 5 wt.%PrF_(3)/V_(2)C-added MgH_(2)sample in 6 min at 240℃.In addition,5 wt.%PrF_(3)/V_(2)C-containing MgH_(2) sample possesses outstanding reversible hydrogen storage capability of 6.5 wt.% after 10 cycles of dehydrogenation and hydrogenation.Microstructure analysis shows that the introduction of Pr improves the stability of V-species(V^(0)and V^(2+))and O-species(lattice oxygen(OL)and vacancy oxygen(OV))formed during ball milling,promotes the interaction between V-species and O-species,and enhances their reversibility,which contributes to the significant improvement in re/dehydrogenation reversibility and cycling stability of MgH_(2).This study provides effective ideas and strategies for the purpose of designing and fabricating high-efficient catalysts for solid-state hydrogen storage materials.展开更多
The D-quadrant organizer sets up the dorsal–ventral(DV)axis and regulates mesodermal development of spiralians.Studies have revealed an important role of mitogen-activated protein kinase(MAPK)signaling in organizer f...The D-quadrant organizer sets up the dorsal–ventral(DV)axis and regulates mesodermal development of spiralians.Studies have revealed an important role of mitogen-activated protein kinase(MAPK)signaling in organizer function,but the related molecules have not been fully revealed.The association between fibroblast growth factor receptor(FGFR)and MAPK signaling in regulating organizer specification has been established in the annelid Owenia fusiformis.Now,comparable studies in other spiralian phyla are required to decipher whether this organizer-inducing function of FGFR is prevalent in Spiralia.Here,we indicate that treatment with the FGFR inhibitor SU5402 resulted in deficiency of organizer specification in the mollusk Lottia peitaihoensis.Subsequently,the bone morphogenetic protein(BMP)signaling gradient and DV patterning were disrupted,suggesting the roles of FGFR in regulating organizer function.Changes in multiple aspects of organizer function(the morphology of vegetal blastomeres,BMP signaling gradient,expression of DV patterning markers,etc.)indicate that these developmental functions have different sensitivities to FGFR/MAPK signaling.Our results reveal a functional role of FGFR in organizer specification as well as DV patterning of Lottia embryos,which expands our knowledge of spiralian organizers.展开更多
基金supported by the National Natural Science Foundation of China(U22A20120,52071135,51871090,U1804135,and 52301269)the Natural Science Foundation of Hebei Province for Innovation Groups Program(C2022203003)Fundamental Research Funds for the Universities of Henan Province(NSFRF220201).
文摘Designing catalysts with high catalytic activity and stability is the key to achieve the commercial application of MgH_(2).Herein,the sulfur doped Ti_(3)C_(2)(S-Ti_(3)C_(2))was successfully prepared by heat treatment of Ti_(3)C_(2)MXene under Ar/H_(2)S atmosphere to facilitate the hydrogen release and uptake from MgH_(2).The S-Ti_(3)C_(2)exhibited pleasant catalytic effect on the hydriding/dehydriding kinetics and cyclic stability of MgH_(2).The addition of 5 wt%S-Ti_(3)C_(2)into MgH_(2)resulted in a reduction of 114℃in the starting dehydriding temperature compared to pure MgH_(2).MgH_(2)+5 wt%S-Ti_(3)C_(2)sample could quickly release 6.6 wt%hydrogen in 17 min at 220℃,and 6.8 wt%H_(2)was absorbed in 25 min at 200℃.Cyclic testing revealed that MgH_(2)+5 wt%S-Ti_(3)C_(2)system achieved a reversible hydrogen capacity of 6.5 wt%.Characterization analysis demonstrated that Ti-species(Ti0,Ti^(2+),Ti-S,and Ti^(3+))as active species significantly lowered the dehydrogenation temperature and promoted the re-/dehydrogenation kinetics of MgH_(2),and sulfur doping can effectively improve the stability of Ti0 and Ti^(3+),contributing to the improvement of cyclic stability of MgH_(2).This study provides strategy for the construction of catalysts for hydrogen storage materials.
基金financially supported by the National Natural Science Foundation of China(21774041 and 51433003)the China Postdoctoral Science Foundation(2018M640681 and 2019T120632)。
文摘Ammonia borane(AB)is an excellent candidate for the chemical storage of hydrogen.However,its practical utilization for hydrogen production is hindered by the need for expensive noble-metal-based catalysts.Herein,we report Co-Co3O4 nanoparticles(NPs)facilely deposited on carbon dots(CDs)as a highly efficient,robust,and noble-metal-free catalyst for the hydrolysis of AB.The incorporation of the multiinterfaces between Co,Co3O4 NPs,and CDs endows this hybrid material with excellent catalytic activity(rB=6816 mLH2 min^-1 gCo^-1)exceeding that of previous non-noble-metal NP systems and even that of some noble-metal NP systems.A further mechanistic study suggests that these interfacial interactions can affect the electronic structures of interfacial atoms and provide abundant adsorption sites for AB and water molecules,resulting in a low energy barrier for the activation of reactive molecules and thus substantial improvement of the catalytic rate.
基金financial support from the National Natural Science Foundation of China(Nos.21905253,51973200,51433003 and 21774041)the China Postdoctoral Science Foundation(2018M640681,2019T120632)+2 种基金JLU Science and Technology Innovative Research Team 2017TD-06Guangdong Provincial Key Laboratory of Optical Information Materials and Technology(No.2017B030301007)the Center of Advanced Analysis & Gene Sequencing,Zhengzhou University。
文摘Ammonia borane(NH_(3)BH_(3),AB) is promising for chemical hydrogen sto rage;however,current systems for rapid hydrogen production are limited by the expensive noble metal catalysts required for AB hydrolysis.Here we report the design and synthesis of a highly efficient and robust non-noble-metal catalyst for the hydrolysis of AB at 298 K(TOF=89.56 molH_(2) min^(-1) molCo^(-1)).Experiments and density functional theory calculations were performed to explore the catalyst’s hybrid nanoparticle heterostructure and its catalytic mechanism.The catalyst comprised nitrogen-doped carbon dots confining CoO and CoP,and exhibited strong interface-induced synergistic catalysis for AB hydrolysis that effectively decreased the energy barriers for the dissociation of both AB and water molecules.The co-doping of N and P introduced numerous defects,and further regulated the reactivity of the carbon layers.The heterogeneous interface design technique presented here provides a new strategy for developing efficient and inexpensive non-noblemetal catalysts that may be applicable in other fields related to energy catalysis.
基金Financial supports from the National Natural Science Foundation of China(No.51871090,U1804135,51671080,21401168 and 51471065)Plan for Scientific Innovation Talent of Henan Province(No.194200510019)are acknowledged.
文摘Ammonia borane(AB) can be catalytically hydrolyzed to provide hydrogen at room temperature due to its high potentaial for hydrogen storage. Non-precious metal heterogeneous catalysts have broad application in the field of energy catalysis. In this article, catalysts precursor is obtained from Co-Ti-resorcinol-formaldehyde resin by sol–gel method. Co/TiO_(2)@N-C(CTC) catalyst is prepared by calcining the precursor under high temperature conditions in nitrogen atmosphere. Co-CoO_x/TiO_(2)@N-C(COTC) is generated by the controllable oxidation reaction of CTC. The catalyst can effectively promote the release of hydrogen during the hydrolytic dehydrogenation of AB. High hydrogen generation at a specific rate of 5905 m L min^(-1) g_(Co)^(-1) is achieved at room temperature. The catalyst retains its 85% initial catalytic activity even for its fifth time use in AB hydrolysis. The synergistic effect among Co, Co_(3)O_(4) and TiO_(2) promotes the rate limiting step with dissociation and activation of water molecules by reducing its activation energy. The applied method in this study promotes the development of non-precious metals in catalysis for utilization in clean energy sources.
基金Supported by the National Natural Science Foundation of China(No.31772845)the China Agriculture Research System(No.CARS-49)+1 种基金the Science and Technology Service Network Initiative of the Chinese Academy of Sciences(No.KFJ-STS-ZDTP-049)the Foundation of Zhejiang Key Laboratory of Exploitation and Preservation of Coastal Bio-Resource(No.J2018001)。
文摘Disease in clams frequently occurred over the last decade and has become a serious threat to the clam aquaculture industry and natural stocks.Mass clam mortality events were reported to be associated with the presence of opportunistic pathogen vibrio.However,the complexity of infection that occurs in the natural environment remains poorly understood.In this study,we smulated a natural disease outbreak by vibrio immersion infection to study the diversity and dynamics of microbiota in the digestive tract of clam Meretrix petechialis during the infection process.Dramatic changes in operational taxonomic unit richness and phylum composition of the bacterial communities were observed during pathogen invasion.In addition,we investigated the potential relationship between microbiota dynamics and host status during disease progression.Results reveal that,at the end stage of vibrio infection,interindividual variation in the digestive tract microbiota increased,as did the diff erence in individual health status.The moribund clams displayed signs of microbial community shifts to low diversity,and the microbial community was characterized by mass proliferation of a few operational taxonomic units.
基金This work was financially supported by the National Natural Science Foundation of China (52122308,21905253,51973200)the Natural Science Foundation of Henan (202300410372).
文摘The defect-free structure of Mo-based materials is a“double-edged sword”,which endows the material with excellent stability,but limits its chemical versatility and application in electrochemical hydrogen evolution reaction(HER).Carbon doping engineering is an attractive strategy to effectively improve the performance of Mo-based catalyst and maintain their stability.Herein,we report a cross-linked porous carbon-doped MoO_(2)(C–MoO_(2))-based catalyst Ru/C–MoO_(2) for electrochemical HER,which is prepared by the convenient redox solid-phase reaction(SPR)of porous RuO_(2)/Mo_(2)C composite precursor.Theoretical studies reveal that due to the presence of carbon atoms,the electronic structure of C–MoO_(2) has been properly adjusted,and the loaded small Ru nanoparticles provide a fast water dissociation rate and moderate H adsorption strength.In electrochemical studies under a pH-universal environment,Ru/C–MoO_(2) electrocatalyst exhibits a low overpotential at a current density of 10 mA cm^(-2) and has a low Tafel slope.Meanwhile,Ru/C-MoO_(2) has excellent stability for more than 100 h at an initial current density of 100 mA cm^(-2).
基金H.Z.and K.Z.contributed equally to this work.Financial supports from the National Natural Science Foundation of China (nos.22075254,52071135,51871090,U1804135,21805071,51671080,and 21401168)Plan for Scientific Inno-vation Talent of Henan Province (no.194200510019)Key Project of Educa-tional Commission of Henan Province (no.19A150025)are acknowledged.
文摘Boron hydrides release an abundant amount of hydrogen in the presence of a suitable catalyst.Accelerating bimolecular activation kinetics is the key to designing cost-effective catalysts for borohydride hydrolysis.In this study,the bimolecular activation of a polar O-Co-P site demonstrated superior hydrogen-generation kinetics(turnover frequency,TOF=37 min−1,298 K)and low activation energy(41.0 kJ mol^(−1))close to that of noble-metal-based catalysts.Through a combination of experiments and theoretical calculations,it was revealed that the activated dangling oxygen atom in the Co–O precursor effectively replaced via surface-phosphorization because of strong electronic interactions between the dangling oxygen and P atoms.This substitution modulated the local coordination environment and electronegativity around the surface Co sites and formed a new polar O-Co-P active site for optimizing the activation kinetics of ammonia borane and water.This strategy based on bimolecular activation may create new avenues in the field of catalysis.
基金supported by the National Natural Science Foundation of China(No.21401168)Foundation of High Level Research Projects of Jiaozuo Teachers College(No.GPY2021-01).
文摘Metal nanoparticles and metal oxides promisingly provide different catalytic active sites at their interfaces.Constructing high-density interfaces is essential to maximize synergies.Herein,a Cu-Co_(3)O_(4) nanoparticles interfacial structure produced via pyrolysis and moderate oxidation from metal-organic frameworks has been designed to boost the intrinsic activity.The Cu-Co_(3)O_(4) nanoparticles composites exhibit a turnover frequency of 57.5 min−1 for ammonia borane hydrolysis,far higher than those of monometallic Cu and Co_(3)O_(4) nanoparticles,showing the synergistic effect of Cu and Co_(3)O_(4) nanoparticles at their interface.Density functional theory calculations and in situ Raman spectroscopy reveal the catalytic mechanism of dual active sites,in which Co_(3)O_(4) nanoparticles at Cu-Co_(3)O_(4) interface efficiently bind and activate water molecules and Cu nanoparticles easily activate NH3BH3 molecules.This study opens up a new pathway for achieving high-efficiency noble metal-free catalysts for hydrogen generation and other heterogeneous catalysis.
基金supported by the National Natural Science Foundation of China(Nos.52102348,22171123,and 22271130)the Science and Technology Innovation Talent Program of University in Henan Province(No.23HASTIT016)+3 种基金the Natural Science Foundation of Henan Province(No.242300420199)International Science and Technology Cooperation Project of Henan Province of China(No.242102520016)the Key Scientific Research Projects of Universities in Henan Province(No.24A350006)the funding support from the National Natural Science Foundation of China-Excellent Young Scientists Fund(Hong Kong and Macao)(No.52122002)。
文摘Two-dimensional(2D)metal-organic frameworks(MOFs)have emerged as promising photosensitizers in photodynamic therapy in recent years.In comparison to bulk MOFs,constructing 2D MOFs can increase the presence of active sites through increasing the surface area ratio.Herein,we report a simple solventmediated synthesis method for preparation of 2D porphyrin-based MOF(In-TCPP)nanosheets without the addition of any surfactants as an efficient photosensitizer for enhancing photodynamic antibacterial therapy.The accurate regulation of the morphology and size of 2D In-TCPP nanosheets can be achieved by varying the ratio of water to N,N-dimethylformamide solvent with the appropriate assistance of pyridine.The optimal synthesized 2D In-TCPP nanosheets exhibit a diameter of 70–120 nm and a thickness of 21.5–27.4 nm.Promisingly,2D In-TCPP nanosheets produce a higher amount of ^(1)O_(2) when exposed to660 nm laser compared to the In-TCPP bulk,indicating that the smaller nanosheets possess more active sites for reactive oxygen species generation and can greatly improve the antibacterial photodynamic therapeutic effect.Both the in vitro and in vivo results prove that the In-TCPP nanosheets can be used as a photosensitizer for efficient photodynamic antibacterial therapy to kill S.aureus and promote wound healing.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.22279118,22279117,52071135,51871090,and U1804135)the Fundamental Research Funds for the Universities of Henan Province(No.NSFRF220201).
文摘The design of high-performance catalysts is the key to the efficient utilization of hydrogen energy.In this work,a PdCu nanoalloy was successfully anchored on TiO_(2)encapsulated with carbon to construct a catalyst.Outstanding kinetics of the hydrolysis of ammonia borane(turnover frequency of 279 mol·min^(-1·)mol_(Pd)^(-1))ranking the third place among Pd-based catalysts was achieved in the absence of alkali.Both experimental research and theoretical calculations reveal a lower activation energy of the B-H bond on the PdCu nanoalloy catalyst than that on pristine Pd and a lower activation energy of the O-H bond than that on pristine Cu.The redistribution of d electron and the shift of the d-band center play a critical role in increasing the electron density of Pd and improving the catalytic performances of Pd_(0.1)Cu_(0.9)/TiO_(2)-porous carbon(Pd_(0.1)Cu_(0.9)/T-PC).This work provides novel insights into highly dual-active alloys and sheds light on the mechanism of dual-active sites in promoting borohydride hydrolysis.
基金supported by the National Natural Science Foundation of China(Nos.U22A20120,52071135,51871090,and U1804135)the Natural Science Foundation of Hebei Province for Innovation Groups Program(No.C2022203003)Fundamental Research Funds for the Universities of Henan Province(No.NSFRF220201).
文摘Magnesium hydride(MgH_(2))is considered as an ideal hydrogen storage material with excellent hydrogen capacity,but the slow kinetics impedes its application.Herein,an efficient additive of V2C MXene-anchored PrF_(3) nanoparticles(PrF_(3)/V_(2)C)was synthesized,which presents excellent catalytic effect in improving the reversibility and stability of hydrogen storage in MgH_(2).The initial dehydrogenation temperature of the 5 wt.% PrF_(3)/V_(2)C-containing MgH_(2)(182℃) is 105℃ lower than that of pure MgH_(2),and 6.5 wt.%hydrogen is rapidly released from 5 wt.%PrF_(3)/V_(2)C-added MgH_(2)sample in 6 min at 240℃.In addition,5 wt.%PrF_(3)/V_(2)C-containing MgH_(2) sample possesses outstanding reversible hydrogen storage capability of 6.5 wt.% after 10 cycles of dehydrogenation and hydrogenation.Microstructure analysis shows that the introduction of Pr improves the stability of V-species(V^(0)and V^(2+))and O-species(lattice oxygen(OL)and vacancy oxygen(OV))formed during ball milling,promotes the interaction between V-species and O-species,and enhances their reversibility,which contributes to the significant improvement in re/dehydrogenation reversibility and cycling stability of MgH_(2).This study provides effective ideas and strategies for the purpose of designing and fabricating high-efficient catalysts for solid-state hydrogen storage materials.
基金supported by the National Natural Science Foundation of China(grant numbers 42206092,42076123)the Earmarked Fund for China Agriculture Research System(grant number CARS-49)the Marine S&T Fund of Shandong Province for Pilot National Laboratory for Marine Science and Technology(Qingdao)(No.LSKJ202203002).
文摘The D-quadrant organizer sets up the dorsal–ventral(DV)axis and regulates mesodermal development of spiralians.Studies have revealed an important role of mitogen-activated protein kinase(MAPK)signaling in organizer function,but the related molecules have not been fully revealed.The association between fibroblast growth factor receptor(FGFR)and MAPK signaling in regulating organizer specification has been established in the annelid Owenia fusiformis.Now,comparable studies in other spiralian phyla are required to decipher whether this organizer-inducing function of FGFR is prevalent in Spiralia.Here,we indicate that treatment with the FGFR inhibitor SU5402 resulted in deficiency of organizer specification in the mollusk Lottia peitaihoensis.Subsequently,the bone morphogenetic protein(BMP)signaling gradient and DV patterning were disrupted,suggesting the roles of FGFR in regulating organizer function.Changes in multiple aspects of organizer function(the morphology of vegetal blastomeres,BMP signaling gradient,expression of DV patterning markers,etc.)indicate that these developmental functions have different sensitivities to FGFR/MAPK signaling.Our results reveal a functional role of FGFR in organizer specification as well as DV patterning of Lottia embryos,which expands our knowledge of spiralian organizers.
