Two new Mn(Ⅱ)coordination polymers,namely{[Mn_(2)(HL)(phen)_(3)(H_(2)O)_(2)]·7.5H_(2)O}_n(1)and[Mn_(4)(HL)_(2)(1,4-bib)_(3)(H_(2)O)_(2)]_n(2),were synthesized under hydrothermal conditions by using Mn(Ⅱ)ions an...Two new Mn(Ⅱ)coordination polymers,namely{[Mn_(2)(HL)(phen)_(3)(H_(2)O)_(2)]·7.5H_(2)O}_n(1)and[Mn_(4)(HL)_(2)(1,4-bib)_(3)(H_(2)O)_(2)]_n(2),were synthesized under hydrothermal conditions by using Mn(Ⅱ)ions and 6-(3',4'-dicarboxylphenoxy)-1,2,4-benzenetricarboxylic acid(H_(5)L)in the presence of N-auxiliary ligands 1,10-phenanthroline(phen)and1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib).The structures of coordination polymers 1 and 2 were characterized by infrared spectroscopy,single-crystal X-ray diffraction,thermogravimetric analysis,and powder X-ray diffraction.Single-crystal X-ray diffraction reveals that 1 has a 1D chain structure based on binuclear Mn(Ⅱ)units,while 2 features a(3,8)-connected 3D network structure based on tetranuclear Mn(Ⅱ)units.Magnetic studies show that 1 and 2exhibit antiferromagnetic interactions between manganese ions.2 shows stronger antiferromagnetic interactions due to the shorter Mn…Mn distances within the tetranuclear manganese units.CCDC:2357601,1;2357602,2.展开更多
Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfull...Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfully synthesized under hydrothermal conditions and characterized structurally by IR spectroscopy,elemental analyses,single-crystal X-ray diffraction,powder X-ray diffraction,and thermogravimetric analysis.The results of single-crystal X-ray diffraction show that complex 1 presents a 1D zigzag chain structure and further extends to a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.Meanwhile,complex 2 has a zero-dimensional structure and also extends to form a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.In addition,both 1and 2 exhibited luminescent properties in the solid state.Furthermore,quantum chemical calculations were carried out on the"molecular fragments"extracted from the crystal structures of 1 and 2 using the PBE0/LANL2DZ method constructed by the Gaussian 16 program.The calculated values signify a significant covalent interaction between the coordination atoms and the Cd(Ⅱ)ions.CCDC:2332173,1;2332176,2.展开更多
A coordination polymer{[Cd(H_(2)dpa)(bpy)]·3H_(2)O}_(n)(Cd-CP)was designed and hydrothermal synthesized based on 4-(2,4-dicarboxyphenoxy)phthalic acid(H_(4)dpa),2,2'-bipyridine(bpy)and Cd(NO_(3))_(2)·4H_...A coordination polymer{[Cd(H_(2)dpa)(bpy)]·3H_(2)O}_(n)(Cd-CP)was designed and hydrothermal synthesized based on 4-(2,4-dicarboxyphenoxy)phthalic acid(H_(4)dpa),2,2'-bipyridine(bpy)and Cd(NO_(3))_(2)·4H_(2)O.The structure was characterized by single-crystal X-ray diffraction,powder X-ray diffraction,elemental analysis,and infrared spectroscopy.Cd-CP belongs to the monoclinic crystal system with the P2_1/c space group and performs in a 1D double-chain structure.The adjacent double chains further form a 3D supramolecular network structure through hydrogen bonding.Thermogravimetric analysis shows that Cd-CP has good thermal stability.Fluorescence analysis showed that Cd-CP had good choosing selectively and was sensitive to metal ions(Fe^(3+)and Zn^(2+)),2,4,6-trinitrophenylhydrazine(TRI),and pyrimethanil(Pth).Interestingly,when Cd-CP was used for fluorescence detection of metal ions,it was found to have a fluorescence quenching effect on Fe^(3+)but had an obvious enhancement effect on Zn^(2+).Therefore,we designed an“on-off-on”logic gate.In addition,the mechanism of fluorescence sensing has been deeply explored.CCDC:2258625.展开更多
Exploring optimal operational schemes for synergistic development is crucial for sustainable management in river basins.This study introduces a multi-objective synergistic optimization framework aimed at analyzing the...Exploring optimal operational schemes for synergistic development is crucial for sustainable management in river basins.This study introduces a multi-objective synergistic optimization framework aimed at analyzing the interplay among flood control,ecological integrity,and desilting objectives under varying watersediment conditions.The framework encompasses multi-objective reservoir optimal operation,scheme decision,and trade-off analysis among competing objectives.To address the optimization model,an elite mutation-based multiobjective particle swarm optimization(MOPSO)algorithm that integrates genetic algorithms(GA)is developed.The coupling coordination degree is employed for optimal scheme decision-making,allowing for the adjustment of weight ratios to investigate the trade-offs between objectives.This research focuses on the Sanmenxia and Xiaolangdi cascade reservoirs in the Yellow River,utilizing three representative hydrological years:1967,1969,and 2002.The findings reveal that:(1)the proposed model effectively generates Pareto fronts for multi-objective operations,facilitating the recommendation of optimal schemes based on coupling coordination degrees;(2)as water-sediment conditions shift from flooding to drought,competition intensifies between the flood control and desilting objectives.While flood control and ecological objectives compete during flood and dry years,they demonstrate synergies in normal years(r=0.22);conversely,ecological and desilting objectives are consistently competitive across all three typical years,with the strongest competition observed in the normal year(r=-0.95);(3)the advantages conferred to ecological objectives increase as water-sediment conditions shift from flooding to drought.However,the promotion of the desilting objective requires more complex trade-offs.This study provides a model and methodological approach for the multi-objective optimization of flood control,sediment management,and ecological considerations in reservoir clusters.Moreover,the methodologies presented herein can be extended to other water resource systems for multi-objective optimization and decision-making.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
The selection and coordinated application of government innovation policies are crucial for guiding the direction of enterprise innovation and unleashing their innovation potential.However,due to the lengthy,voluminou...The selection and coordinated application of government innovation policies are crucial for guiding the direction of enterprise innovation and unleashing their innovation potential.However,due to the lengthy,voluminous,complex,and unstructured nature of regional innovation policy texts,traditional policy classification methods often overlook the reality that these texts cover multiple policy topics,leading to lack of objectivity.In contrast,topic mining technology can handle large-scale textual data,overcoming challenges such as the abundance of policy content and difficulty in classification.Although topic models can partition numerous policy texts into topics,they cannot analyze the interplay among policy topics and the impact of policy topic coordination on enterprise innovation in detail.Therefore,we propose a big data analysis scheme for policy coordination paths based on the latent Dirichlet allocation(LDA)model and the fuzzyset qualitative comparative analysis(fsQCA)method by combining topic models with qualitative comparative analysis.The LDA model was employed to derive the topic distribution of each document and the word distribution of each topic and enable automatic classi-fication through algorithms,providing reliable and objective textual classification results.Subsequently,the fsQCA method was used to analyze the coordination paths and dynamic characteristics.Finally,experimental analysis was conducted using innovation policy text data from 31 provincial-level administrative regions in China from 2012 to 2021 as research samples.The results suggest that the proposed method effectively partitions innovation policy topics and analyzes the policy configuration,driving enterprise innovation in different regions.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
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
Two new coordination polymers,[Ni(Hpdc)(bib)(H_(2)O)]_(n)(1)and{[Ni(bib)_(3)](ClO_(4))_(2)}_(n)(2),were prepared by mixing Ni^(2+),3,5⁃pyrazoledicarboxylic acid(H3pdc)/p⁃nitrobenzoic acid and 1,4⁃bis(imidazol⁃1⁃ylmeth...Two new coordination polymers,[Ni(Hpdc)(bib)(H_(2)O)]_(n)(1)and{[Ni(bib)_(3)](ClO_(4))_(2)}_(n)(2),were prepared by mixing Ni^(2+),3,5⁃pyrazoledicarboxylic acid(H3pdc)/p⁃nitrobenzoic acid and 1,4⁃bis(imidazol⁃1⁃ylmethyl)butane(bib)by a hydrothermal method,respectively.X⁃ray crystallography reveals a 2D network constructed by six⁃coordinated Ni(Ⅱ)centers,bib,and Hpdc2-ligands in complex 1,while a 2D network is built by Ni(Ⅱ)and bib ligands in 2.Furthermore,the quantum⁃chemical calculations have been performed on‘molecular fragments’extracted from the crystal structure of 1 using the PBE0/LANL2DZ method in Gaussian 16 and the VASP program.CCDC:2343794,1;2343798,2.展开更多
Controllable regulation of the reconstruction process for the pre-catalysts towards oxygen evolution remains as a great challenge.In this study,we report a bi-ligand strategy to facilitate the structural transformatio...Controllable regulation of the reconstruction process for the pre-catalysts towards oxygen evolution remains as a great challenge.In this study,we report a bi-ligand strategy to facilitate the structural transformation of coordination compounds to metal oxyhydroxides during oxygen evolution with enhanced activity.A coordination compound consisting of 1,10-ferrocene acid(Fc)and Ni^(2+)was synthesized,in which terephthalic acid was introduced.The second ligand of terephthalic acid facilitates the reconstruction process,inducing an enhanced catalytic activity.In 1 mol·L^(-1)KOH aqueous solution,the optimized catalyst can drive a current density of 10 mA·cm^(-2)under a lower overpotential of 220 mV.Using this catalyst,zinc-air batteries can be prepared.The obtained zinc-air battery presents a large specific capacity of 718 mA·h·g^(-1)with excellent cycling stability for over 100 h far exceeding that of Pt/C+RuO_(2)battery fabricated with commercial catalysts.The excellent performance and low cost of this catalyst will open up broad prospects for the development of advanced systems for water electrolysis and zinc air batteries.展开更多
Two coordination polymers were synthesized by hydrothermal reaction,namely,[Cd(H_(3)cpbda)(2,2′‑bipy)(H_(2)O)]_(n)(1)and[Mn(H_(3)cpbda)(phen)(H_(2)O)]_(n)(2),where H_(5)cpbda=5,5′‑[(5‑carboxy‑1,3‑phenyl)bis(oxy)]tri...Two coordination polymers were synthesized by hydrothermal reaction,namely,[Cd(H_(3)cpbda)(2,2′‑bipy)(H_(2)O)]_(n)(1)and[Mn(H_(3)cpbda)(phen)(H_(2)O)]_(n)(2),where H_(5)cpbda=5,5′‑[(5‑carboxy‑1,3‑phenyl)bis(oxy)]triisophthalic acid,2,2′‑bipy=2,2′‑bipyridine,phen=1,10‑phenanthroline.The two complexes were characterized by single‑crystal X‑ray diffraction,powder diffraction,infrared spectroscopy,and thermogravimetric analysis.Complexes 1 and 2 are“V”‑shaped 1D chains,and the molecules form 2D(1)and 3D framework(2)structures through weakπ…πstacking.Furthermore,complex 1 was dispersed in an aqueous solution and its fluorescence intensity demonstrated excellent stability.Complex 1 can specifically detect ciprofloxacin in urine with a detection limit of 1.91×10^(-8)mol·L^(-1).CCDC:2359498,1;2359499,2.展开更多
Unlike the traditional decentralized channel,the drop-shipping channel entails a retailer relaying consumers’orders to the manufacturer,which proceeds to stock the orders and directly ship them to the consumers.This ...Unlike the traditional decentralized channel,the drop-shipping channel entails a retailer relaying consumers’orders to the manufacturer,which proceeds to stock the orders and directly ship them to the consumers.This study explores supply chain coordination and product quality in drop-shipping and traditional channels.Specifically,we analyze the performance of both channels under wholesale price and revenue-sharing contracts.Our study yields several key findings.First,the revenue-sharing contract can coordinate both traditional and drop-shipping channels,effectively increasing supply chain performance.Second,given the channel structure,the retailer prefers the wholesale price contract,whereas the manufacturer prefers the revenue-sharing contract.Third,product quality is higher in the drop-shipping channel when demand uncertainty is high.Finally,the implementation of the revenue-sharing contract increases product quality in the traditional channel,whereas it keeps product quality unchanged in the drop-shipping channel.展开更多
With the increase of people’s demand,it is extremely desired for developing high-safety,widetemperature-range and high-energy-density lithium batteries,but huge challenges are remained due to shrinkage and combustion...With the increase of people’s demand,it is extremely desired for developing high-safety,widetemperature-range and high-energy-density lithium batteries,but huge challenges are remained due to shrinkage and combustion of commonly used polyolefin separators at high temperatures,as well as narrow usable temperature range and high flammability of conventionally commercialized liquid electrolytes.In this work,we report a multifunctional separator mainly consisting of Zn^(2+)-phytate coordination complex nanoparticles and bacterial cellulose nanofibers,named the BZP separator,which possesses high porosity,excellent thermotolerance,good flame retardancy,abilities of anion binding and Ni^(2+)capturing.Through cooperating with the fluoride-free wide-temperature-range electrolyte,Li//LiFePO_(4) cells not only deliver discharge capacities of 110.39 mA h g^(-1)and 113.25 mA h g^(-1)after 2200 cycles (2 C) and1600 cycles (5 C) at 25℃,with capacity retentions of 76.59%and 86.09%,respectively,but also exhibit excellent cycling performance at 80℃ and-40℃.Significantly,the Li//NCM811 cell with a loading of7.8 mg cm^(-2)delivers a discharge capacity of 146.64 mA h g^(-1)after 200 cycles at 0.5 C,with a capacity retention of 89.03%.In addition,pouch cells can work at 120℃ and have low flammability.展开更多
The high energy coordination compounds Cu(TZCA)_(2)(ClO_(4))_(2)(ECCs-1) was prepared by 1H-tetrazole-5-carbohydrazide(TZCA) with a high energy skeleton and a strong coordination ability group.At the same time,the rea...The high energy coordination compounds Cu(TZCA)_(2)(ClO_(4))_(2)(ECCs-1) was prepared by 1H-tetrazole-5-carbohydrazide(TZCA) with a high energy skeleton and a strong coordination ability group.At the same time,the reaction activity of the ligand was explored,and the single crystal structure of it and intermediate were obtained.The structures of all substances were characterized by IR and EA.And the structure and composition of ECCs-1 are confirmed by ESP,AC,SEM and ICP-OES.Physical and chemical properties tests show that ECCs-1 has an acceptable thermal stability(T_(d)=177℃) and extremely sensitive mechanical stimulation(IS=1 J,FS=5 N).The comprehensive performance test results show that ECCs-1 has excellent initiation ability.In addition,the decomposition mechanism of ECCs-1 is explored from two aspects of experiment and theoretical calculation.展开更多
Aiming at the problem that it is difficult to generate the dynamic decoupling equation of the parallel six-dimensional acceleration sensing mechanism,two typical parallel six-dimensional acceleration sensing mechanism...Aiming at the problem that it is difficult to generate the dynamic decoupling equation of the parallel six-dimensional acceleration sensing mechanism,two typical parallel six-dimensional acceleration sensing mechanisms are taken as examples.By analyzing the scale constraint relationship between the hinge points on the mass block and the hinge points on the base of the sensing mechanism,a new method for establishing the dynamic equation of the sensing mechanism is proposed.Firstly,based on the scale constraint relationship between the hinge points on the mass block and the hinge points on the base of the sensing mechanism,the expression of the branch rod length is obtained.The inherent constraint relationship between the branches is excavated and the branch coordination closed chain of the“12-6”configuration is constructed.The output coordination equation of the sensing mechanism is successfully derived.Secondly,the dynamic equations of“12-4”and“12-6”configurations are constructed by the Newton-Euler method,and the forward decoupling equations of the two configurations are solved by combining the dynamic equations and the output coordination equations.Finally,the virtual prototype experiment is carried out,and the maximum reference errors of the forward decoupling equations of the two configuration sensing mechanisms are 4.23%and 6.53%,respectively.The results show that the proposed method is effective and feasible,and meets the real-time requirements.展开更多
Suppression of uncontrollable dendrite growth and water-induced side reactions of Zn metal anodes is crucial for achieving long-lasting cycling stability and facilitating the practical implementations of aqueous Zn-me...Suppression of uncontrollable dendrite growth and water-induced side reactions of Zn metal anodes is crucial for achieving long-lasting cycling stability and facilitating the practical implementations of aqueous Zn-metal batteries.To address these challenges,we report in this study a functional nitro-cellulose interfacial layer(NCIL)on the surface of Zn anodes enlightened by a nitro-coordination chemistry strategy.The NCIL exhibits strong zincophilicity and superior coordination capability with Zn^(2+)due to the highly electronegative and highly nucleophilic nature of the nitro functional group.This characteristic facilitates a rapid Zn-ion desolvation process and homogeneous Zn plating,effectively preventing H_(2) evolution and dendrite formation.Additionally,the negatively charged surface of NCIL acts as a shield,repelling SO_(4)^(2-)anions and inhibiting corrosive reactions on the Zn surface.Remarkably,reversible and stable Zn plating/stripping is achieved for over 5100 h at a current density of 1 mA cm^(-2),which is nearly 30 times longer than that of bare Zn anodes.Furthermore,the Zn/V_(2)O_(5) full cells with the functional interface layer deliver a high-capacity retention of 80.3%for over 10,000 cycles at 5 A g^(-1).This research offers valuable insights for the rational development of advanced protective interface layers in order to achieve ultra-long-lifeZnmetal batteries.展开更多
Single metal atoms anchored on nitrogen-doped carbon materials(M-N_(4))have been identified as effective active sites for catalyzing the two-electron oxygen reduction reaction(2e-ORR).However,the relationship between ...Single metal atoms anchored on nitrogen-doped carbon materials(M-N_(4))have been identified as effective active sites for catalyzing the two-electron oxygen reduction reaction(2e-ORR).However,the relationship between the local atomic/electronic environments of the M-N_(4) sites(metal atoms coordinated with different types of N species)and their catalytic activity for 2e-ORR has rarely been elaborated clearly,which imposes significant ambiguity for the rational design of catalysts.Herein,guided by the comprehensive density-functional theory calculations and predictions,a series of Zn-N_(4) single-atom catalysts(SACs)are designed with pyrrole/pyridine-N(N_(Po)/N_(Pd))synergistic coordination and prepared by controlling the pyrolysis temperature(600,700,and 800℃),Among them,the dominated Zn-N_(4) configurations with rationally combined N_(Po)/N_(Pd)coordination show~*OOH adsorption strength close to the optimal value,much superior to those with mono N species.Thus,the as-prepared catalyst exhibits a high H_(2)O_(2) selectivity of over 90%both in neutral and alkaline environments,with a superb H_(2)O_(2) yield of up to 33.63 mol g^(-1)h^(-1)in an alkaline with flow cell.More importantly,a new descriptor,dz^(2)+s band center,has been proposed,which is especially feasible for predicting the activity for metal types with fully occupied s and d orbitals.This work thus presents clear guidance for the rational design of highly active SACs toward ORR and provides a complement to the d-band theory for more accurately predicting the catalytic activity of the materials.展开更多
One of the greatest challenges in the agroecosystem is to improve cropland intensification while preserving agroecosystem services.While many studies have investigated the effect of cropland intensification on agroeco...One of the greatest challenges in the agroecosystem is to improve cropland intensification while preserving agroecosystem services.While many studies have investigated the effect of cropland intensification on agroecosystem service,the interactive coupling and coordination among these factors remain largely unexplored.In view of this,this study performed a case study of the Loess Plateau in Shaanxi Province,China and constructed comprehensive evaluation models to quantify the cropland intensification and agroecosystem service in this area.Balance analysis and the coupling coordination degree model were used to evaluate the interactive relationship between cropland intensification and agroecosystem service,and statistical analysis and spatial autocorrelation were used to analyze the spatial characteristics and potential mechanism of the coupling coordination.Results show that both the cropland intensification and agroecosystem service in the study area were relatively low yet gradually increased from 2000 to 2020.Agroecosystem service lag was identified as the dominant unbalanced development type.Improving the supply capacity of agroecosystem services plays a key role in the balanced development of cropland in the Loess Plateau.The coupling coordination degree between cropland intensification and agroecosystem service ranges from basic coordination to serious incoordination.Therefore,cropland intensification practices in the area should be optimized to enhance this coordination degree.An upward trend was also observed in the coupling coordination degree from2000 to 2020.The withdrawal of marginal cropland in the Grain for Green program is one of the most important reasons for this trend,especially for the northern region.Around 83.6%of the high-high clusters are concentrated in the southern region of the Loess Plateau,whereas 70.5%of the low-low clusters are distributed in the northern region.These clustering characteristics are mainly attributed to the environmental suitability of these areas for agriculture and their degree of economic development.展开更多
Currently,the iron chromium redox flow battery(ICRFB)has become a research hotspot in the energy storage field owing to its low cost and easily-scaled-up.However,the activity of electrolyte is still ambiguous due to i...Currently,the iron chromium redox flow battery(ICRFB)has become a research hotspot in the energy storage field owing to its low cost and easily-scaled-up.However,the activity of electrolyte is still ambiguous due to its complicated solution environment.Herein,we performed a pioneering investigation on the coordination behavior and transformation mechanism of Cr^(3+)in electrolyte and prediction of impurity ions impact through quantum chemistry computations.Based on the structure and symmetry of electrostatic potential distribution,the activity of different Cr^(3+)complex ions is confirmed as[Cr(H2O)5Cl]^(2+)>[Cr(H2O)4Cl2]+>[Cr(H2O)6]^(3+).The transformation mechanism between[Cr(H2O)6]^(3+)and[Cr(H2O)5Cl]^(2+)is revealed.We find the metal impurity ions(especially Mg^(2+))can exacerbate the electrolyte deactivation by reducing the transformation energy barrier from[Cr(H2O)5Cl]^(2+)(24.38 kcal mol^(−1))to[Cr(H2O)6]^(3+)(16.23 kcal mol^(−1)).The solvent radial distribution and mean square displacement in different solvent environments are discussed and we conclude that the coordination configuration limits the diffusivity of Cr^(3+).This work provides new insights into the activity of electrolyte,laying a fundamental sense for the electrolyte in ICRFB.展开更多
文摘Two new Mn(Ⅱ)coordination polymers,namely{[Mn_(2)(HL)(phen)_(3)(H_(2)O)_(2)]·7.5H_(2)O}_n(1)and[Mn_(4)(HL)_(2)(1,4-bib)_(3)(H_(2)O)_(2)]_n(2),were synthesized under hydrothermal conditions by using Mn(Ⅱ)ions and 6-(3',4'-dicarboxylphenoxy)-1,2,4-benzenetricarboxylic acid(H_(5)L)in the presence of N-auxiliary ligands 1,10-phenanthroline(phen)and1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib).The structures of coordination polymers 1 and 2 were characterized by infrared spectroscopy,single-crystal X-ray diffraction,thermogravimetric analysis,and powder X-ray diffraction.Single-crystal X-ray diffraction reveals that 1 has a 1D chain structure based on binuclear Mn(Ⅱ)units,while 2 features a(3,8)-connected 3D network structure based on tetranuclear Mn(Ⅱ)units.Magnetic studies show that 1 and 2exhibit antiferromagnetic interactions between manganese ions.2 shows stronger antiferromagnetic interactions due to the shorter Mn…Mn distances within the tetranuclear manganese units.CCDC:2357601,1;2357602,2.
文摘Two new transition-metal coordination polymers,{[Cd(oba)(L)_(2)]·H_(2)O}_n(1)and[Cd(4-nph)(L)_(2)]_n(2)(H_(2)oba=4,4'-oxydibenzoic acid,4-H_(2)nph=4-nitrophthalic acid,L=2,2'-biimidazole),were successfully synthesized under hydrothermal conditions and characterized structurally by IR spectroscopy,elemental analyses,single-crystal X-ray diffraction,powder X-ray diffraction,and thermogravimetric analysis.The results of single-crystal X-ray diffraction show that complex 1 presents a 1D zigzag chain structure and further extends to a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.Meanwhile,complex 2 has a zero-dimensional structure and also extends to form a 2D network through N—H…O hydrogen bonds andπ-πstacking interactions.In addition,both 1and 2 exhibited luminescent properties in the solid state.Furthermore,quantum chemical calculations were carried out on the"molecular fragments"extracted from the crystal structures of 1 and 2 using the PBE0/LANL2DZ method constructed by the Gaussian 16 program.The calculated values signify a significant covalent interaction between the coordination atoms and the Cd(Ⅱ)ions.CCDC:2332173,1;2332176,2.
文摘A coordination polymer{[Cd(H_(2)dpa)(bpy)]·3H_(2)O}_(n)(Cd-CP)was designed and hydrothermal synthesized based on 4-(2,4-dicarboxyphenoxy)phthalic acid(H_(4)dpa),2,2'-bipyridine(bpy)and Cd(NO_(3))_(2)·4H_(2)O.The structure was characterized by single-crystal X-ray diffraction,powder X-ray diffraction,elemental analysis,and infrared spectroscopy.Cd-CP belongs to the monoclinic crystal system with the P2_1/c space group and performs in a 1D double-chain structure.The adjacent double chains further form a 3D supramolecular network structure through hydrogen bonding.Thermogravimetric analysis shows that Cd-CP has good thermal stability.Fluorescence analysis showed that Cd-CP had good choosing selectively and was sensitive to metal ions(Fe^(3+)and Zn^(2+)),2,4,6-trinitrophenylhydrazine(TRI),and pyrimethanil(Pth).Interestingly,when Cd-CP was used for fluorescence detection of metal ions,it was found to have a fluorescence quenching effect on Fe^(3+)but had an obvious enhancement effect on Zn^(2+).Therefore,we designed an“on-off-on”logic gate.In addition,the mechanism of fluorescence sensing has been deeply explored.CCDC:2258625.
基金National Natural Science Foundation of China,Grant/Award Number:U2243228The Belt and Road Special Foundation of the National Key Laboratory of Water Disaster Prevention,Grant/Award Number:2022nkms04+1 种基金MOE(Ministry of Education in China)Liberal Arts and Social Sciences Foundation,Grant/Award Number:23YJCZH332Natural Science Foundation of Anhui Province,Grant/Award Numbers:2208085US03,2308085US13。
文摘Exploring optimal operational schemes for synergistic development is crucial for sustainable management in river basins.This study introduces a multi-objective synergistic optimization framework aimed at analyzing the interplay among flood control,ecological integrity,and desilting objectives under varying watersediment conditions.The framework encompasses multi-objective reservoir optimal operation,scheme decision,and trade-off analysis among competing objectives.To address the optimization model,an elite mutation-based multiobjective particle swarm optimization(MOPSO)algorithm that integrates genetic algorithms(GA)is developed.The coupling coordination degree is employed for optimal scheme decision-making,allowing for the adjustment of weight ratios to investigate the trade-offs between objectives.This research focuses on the Sanmenxia and Xiaolangdi cascade reservoirs in the Yellow River,utilizing three representative hydrological years:1967,1969,and 2002.The findings reveal that:(1)the proposed model effectively generates Pareto fronts for multi-objective operations,facilitating the recommendation of optimal schemes based on coupling coordination degrees;(2)as water-sediment conditions shift from flooding to drought,competition intensifies between the flood control and desilting objectives.While flood control and ecological objectives compete during flood and dry years,they demonstrate synergies in normal years(r=0.22);conversely,ecological and desilting objectives are consistently competitive across all three typical years,with the strongest competition observed in the normal year(r=-0.95);(3)the advantages conferred to ecological objectives increase as water-sediment conditions shift from flooding to drought.However,the promotion of the desilting objective requires more complex trade-offs.This study provides a model and methodological approach for the multi-objective optimization of flood control,sediment management,and ecological considerations in reservoir clusters.Moreover,the methodologies presented herein can be extended to other water resource systems for multi-objective optimization and decision-making.
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.
文摘The selection and coordinated application of government innovation policies are crucial for guiding the direction of enterprise innovation and unleashing their innovation potential.However,due to the lengthy,voluminous,complex,and unstructured nature of regional innovation policy texts,traditional policy classification methods often overlook the reality that these texts cover multiple policy topics,leading to lack of objectivity.In contrast,topic mining technology can handle large-scale textual data,overcoming challenges such as the abundance of policy content and difficulty in classification.Although topic models can partition numerous policy texts into topics,they cannot analyze the interplay among policy topics and the impact of policy topic coordination on enterprise innovation in detail.Therefore,we propose a big data analysis scheme for policy coordination paths based on the latent Dirichlet allocation(LDA)model and the fuzzyset qualitative comparative analysis(fsQCA)method by combining topic models with qualitative comparative analysis.The LDA model was employed to derive the topic distribution of each document and the word distribution of each topic and enable automatic classi-fication through algorithms,providing reliable and objective textual classification results.Subsequently,the fsQCA method was used to analyze the coordination paths and dynamic characteristics.Finally,experimental analysis was conducted using innovation policy text data from 31 provincial-level administrative regions in China from 2012 to 2021 as research samples.The results suggest that the proposed method effectively partitions innovation policy topics and analyzes the policy configuration,driving enterprise innovation in different regions.
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.
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Two new coordination polymers,[Ni(Hpdc)(bib)(H_(2)O)]_(n)(1)and{[Ni(bib)_(3)](ClO_(4))_(2)}_(n)(2),were prepared by mixing Ni^(2+),3,5⁃pyrazoledicarboxylic acid(H3pdc)/p⁃nitrobenzoic acid and 1,4⁃bis(imidazol⁃1⁃ylmethyl)butane(bib)by a hydrothermal method,respectively.X⁃ray crystallography reveals a 2D network constructed by six⁃coordinated Ni(Ⅱ)centers,bib,and Hpdc2-ligands in complex 1,while a 2D network is built by Ni(Ⅱ)and bib ligands in 2.Furthermore,the quantum⁃chemical calculations have been performed on‘molecular fragments’extracted from the crystal structure of 1 using the PBE0/LANL2DZ method in Gaussian 16 and the VASP program.CCDC:2343794,1;2343798,2.
基金the National Natural Science Foundation of China(21776115,51902140)Six talent peaks project in Jiangsu Province(XCL-2018-017)Open Project of Key Laboratory of Advanced Electrode Materials for Novel Solar Cells for Petroleum and Chemical Industry of China(2024A05D).
文摘Controllable regulation of the reconstruction process for the pre-catalysts towards oxygen evolution remains as a great challenge.In this study,we report a bi-ligand strategy to facilitate the structural transformation of coordination compounds to metal oxyhydroxides during oxygen evolution with enhanced activity.A coordination compound consisting of 1,10-ferrocene acid(Fc)and Ni^(2+)was synthesized,in which terephthalic acid was introduced.The second ligand of terephthalic acid facilitates the reconstruction process,inducing an enhanced catalytic activity.In 1 mol·L^(-1)KOH aqueous solution,the optimized catalyst can drive a current density of 10 mA·cm^(-2)under a lower overpotential of 220 mV.Using this catalyst,zinc-air batteries can be prepared.The obtained zinc-air battery presents a large specific capacity of 718 mA·h·g^(-1)with excellent cycling stability for over 100 h far exceeding that of Pt/C+RuO_(2)battery fabricated with commercial catalysts.The excellent performance and low cost of this catalyst will open up broad prospects for the development of advanced systems for water electrolysis and zinc air batteries.
文摘Two coordination polymers were synthesized by hydrothermal reaction,namely,[Cd(H_(3)cpbda)(2,2′‑bipy)(H_(2)O)]_(n)(1)and[Mn(H_(3)cpbda)(phen)(H_(2)O)]_(n)(2),where H_(5)cpbda=5,5′‑[(5‑carboxy‑1,3‑phenyl)bis(oxy)]triisophthalic acid,2,2′‑bipy=2,2′‑bipyridine,phen=1,10‑phenanthroline.The two complexes were characterized by single‑crystal X‑ray diffraction,powder diffraction,infrared spectroscopy,and thermogravimetric analysis.Complexes 1 and 2 are“V”‑shaped 1D chains,and the molecules form 2D(1)and 3D framework(2)structures through weakπ…πstacking.Furthermore,complex 1 was dispersed in an aqueous solution and its fluorescence intensity demonstrated excellent stability.Complex 1 can specifically detect ciprofloxacin in urine with a detection limit of 1.91×10^(-8)mol·L^(-1).CCDC:2359498,1;2359499,2.
基金supported by the Key Fund Project for Youth Innovation of USTC(WK2040000042).
文摘Unlike the traditional decentralized channel,the drop-shipping channel entails a retailer relaying consumers’orders to the manufacturer,which proceeds to stock the orders and directly ship them to the consumers.This study explores supply chain coordination and product quality in drop-shipping and traditional channels.Specifically,we analyze the performance of both channels under wholesale price and revenue-sharing contracts.Our study yields several key findings.First,the revenue-sharing contract can coordinate both traditional and drop-shipping channels,effectively increasing supply chain performance.Second,given the channel structure,the retailer prefers the wholesale price contract,whereas the manufacturer prefers the revenue-sharing contract.Third,product quality is higher in the drop-shipping channel when demand uncertainty is high.Finally,the implementation of the revenue-sharing contract increases product quality in the traditional channel,whereas it keeps product quality unchanged in the drop-shipping channel.
基金supported by the National Natural Science Foundation of China (22275131)the Institutional Research Fund from Sichuan University (2021SCUNL201)+1 种基金the 111 Project (B20001)the Fundamental Research Funds for the Central Universities。
文摘With the increase of people’s demand,it is extremely desired for developing high-safety,widetemperature-range and high-energy-density lithium batteries,but huge challenges are remained due to shrinkage and combustion of commonly used polyolefin separators at high temperatures,as well as narrow usable temperature range and high flammability of conventionally commercialized liquid electrolytes.In this work,we report a multifunctional separator mainly consisting of Zn^(2+)-phytate coordination complex nanoparticles and bacterial cellulose nanofibers,named the BZP separator,which possesses high porosity,excellent thermotolerance,good flame retardancy,abilities of anion binding and Ni^(2+)capturing.Through cooperating with the fluoride-free wide-temperature-range electrolyte,Li//LiFePO_(4) cells not only deliver discharge capacities of 110.39 mA h g^(-1)and 113.25 mA h g^(-1)after 2200 cycles (2 C) and1600 cycles (5 C) at 25℃,with capacity retentions of 76.59%and 86.09%,respectively,but also exhibit excellent cycling performance at 80℃ and-40℃.Significantly,the Li//NCM811 cell with a loading of7.8 mg cm^(-2)delivers a discharge capacity of 146.64 mA h g^(-1)after 200 cycles at 0.5 C,with a capacity retention of 89.03%.In addition,pouch cells can work at 120℃ and have low flammability.
基金projects of National Natural Science Foundation of China (Grant Nos.22175025 and 21905023) for their generous financial support。
文摘The high energy coordination compounds Cu(TZCA)_(2)(ClO_(4))_(2)(ECCs-1) was prepared by 1H-tetrazole-5-carbohydrazide(TZCA) with a high energy skeleton and a strong coordination ability group.At the same time,the reaction activity of the ligand was explored,and the single crystal structure of it and intermediate were obtained.The structures of all substances were characterized by IR and EA.And the structure and composition of ECCs-1 are confirmed by ESP,AC,SEM and ICP-OES.Physical and chemical properties tests show that ECCs-1 has an acceptable thermal stability(T_(d)=177℃) and extremely sensitive mechanical stimulation(IS=1 J,FS=5 N).The comprehensive performance test results show that ECCs-1 has excellent initiation ability.In addition,the decomposition mechanism of ECCs-1 is explored from two aspects of experiment and theoretical calculation.
基金supported in part by the National Natural Science Foundation of China(No.51405237)。
文摘Aiming at the problem that it is difficult to generate the dynamic decoupling equation of the parallel six-dimensional acceleration sensing mechanism,two typical parallel six-dimensional acceleration sensing mechanisms are taken as examples.By analyzing the scale constraint relationship between the hinge points on the mass block and the hinge points on the base of the sensing mechanism,a new method for establishing the dynamic equation of the sensing mechanism is proposed.Firstly,based on the scale constraint relationship between the hinge points on the mass block and the hinge points on the base of the sensing mechanism,the expression of the branch rod length is obtained.The inherent constraint relationship between the branches is excavated and the branch coordination closed chain of the“12-6”configuration is constructed.The output coordination equation of the sensing mechanism is successfully derived.Secondly,the dynamic equations of“12-4”and“12-6”configurations are constructed by the Newton-Euler method,and the forward decoupling equations of the two configurations are solved by combining the dynamic equations and the output coordination equations.Finally,the virtual prototype experiment is carried out,and the maximum reference errors of the forward decoupling equations of the two configuration sensing mechanisms are 4.23%and 6.53%,respectively.The results show that the proposed method is effective and feasible,and meets the real-time requirements.
基金supported by the National Natural Science Foundation of China (No. 22005216 and 52172241)the General Research Fund of Hong Kong (No. CityU 11308321)Tianjin Research Innovation Project for Postgraduate Students (No.2022BKY130)
文摘Suppression of uncontrollable dendrite growth and water-induced side reactions of Zn metal anodes is crucial for achieving long-lasting cycling stability and facilitating the practical implementations of aqueous Zn-metal batteries.To address these challenges,we report in this study a functional nitro-cellulose interfacial layer(NCIL)on the surface of Zn anodes enlightened by a nitro-coordination chemistry strategy.The NCIL exhibits strong zincophilicity and superior coordination capability with Zn^(2+)due to the highly electronegative and highly nucleophilic nature of the nitro functional group.This characteristic facilitates a rapid Zn-ion desolvation process and homogeneous Zn plating,effectively preventing H_(2) evolution and dendrite formation.Additionally,the negatively charged surface of NCIL acts as a shield,repelling SO_(4)^(2-)anions and inhibiting corrosive reactions on the Zn surface.Remarkably,reversible and stable Zn plating/stripping is achieved for over 5100 h at a current density of 1 mA cm^(-2),which is nearly 30 times longer than that of bare Zn anodes.Furthermore,the Zn/V_(2)O_(5) full cells with the functional interface layer deliver a high-capacity retention of 80.3%for over 10,000 cycles at 5 A g^(-1).This research offers valuable insights for the rational development of advanced protective interface layers in order to achieve ultra-long-lifeZnmetal batteries.
基金National Natural Science Foundation of China(No.22379111 and 22179093)。
文摘Single metal atoms anchored on nitrogen-doped carbon materials(M-N_(4))have been identified as effective active sites for catalyzing the two-electron oxygen reduction reaction(2e-ORR).However,the relationship between the local atomic/electronic environments of the M-N_(4) sites(metal atoms coordinated with different types of N species)and their catalytic activity for 2e-ORR has rarely been elaborated clearly,which imposes significant ambiguity for the rational design of catalysts.Herein,guided by the comprehensive density-functional theory calculations and predictions,a series of Zn-N_(4) single-atom catalysts(SACs)are designed with pyrrole/pyridine-N(N_(Po)/N_(Pd))synergistic coordination and prepared by controlling the pyrolysis temperature(600,700,and 800℃),Among them,the dominated Zn-N_(4) configurations with rationally combined N_(Po)/N_(Pd)coordination show~*OOH adsorption strength close to the optimal value,much superior to those with mono N species.Thus,the as-prepared catalyst exhibits a high H_(2)O_(2) selectivity of over 90%both in neutral and alkaline environments,with a superb H_(2)O_(2) yield of up to 33.63 mol g^(-1)h^(-1)in an alkaline with flow cell.More importantly,a new descriptor,dz^(2)+s band center,has been proposed,which is especially feasible for predicting the activity for metal types with fully occupied s and d orbitals.This work thus presents clear guidance for the rational design of highly active SACs toward ORR and provides a complement to the d-band theory for more accurately predicting the catalytic activity of the materials.
基金Under the auspices of the National Natural Science Foundation of China(No.41901262)Natural Science Basic Research Program of Shaanxi(No.2024JC-YBQN-0300)Fundamental Research Funds for the Central Universities(No.GK202103125,GK202207005)。
文摘One of the greatest challenges in the agroecosystem is to improve cropland intensification while preserving agroecosystem services.While many studies have investigated the effect of cropland intensification on agroecosystem service,the interactive coupling and coordination among these factors remain largely unexplored.In view of this,this study performed a case study of the Loess Plateau in Shaanxi Province,China and constructed comprehensive evaluation models to quantify the cropland intensification and agroecosystem service in this area.Balance analysis and the coupling coordination degree model were used to evaluate the interactive relationship between cropland intensification and agroecosystem service,and statistical analysis and spatial autocorrelation were used to analyze the spatial characteristics and potential mechanism of the coupling coordination.Results show that both the cropland intensification and agroecosystem service in the study area were relatively low yet gradually increased from 2000 to 2020.Agroecosystem service lag was identified as the dominant unbalanced development type.Improving the supply capacity of agroecosystem services plays a key role in the balanced development of cropland in the Loess Plateau.The coupling coordination degree between cropland intensification and agroecosystem service ranges from basic coordination to serious incoordination.Therefore,cropland intensification practices in the area should be optimized to enhance this coordination degree.An upward trend was also observed in the coupling coordination degree from2000 to 2020.The withdrawal of marginal cropland in the Grain for Green program is one of the most important reasons for this trend,especially for the northern region.Around 83.6%of the high-high clusters are concentrated in the southern region of the Loess Plateau,whereas 70.5%of the low-low clusters are distributed in the northern region.These clustering characteristics are mainly attributed to the environmental suitability of these areas for agriculture and their degree of economic development.
基金Fundamental Research Funds for the Central Universities(2023MS125)。
文摘Currently,the iron chromium redox flow battery(ICRFB)has become a research hotspot in the energy storage field owing to its low cost and easily-scaled-up.However,the activity of electrolyte is still ambiguous due to its complicated solution environment.Herein,we performed a pioneering investigation on the coordination behavior and transformation mechanism of Cr^(3+)in electrolyte and prediction of impurity ions impact through quantum chemistry computations.Based on the structure and symmetry of electrostatic potential distribution,the activity of different Cr^(3+)complex ions is confirmed as[Cr(H2O)5Cl]^(2+)>[Cr(H2O)4Cl2]+>[Cr(H2O)6]^(3+).The transformation mechanism between[Cr(H2O)6]^(3+)and[Cr(H2O)5Cl]^(2+)is revealed.We find the metal impurity ions(especially Mg^(2+))can exacerbate the electrolyte deactivation by reducing the transformation energy barrier from[Cr(H2O)5Cl]^(2+)(24.38 kcal mol^(−1))to[Cr(H2O)6]^(3+)(16.23 kcal mol^(−1)).The solvent radial distribution and mean square displacement in different solvent environments are discussed and we conclude that the coordination configuration limits the diffusivity of Cr^(3+).This work provides new insights into the activity of electrolyte,laying a fundamental sense for the electrolyte in ICRFB.
