Zeolites with ordered porous structure of molecular size are widely employed as commercial adsorbents and catalysts.On the other hand,the zeolite matrix is regarded as an ideal scaffold for hosting coordinatively unsa...Zeolites with ordered porous structure of molecular size are widely employed as commercial adsorbents and catalysts.On the other hand,the zeolite matrix is regarded as an ideal scaffold for hosting coordinatively unsaturated sites.Remarkable achievements have been made dealing with the construction,characterization and catalytic applications of coordinatively unsaturated sites in zeolite matrix.Herein,a literature overview of recent progresses on this important topic is presented from the specific view of coordination chemistry.Different strategies to construction coordinatively unsaturated sites in zeolite matrix,in zeolite framework or extraframework positions,are first introduced and their characteristics are compared.Then,spectroscopic techniques to determine the existing states of cation sites and their transformations in zeolite matrix are discussed.In the last section,the catalytic applications of coordinatively unsaturated sites in zeolite matrix for various important chemical transformations are summarized.展开更多
The low intrinsic activity of Fenton catalytic site and high demand for light-energy input inhibit the organic-pollution control efficiency of photo-Fenton process.Here,through structural design with density functiona...The low intrinsic activity of Fenton catalytic site and high demand for light-energy input inhibit the organic-pollution control efficiency of photo-Fenton process.Here,through structural design with density functional theory(DFT)calculations,Ce is predicted to enable the construction of coordinatively unsaturated metal centers(CUCs)in Prussian blue analogue(PBA),which can strongly adsorb H_(2)O_(2)and donate sufficient electrons for directly splitting the O-O bond to produceOH.Using a substitution-co-assembly strategy,binary Ce-Fe PBA is then prepared,which rapidly degrades sulfamethoxazole with the pseudo-first-order kinetic rate constant exceeding reported values by 1-2 orders of magnitude.Meanwhile,the photogenerated electrons reduce Fe(Ⅲ)and Ce(Ⅳ)to promote the metal valence cycle in CUCs and make sulfamethoxazole degradation efficiency only lose 6.04%in 5 runs.Overall,by introducing rare earth metals into transition metal-organic frameworks,this work guides the whole process for highly active CUCs from design and construction to mechanism exploration with DFT calculations,enabling ultrafast and stable photo-Fenton catalysis.展开更多
Some Schiff-base cobalt(Ⅱ)chelates like ethylenebis[(2-hydroxy-3- methoxy-5-methylphenyl)methylideneiminato]Cobalt(Ⅱ)were coordioatively anchored onto poly(4-vinylpyridine-co-styrene)in diglyme solution and the diox...Some Schiff-base cobalt(Ⅱ)chelates like ethylenebis[(2-hydroxy-3- methoxy-5-methylphenyl)methylideneiminato]Cobalt(Ⅱ)were coordioatively anchored onto poly(4-vinylpyridine-co-styrene)in diglyme solution and the dioxygen-affinity of the resulting polymeric complexes were measured in situ.展开更多
Zeolitic-imidazole frameworks(ZIFs)derivations have widely emerged as an efficient air cathode of zinc-air batteries(ZABs)due to excellent bifunctional oxygen electrocatalysis performance.However,they are not stable e...Zeolitic-imidazole frameworks(ZIFs)derivations have widely emerged as an efficient air cathode of zinc-air batteries(ZABs)due to excellent bifunctional oxygen electrocatalysis performance.However,they are not stable enough for long-term operation of rechargeable ZABs because of weak association with current collector,especially under bending conditions for flexible ZAB devices.Here,we show that by purposely designing coordinatively unsaturated ZIFs via a facile morphology regulation,which can be chemically linked on acid-treated carbon cloth,a stable Co-N-C air cathode is therefore derived where Co nanoparticles(NPs)are uniformly confined within the Co-N-C matrix on carbon cloth(Co/Co-N-C/CC).Specifically,when without being stabilized from carbon cloth,the pyrolysis of ZIFs with different unsaturated coordination levels has a negligible impact on the bifunctional oxygen-catalyzed performance.The optimal Co/Co-N-C/CC catalyst assembled ZAB possesses a large open circuit voltage of 1.415 V and a high peak power density of 163 mW·cm^(−2) as well as excellent cycling durability upon 630 discharge–charge cycles with 61%voltage efficiency remained,largely exceeding those of a benchmark Pt/C-IrO_(2) catalyst assembled ZAB.The synergy between Co NPs and active Co-N-C sites via electronic interaction induces the outstanding bifunctional oxygen-catalyzed activity and cathode performance.The present work highlights the importance of unsaturated coordination structures in ZIFs precursors for the performance of derived nanostructures in integrated electrodes.展开更多
Schizophrenia is a severely impacting serious mental illness that presents numerous difficulties to those who suffer from it, their families, and society. While much effort has been invested in understanding successfu...Schizophrenia is a severely impacting serious mental illness that presents numerous difficulties to those who suffer from it, their families, and society. While much effort has been invested in understanding successful treatments, it is still a major issue in public health. This review assesses the advances and issues in the management of schizophrenia in the 21st century, paying special attention to drugs, psychosocial techniques, and connected specialty care. Medications for antipsychotics and psychosocial procedures have shown potential to relieve symptoms and improve functioning, while Recovery-Oriented Care and Psychological Trauma Recovery focus on early diagnosis, combined treatment, and sustained attention. However, many questions remain that need to be answered, including access to care, unmet needs, and discrepancies. Today’s neuroscience research, along with genetic studies and novel therapy options, such as long-acting injectable antipsychotics or telepsychiatry, offers the possibility of further progress being made. Future research exploring fields such as neuroscience, genetics, and implementation science could lead to increasingly effective strategies for people with schizophrenia.展开更多
This paper concerns the exponential attitude-orbit coordinated control problems for gravitational-wave detection formation spacecraft systems.Notably,the large-scale communication delays resulting from oversized inter...This paper concerns the exponential attitude-orbit coordinated control problems for gravitational-wave detection formation spacecraft systems.Notably,the large-scale communication delays resulting from oversized inter-satellite distance of space-based laser interferometers are first modeled.Subject to the delayed communication behaviors,a new delay-dependent attitude-orbit coordinated controller is designed.Moreover,by reconstructing the less conservative Lyapunov-Krasovskii functional and free-weight matrices,sufficient criteria are derived to ensure the exponential stability of the closed-loop relative translation and attitude error system.Finally,a simulation example is employed to illustrate the numerical validity of the proposed controller for in-orbit detection missions.展开更多
This paper proposed a new libration decoupling analytical speed function(LD-ASF)in lieu of the classic analytical speed function to control the climber's speed along a partial space elevator to improve libration s...This paper proposed a new libration decoupling analytical speed function(LD-ASF)in lieu of the classic analytical speed function to control the climber's speed along a partial space elevator to improve libration stability in cargo transportation.The LD-ASF is further optimized for payload transportation efficiency by a novel coordinate game theory to balance competing control objectives among payload transport speed,stable end body's libration,and overall control input via model predictive control.The transfer period is divided into several sections to reduce computational burden.The validity and efficacy of the proposed LD-ASF and coordinate game-based model predictive control are demonstrated by computer simulation.Numerical results reveal that the optimized LD-ASF results in higher transportation speed,stable end body's libration,lower thrust fuel consumption,and more flexible optimization space than the classic analytical speed function.展开更多
Photocatalytic oxygen reduction for hydrogen peroxide(H_(2)O_(2))synthesis presents a green and costeffective production method.However,achieving highly selective H_(2)O_(2)synthesis remains challenging,necessitating ...Photocatalytic oxygen reduction for hydrogen peroxide(H_(2)O_(2))synthesis presents a green and costeffective production method.However,achieving highly selective H_(2)O_(2)synthesis remains challenging,necessitating precise control over free radical reaction pathways and minimizing undesirable oxidative by-products.Herein,we report for the visible light-driven simultaneous co-photocatalytic reduction of O2to H_(2)O_(2)and oxidation of biomass using the atomic rubidium-nitride modified carbon nitride(CNRb).The optimized CNRb catalyst demonstrates a record photoreduction rate of 8.01 mM h^(-1)for H_(2)O_(2)generation and photooxidation rate of 3.75 mM h^(-1)for furfuryl alcohol to furoic acid,achieving a remarkable solar-to-chemical conversion(SCC)efficiency of up to 2.27%.Experimental characterizations and DFT calculation disclosed that the introducing atomic Rb–N configurations allows for the high-selective generation of superoxide radicals while suppressing hydroxyl free radical formation.This is because the Rb–N serves as the new alternative site to perceive a stronger connection position for O2adsorption and reinforce the capability to extract protons,thereby triggering a high selective redox product formation.This study holds great potential in precisely regulating reactive radical processes at the atomic level,thereby paving the way for efficient synthesis of H_(2)O_(2)coupled with biomass valorization.展开更多
Developing cost-effective and high-efficiency oxygen reduction reaction(ORR)catalysts is imperative for promoting the substantial progress of fuel cells and metal-air batteries.The coordination and geometric engineeri...Developing cost-effective and high-efficiency oxygen reduction reaction(ORR)catalysts is imperative for promoting the substantial progress of fuel cells and metal-air batteries.The coordination and geometric engineering of single-atom catalysts(SACs)occurred the promising approach to overcome the thermodynamics and kinetics problems in high-efficiency electrocatalysis.Herein,we rationally constructed atomically dispersed Co atoms on porous N-enriched graphene material C_(2)N(CoSA-C2N)for efficient oxygen reduction reaction(ORR).Systematic characterizations demonstrated the active sites for CoSA-C2N is as identified as coordinatively unsaturated Co-N_(2)moiety,which exhibits ORR intrinsic activity.Structurally,the porous N-enriched graphene framework in C_(2)N could effectively increase the accessibility to the active sites and promote mass transfer rate,contributing to improved ORR kinetics.Consequently,CoSA-C_(2)N exhibited superior ORR performance in both acidic and alkaline conditions as well as impressive long-term durability.The coordination and geometric engineering of SACs will provide a novel approach to advanced catalysts for energy related applications.展开更多
Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utiliz...Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.展开更多
Electrocatalytic nitrate reduction reaction has attracted increasing attention due to its goal of low carbon emission and environmental protection.Here,we report an efficient NitRR catalyst composed of single Mn sites...Electrocatalytic nitrate reduction reaction has attracted increasing attention due to its goal of low carbon emission and environmental protection.Here,we report an efficient NitRR catalyst composed of single Mn sites with atomically dispersed oxygen(O)coordination on bacterial cellulose-converted graphitic carbon(Mn-O-C).Evidence of the atomically dispersed Mn-(O-C_(2))_(4)moieties embedding in the exposed basal plane of carbon surface is confirmed by X-ray absorption spectroscopy.As a result,the as-synthesized Mn-O-C catalyst exhibits superior NitRR activity with an NH_(3)yield rate(RNH_(3))of 1476.9±62.6μg h^(−1)cm^(−2)at−0.7 V(vs.reversible hydrogen electrode,RHE)and a faradaic efficiency(FE)of 89.0±3.8%at−0.5 V(vs.RHE)under ambient conditions.Further,when evaluated with a practical flow cell,Mn-O-C shows a high RNH_(3)of 3706.7±552.0μg h^(−1)cm^(−2)at a current density of 100 mA cm−2,2.5 times of that in the H cell.The in situ FT-IR and Raman spectroscopic studies combined with theoretical calculations indicate that the Mn-(O-C_(2))_(4)sites not only effectively inhibit the competitive hydrogen evolution reaction,but also greatly promote the adsorption and activation of nitrate(NO_(3)^(−)),thus boosting both the FE and selectivity of NH_(3)over Mn-(O-C_(2))_(4)sites.展开更多
Vehicles operating in space need to withstand extreme thermal and electromagnetic environments in light of the burgeoning of space science and technology.It is imperatively desired to high insulation materials with li...Vehicles operating in space need to withstand extreme thermal and electromagnetic environments in light of the burgeoning of space science and technology.It is imperatively desired to high insulation materials with lightweight and extensive mechanical properties.Herein,a boron-silica-tantalum ternary hybrid phenolic aerogel(BSiTa-PA)with exceptional thermal stability,extensive mechanical strength,low thermal conductivity(49.6 mW m^(-1)K^(-1)),and heightened ablative resistance is prepared by an expeditious method.After extremely thermal erosion,the obtained carbon aerogel demonstrates noteworthy electromagnetic interference(EMI)shielding performance with an efficiency of 31.6 dB,accompanied by notable loading property with specific modulus of 272.8 kN·m kg^(-1).This novel design concept has laid the foundation for the development of insulation materials in more complex extreme environments.展开更多
Three zincand cobaltcoordination polymers,namely{[Zn_(2)(μ_(6)-adip)(phen)_(2)]·4H_(2)O}_(n)(1),{[Co_(2)(μ_(6)-adip)(bipy)_(2)]·4H_(2)O}_(n)(2),and[Co_(2)(μ4-adip)(μ-bpa)_(2)]_(n)(3)have been constructed...Three zincand cobaltcoordination polymers,namely{[Zn_(2)(μ_(6)-adip)(phen)_(2)]·4H_(2)O}_(n)(1),{[Co_(2)(μ_(6)-adip)(bipy)_(2)]·4H_(2)O}_(n)(2),and[Co_(2)(μ4-adip)(μ-bpa)_(2)]_(n)(3)have been constructed hydrothermally using H4adip(H4adip=5,5′-azanediyldiisophthalic acid),phen(phen=1,10-phenanthroline),bipy(bipy=2,2′-bipyridine),bpa(bpa=bis(4-pyridyl)amine),and zinc and cobalt chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffrac-tion analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the orthorhom-bic system Pnna(1 and 2)or P21212(3)space groups.All compounds exhibit 3D frameworks.The catalytic perfor-mances in the Henry reaction of these compounds were investigated.Compound 3 exhibited an effective catalytic activity in the Henry reaction at 70℃.CCDC:2339391,1;2339392,2;2339393,3.展开更多
Touch-sensitive screens are crucial components of wearable devices.Materials such as reduced graphene oxide(rGO),carbon nanotubes(CNTs),and graphene offer promising solutions for flexible touch-sensitive screens.Howev...Touch-sensitive screens are crucial components of wearable devices.Materials such as reduced graphene oxide(rGO),carbon nanotubes(CNTs),and graphene offer promising solutions for flexible touch-sensitive screens.However,when stacked with flexible substrates to form multilayered capacitive touching sensors,these materials often suffer from substrate delamination in response to deformation;this is due to the materials having different Young’s modulus values.Delamination results in failure to offer accurate touch screen recognition.In this work,we demonstrate an induced charge-based mutual capacitive touching sensor capable of high-precision touch sensing.This is enabled by electron trapping and polarization effects related to mixed-coordinated bonding between copper nanoparticles and vertically grown graphene nanosheets.Here,we used an electron cyclotron resonance system to directly fabricate graphene-metal nanofilms(GMNFs)using carbon and copper,which are firmly adhered to flexible substrates.After being subjected to 3000 bending actions,we observed almost no change in touch sensitivity.The screen interaction system,which has a signal-to-noise ratio of 41.16 dB and resolution of 650 dpi,was tested using a handwritten Chinese character recognition trial and achieved an accuracy of 94.82%.Taken together,these results show the promise of touch-sensitive screens that use directly fabricated GMNFs for wearable devices.展开更多
Atom-level modulation of the coordination environment for single-atom catalysts(SACs)is considered as an effective strategy for elevating the catalytic performance.For the MNxsite,breaking the symmetrical geometry and...Atom-level modulation of the coordination environment for single-atom catalysts(SACs)is considered as an effective strategy for elevating the catalytic performance.For the MNxsite,breaking the symmetrical geometry and charge distribution by introducing relatively weak electronegative atoms into the first/second shell is an efficient way,but it remains challenging for elucidating the underlying mechanism of interaction.Herein,a practical strategy was reported to rationally design single cobalt atoms coordinated with both phosphorus and nitrogen atoms in a hierarchically porous carbon derived from metal-organic frameworks.X-ray absorption spectrum reveals that atomically dispersed Co sites are coordinated with four N atoms in the first shell and varying numbers of P atoms in the second shell(denoted as Co-N/P-C).The prepared catalyst exhibits excellent oxygen reduction reaction(ORR)activity as well as zinc-air battery performance.The introduction of P atoms in the Co-SACs weakens the interaction between Co and N,significantly promoting the adsorption process of ^(*)OOH,resulting in the acceleration of reaction kinetics and reduction of thermodynamic barrier,responsible for the increased intrinsic activity.Our discovery provides insights into an ultimate design of single-atom catalysts with adjustable electrocatalytic activities for efficient electrochemical energy conversion.展开更多
Three zinc(Ⅱ),cobalt(Ⅱ),and nickel(Ⅱ)coordination polymers,namely[Zn(μ^(3-)cpna)(μ-dpea)_(0.5)]_(n)(1),[Co(μ^(3-)cpna)(μ-dpey)_(0.5)]_(n)(2),and[Ni(μ^(3-)cpna)(μ-dpey)_(0.5)(H_(2)O)]_(n)(3),have been construc...Three zinc(Ⅱ),cobalt(Ⅱ),and nickel(Ⅱ)coordination polymers,namely[Zn(μ^(3-)cpna)(μ-dpea)_(0.5)]_(n)(1),[Co(μ^(3-)cpna)(μ-dpey)_(0.5)]_(n)(2),and[Ni(μ^(3-)cpna)(μ-dpey)_(0.5)(H_(2)O)]_(n)(3),have been constructed hydrothermally using H_(2)cpna(5-(4-carboxyphenoxy)nicotinic acid),dpea(1,2-di(4-pyridyl)ethane),dpey(1,2-di(4-pyridyl)ethylene),and zinc,cobalt,and nickel chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the triclinic system,space group P1.Compounds 1-3 show 2D layer structures.The catalytic activities in the Knoevenagel condensation reaction of these compounds were investigated.Compounds 1 and 2 exhibit effective catalytic activities in the Knoevenagel condensa-tion reaction at room temperature.For this reaction,various parameters were optimized,followed by the investiga-tion of the substrate scope.CCDC:2335676,1;2335677,2;2335678,3.展开更多
基金supported by the National Natural Science Fundation of China(21722303,21421001)the Municipal Natural Science Fund of Tianjin(18JCJQJC47400,18JCZDJC37400)111 Project(B12015,B18030)~~
文摘Zeolites with ordered porous structure of molecular size are widely employed as commercial adsorbents and catalysts.On the other hand,the zeolite matrix is regarded as an ideal scaffold for hosting coordinatively unsaturated sites.Remarkable achievements have been made dealing with the construction,characterization and catalytic applications of coordinatively unsaturated sites in zeolite matrix.Herein,a literature overview of recent progresses on this important topic is presented from the specific view of coordination chemistry.Different strategies to construction coordinatively unsaturated sites in zeolite matrix,in zeolite framework or extraframework positions,are first introduced and their characteristics are compared.Then,spectroscopic techniques to determine the existing states of cation sites and their transformations in zeolite matrix are discussed.In the last section,the catalytic applications of coordinatively unsaturated sites in zeolite matrix for various important chemical transformations are summarized.
基金supported by the National Natural Science Foundation of China(No.22072064,51522805,51908273,and 22176086)the State Key Laboratory of Pollution Control and Resource Reuse(PCRR-ZZ-202106)Start-Up Funds for Jiangsu Distinguished Professor.
文摘The low intrinsic activity of Fenton catalytic site and high demand for light-energy input inhibit the organic-pollution control efficiency of photo-Fenton process.Here,through structural design with density functional theory(DFT)calculations,Ce is predicted to enable the construction of coordinatively unsaturated metal centers(CUCs)in Prussian blue analogue(PBA),which can strongly adsorb H_(2)O_(2)and donate sufficient electrons for directly splitting the O-O bond to produceOH.Using a substitution-co-assembly strategy,binary Ce-Fe PBA is then prepared,which rapidly degrades sulfamethoxazole with the pseudo-first-order kinetic rate constant exceeding reported values by 1-2 orders of magnitude.Meanwhile,the photogenerated electrons reduce Fe(Ⅲ)and Ce(Ⅳ)to promote the metal valence cycle in CUCs and make sulfamethoxazole degradation efficiency only lose 6.04%in 5 runs.Overall,by introducing rare earth metals into transition metal-organic frameworks,this work guides the whole process for highly active CUCs from design and construction to mechanism exploration with DFT calculations,enabling ultrafast and stable photo-Fenton catalysis.
文摘Some Schiff-base cobalt(Ⅱ)chelates like ethylenebis[(2-hydroxy-3- methoxy-5-methylphenyl)methylideneiminato]Cobalt(Ⅱ)were coordioatively anchored onto poly(4-vinylpyridine-co-styrene)in diglyme solution and the dioxygen-affinity of the resulting polymeric complexes were measured in situ.
基金supported by the Fundamental Research Funds for the Central Universities(No.40120631)Natural Science Foundation of Hubei Province(No.20211j0188).
文摘Zeolitic-imidazole frameworks(ZIFs)derivations have widely emerged as an efficient air cathode of zinc-air batteries(ZABs)due to excellent bifunctional oxygen electrocatalysis performance.However,they are not stable enough for long-term operation of rechargeable ZABs because of weak association with current collector,especially under bending conditions for flexible ZAB devices.Here,we show that by purposely designing coordinatively unsaturated ZIFs via a facile morphology regulation,which can be chemically linked on acid-treated carbon cloth,a stable Co-N-C air cathode is therefore derived where Co nanoparticles(NPs)are uniformly confined within the Co-N-C matrix on carbon cloth(Co/Co-N-C/CC).Specifically,when without being stabilized from carbon cloth,the pyrolysis of ZIFs with different unsaturated coordination levels has a negligible impact on the bifunctional oxygen-catalyzed performance.The optimal Co/Co-N-C/CC catalyst assembled ZAB possesses a large open circuit voltage of 1.415 V and a high peak power density of 163 mW·cm^(−2) as well as excellent cycling durability upon 630 discharge–charge cycles with 61%voltage efficiency remained,largely exceeding those of a benchmark Pt/C-IrO_(2) catalyst assembled ZAB.The synergy between Co NPs and active Co-N-C sites via electronic interaction induces the outstanding bifunctional oxygen-catalyzed activity and cathode performance.The present work highlights the importance of unsaturated coordination structures in ZIFs precursors for the performance of derived nanostructures in integrated electrodes.
文摘Schizophrenia is a severely impacting serious mental illness that presents numerous difficulties to those who suffer from it, their families, and society. While much effort has been invested in understanding successful treatments, it is still a major issue in public health. This review assesses the advances and issues in the management of schizophrenia in the 21st century, paying special attention to drugs, psychosocial techniques, and connected specialty care. Medications for antipsychotics and psychosocial procedures have shown potential to relieve symptoms and improve functioning, while Recovery-Oriented Care and Psychological Trauma Recovery focus on early diagnosis, combined treatment, and sustained attention. However, many questions remain that need to be answered, including access to care, unmet needs, and discrepancies. Today’s neuroscience research, along with genetic studies and novel therapy options, such as long-acting injectable antipsychotics or telepsychiatry, offers the possibility of further progress being made. Future research exploring fields such as neuroscience, genetics, and implementation science could lead to increasingly effective strategies for people with schizophrenia.
基金supported by the Na⁃tional Key R&D Program of China(No.2022YFC2204800)the Graduate Student Independent Exploration and Innovation Program of Central South University(No.2024ZZTS 0767).
文摘This paper concerns the exponential attitude-orbit coordinated control problems for gravitational-wave detection formation spacecraft systems.Notably,the large-scale communication delays resulting from oversized inter-satellite distance of space-based laser interferometers are first modeled.Subject to the delayed communication behaviors,a new delay-dependent attitude-orbit coordinated controller is designed.Moreover,by reconstructing the less conservative Lyapunov-Krasovskii functional and free-weight matrices,sufficient criteria are derived to ensure the exponential stability of the closed-loop relative translation and attitude error system.Finally,a simulation example is employed to illustrate the numerical validity of the proposed controller for in-orbit detection missions.
基金funded by the National Natural Science Foundation of China(12102487)Basic and Applied Basic Research Foundation of Guangdong Province,China(2023A1515012339)+1 种基金Shenzhen Science and Technology Program(ZDSYS20210623091808026)the Discovery Grant(RGPIN-2024-06290)of the Natural Sciences and Engineering Research Council of Canada。
文摘This paper proposed a new libration decoupling analytical speed function(LD-ASF)in lieu of the classic analytical speed function to control the climber's speed along a partial space elevator to improve libration stability in cargo transportation.The LD-ASF is further optimized for payload transportation efficiency by a novel coordinate game theory to balance competing control objectives among payload transport speed,stable end body's libration,and overall control input via model predictive control.The transfer period is divided into several sections to reduce computational burden.The validity and efficacy of the proposed LD-ASF and coordinate game-based model predictive control are demonstrated by computer simulation.Numerical results reveal that the optimized LD-ASF results in higher transportation speed,stable end body's libration,lower thrust fuel consumption,and more flexible optimization space than the classic analytical speed function.
基金National Natural Science Foundation of China(22309032,22109120,and 62104170)Guangdong Basic and Applied Basic Research Foundation(2022A1515011737)+2 种基金Science and Technology Program of Guangzhou(2023A04J1395)GDAS’Project of Science and Technology Development(2021GDASYL-20210102010)Zhejiang Provincial Natural Science Foundation of China(LY23F040001)。
文摘Photocatalytic oxygen reduction for hydrogen peroxide(H_(2)O_(2))synthesis presents a green and costeffective production method.However,achieving highly selective H_(2)O_(2)synthesis remains challenging,necessitating precise control over free radical reaction pathways and minimizing undesirable oxidative by-products.Herein,we report for the visible light-driven simultaneous co-photocatalytic reduction of O2to H_(2)O_(2)and oxidation of biomass using the atomic rubidium-nitride modified carbon nitride(CNRb).The optimized CNRb catalyst demonstrates a record photoreduction rate of 8.01 mM h^(-1)for H_(2)O_(2)generation and photooxidation rate of 3.75 mM h^(-1)for furfuryl alcohol to furoic acid,achieving a remarkable solar-to-chemical conversion(SCC)efficiency of up to 2.27%.Experimental characterizations and DFT calculation disclosed that the introducing atomic Rb–N configurations allows for the high-selective generation of superoxide radicals while suppressing hydroxyl free radical formation.This is because the Rb–N serves as the new alternative site to perceive a stronger connection position for O2adsorption and reinforce the capability to extract protons,thereby triggering a high selective redox product formation.This study holds great potential in precisely regulating reactive radical processes at the atomic level,thereby paving the way for efficient synthesis of H_(2)O_(2)coupled with biomass valorization.
基金supported by the National Natural Science Foundation of China(Nos.22201262 and 51902013)Natural Science Foundation of Henan Province(No.222300420290)+1 种基金Foundation of Department of Science and Technology of Guizhou province(No.[2019]1297)Engineering Research Center of Guihzou province(No.[2018]487).
文摘Developing cost-effective and high-efficiency oxygen reduction reaction(ORR)catalysts is imperative for promoting the substantial progress of fuel cells and metal-air batteries.The coordination and geometric engineering of single-atom catalysts(SACs)occurred the promising approach to overcome the thermodynamics and kinetics problems in high-efficiency electrocatalysis.Herein,we rationally constructed atomically dispersed Co atoms on porous N-enriched graphene material C_(2)N(CoSA-C2N)for efficient oxygen reduction reaction(ORR).Systematic characterizations demonstrated the active sites for CoSA-C2N is as identified as coordinatively unsaturated Co-N_(2)moiety,which exhibits ORR intrinsic activity.Structurally,the porous N-enriched graphene framework in C_(2)N could effectively increase the accessibility to the active sites and promote mass transfer rate,contributing to improved ORR kinetics.Consequently,CoSA-C_(2)N exhibited superior ORR performance in both acidic and alkaline conditions as well as impressive long-term durability.The coordination and geometric engineering of SACs will provide a novel approach to advanced catalysts for energy related applications.
基金supported by the National Natural Science Foundation of China(22234005,21974070)the Natural Science Foundation of Jiangsu Province(BK20222015)。
文摘Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.
基金the financial support from the Natural Science Foundation of China(Grant No.52172106)Anhui Provincial Natural Science Foundation(Grant Nos.2108085QB60 and 2108085QB61)China Postdoctoral Science Foundation(Grant Nos.2020M682057 and 2023T160651).
文摘Electrocatalytic nitrate reduction reaction has attracted increasing attention due to its goal of low carbon emission and environmental protection.Here,we report an efficient NitRR catalyst composed of single Mn sites with atomically dispersed oxygen(O)coordination on bacterial cellulose-converted graphitic carbon(Mn-O-C).Evidence of the atomically dispersed Mn-(O-C_(2))_(4)moieties embedding in the exposed basal plane of carbon surface is confirmed by X-ray absorption spectroscopy.As a result,the as-synthesized Mn-O-C catalyst exhibits superior NitRR activity with an NH_(3)yield rate(RNH_(3))of 1476.9±62.6μg h^(−1)cm^(−2)at−0.7 V(vs.reversible hydrogen electrode,RHE)and a faradaic efficiency(FE)of 89.0±3.8%at−0.5 V(vs.RHE)under ambient conditions.Further,when evaluated with a practical flow cell,Mn-O-C shows a high RNH_(3)of 3706.7±552.0μg h^(−1)cm^(−2)at a current density of 100 mA cm−2,2.5 times of that in the H cell.The in situ FT-IR and Raman spectroscopic studies combined with theoretical calculations indicate that the Mn-(O-C_(2))_(4)sites not only effectively inhibit the competitive hydrogen evolution reaction,but also greatly promote the adsorption and activation of nitrate(NO_(3)^(−)),thus boosting both the FE and selectivity of NH_(3)over Mn-(O-C_(2))_(4)sites.
基金the support from the Joint Fund of Advanced Aerospace Manufacturing Technology Research of National Natural Science Foundation of China(U1837601)National Natural Science Foundation of China(52273255)+3 种基金NASF Joint Fund of National Natural Science Foundation of China and China Academy of Engineering Physics(U2130118)China Postdoctoral Science Foundation(2023M732029)Innovation Foundation for Doctor Dissertation of Northwestern Polytechnical University(CX2023092)Undergraduate Innovation&Business Program in Northwestern Polytechnical University(XN2022226)。
文摘Vehicles operating in space need to withstand extreme thermal and electromagnetic environments in light of the burgeoning of space science and technology.It is imperatively desired to high insulation materials with lightweight and extensive mechanical properties.Herein,a boron-silica-tantalum ternary hybrid phenolic aerogel(BSiTa-PA)with exceptional thermal stability,extensive mechanical strength,low thermal conductivity(49.6 mW m^(-1)K^(-1)),and heightened ablative resistance is prepared by an expeditious method.After extremely thermal erosion,the obtained carbon aerogel demonstrates noteworthy electromagnetic interference(EMI)shielding performance with an efficiency of 31.6 dB,accompanied by notable loading property with specific modulus of 272.8 kN·m kg^(-1).This novel design concept has laid the foundation for the development of insulation materials in more complex extreme environments.
文摘Three zincand cobaltcoordination polymers,namely{[Zn_(2)(μ_(6)-adip)(phen)_(2)]·4H_(2)O}_(n)(1),{[Co_(2)(μ_(6)-adip)(bipy)_(2)]·4H_(2)O}_(n)(2),and[Co_(2)(μ4-adip)(μ-bpa)_(2)]_(n)(3)have been constructed hydrothermally using H4adip(H4adip=5,5′-azanediyldiisophthalic acid),phen(phen=1,10-phenanthroline),bipy(bipy=2,2′-bipyridine),bpa(bpa=bis(4-pyridyl)amine),and zinc and cobalt chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffrac-tion analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the orthorhom-bic system Pnna(1 and 2)or P21212(3)space groups.All compounds exhibit 3D frameworks.The catalytic perfor-mances in the Henry reaction of these compounds were investigated.Compound 3 exhibited an effective catalytic activity in the Henry reaction at 70℃.CCDC:2339391,1;2339392,2;2339393,3.
基金supported by the National Natural Science Foundation of China(Nos.52275565,52105593,and 62104155)the Natural Science Foundation of Guangdong Province,China(No.2022A1515011667)+2 种基金the Shenzhen Foundation Research Key Project(No.JCYJ20200109114244249)the Youth Talent Fund of Guangdong Province,China(No.2023A1515030292)the Shenzhen Excellent Youth Basic Research Fund(No.RCYX20231211090249068).
文摘Touch-sensitive screens are crucial components of wearable devices.Materials such as reduced graphene oxide(rGO),carbon nanotubes(CNTs),and graphene offer promising solutions for flexible touch-sensitive screens.However,when stacked with flexible substrates to form multilayered capacitive touching sensors,these materials often suffer from substrate delamination in response to deformation;this is due to the materials having different Young’s modulus values.Delamination results in failure to offer accurate touch screen recognition.In this work,we demonstrate an induced charge-based mutual capacitive touching sensor capable of high-precision touch sensing.This is enabled by electron trapping and polarization effects related to mixed-coordinated bonding between copper nanoparticles and vertically grown graphene nanosheets.Here,we used an electron cyclotron resonance system to directly fabricate graphene-metal nanofilms(GMNFs)using carbon and copper,which are firmly adhered to flexible substrates.After being subjected to 3000 bending actions,we observed almost no change in touch sensitivity.The screen interaction system,which has a signal-to-noise ratio of 41.16 dB and resolution of 650 dpi,was tested using a handwritten Chinese character recognition trial and achieved an accuracy of 94.82%.Taken together,these results show the promise of touch-sensitive screens that use directly fabricated GMNFs for wearable devices.
基金supported by the National Natural Science Foundation of China(51872115,12234018 and 52101256)Beijing Synchrotron Radiation Facility(BSRF,4B9A)。
文摘Atom-level modulation of the coordination environment for single-atom catalysts(SACs)is considered as an effective strategy for elevating the catalytic performance.For the MNxsite,breaking the symmetrical geometry and charge distribution by introducing relatively weak electronegative atoms into the first/second shell is an efficient way,but it remains challenging for elucidating the underlying mechanism of interaction.Herein,a practical strategy was reported to rationally design single cobalt atoms coordinated with both phosphorus and nitrogen atoms in a hierarchically porous carbon derived from metal-organic frameworks.X-ray absorption spectrum reveals that atomically dispersed Co sites are coordinated with four N atoms in the first shell and varying numbers of P atoms in the second shell(denoted as Co-N/P-C).The prepared catalyst exhibits excellent oxygen reduction reaction(ORR)activity as well as zinc-air battery performance.The introduction of P atoms in the Co-SACs weakens the interaction between Co and N,significantly promoting the adsorption process of ^(*)OOH,resulting in the acceleration of reaction kinetics and reduction of thermodynamic barrier,responsible for the increased intrinsic activity.Our discovery provides insights into an ultimate design of single-atom catalysts with adjustable electrocatalytic activities for efficient electrochemical energy conversion.
文摘Three zinc(Ⅱ),cobalt(Ⅱ),and nickel(Ⅱ)coordination polymers,namely[Zn(μ^(3-)cpna)(μ-dpea)_(0.5)]_(n)(1),[Co(μ^(3-)cpna)(μ-dpey)_(0.5)]_(n)(2),and[Ni(μ^(3-)cpna)(μ-dpey)_(0.5)(H_(2)O)]_(n)(3),have been constructed hydrothermally using H_(2)cpna(5-(4-carboxyphenoxy)nicotinic acid),dpea(1,2-di(4-pyridyl)ethane),dpey(1,2-di(4-pyridyl)ethylene),and zinc,cobalt,and nickel chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and single-crystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three compounds crystallize in the triclinic system,space group P1.Compounds 1-3 show 2D layer structures.The catalytic activities in the Knoevenagel condensation reaction of these compounds were investigated.Compounds 1 and 2 exhibit effective catalytic activities in the Knoevenagel condensa-tion reaction at room temperature.For this reaction,various parameters were optimized,followed by the investiga-tion of the substrate scope.CCDC:2335676,1;2335677,2;2335678,3.
