In this article the affiliation of Jin-Ke Shen,Nai-Teng Wu,Li-Yuan Wang,Gang Jiang,Jin Li,Gui-Long Liu,Xian-Ming Liu were incorrectly given as:State Key Laboratory of Chemistry and Utilization of Carbon Based Energy R...In this article the affiliation of Jin-Ke Shen,Nai-Teng Wu,Li-Yuan Wang,Gang Jiang,Jin Li,Gui-Long Liu,Xian-Ming Liu were incorrectly given as:State Key Laboratory of Chemistry and Utilization of Carbon Based Energy Resources,School of Chemical Engineering and Technology,Xinjiang University,Urumqi 830046,China.展开更多
Sn-based metal organic complexes with coordination bonds,multi-active sites,and high theoretical capacity have attracted much attention as promising anodes for lithium ion batteries.However,the low electrical conducti...Sn-based metal organic complexes with coordination bonds,multi-active sites,and high theoretical capacity have attracted much attention as promising anodes for lithium ion batteries.However,the low electrical conductivity and huge volume changes restricted their electrochemical stability and practical utilization.Herein,Snbased anode with superior electrochemical performance,including a high reversible capacity of 1050.1 mAh·g^(-1)at 2 A·g^(-1)and a stable capacity of 1105.5 mAh·g^(-1)after 500 cycles at 1 A·g^(-1),was fabricated via a low-temperature calcination strategy from Sn metal organic complexes.The low-temperature calcination process regulates Sn-O bond and prevents the agglomeration of SnO_(2),generating highly dispersed SnO_(2) decorated metal organic complexes and providing sufficient active sites for ion storage.Ex situ characterizations expound that the undecomposed Sn-based metal organic complexes could be transformed into SnO_(2) during lithiation and delithiation,which enhances the electrical conductivity and induces a strong pseudo-capacitive behavior,accelerating the electrochemical kinetics;the multiple solid electrolyte interface with inflexible LiF and flexible ROCO_(2)Li buffers the volume variation of the electrode,resulting in its high electrochemical stability.This work provides a simple strategy for preparing excellent Sn-based anodes from metal organic complexes and reveals the lithium storage mechanism of the prepared Snbased anode.展开更多
Organic redox compounds are attractive cathode materials in aqueous zinc-ion batteries owing to their low cost,environmental friendliness,multiple-electron-transfer reactions,and resource sustainability.However,the re...Organic redox compounds are attractive cathode materials in aqueous zinc-ion batteries owing to their low cost,environmental friendliness,multiple-electron-transfer reactions,and resource sustainability.However,the realized energy density is constrained by the limited capacity and low voltage.Herein,copper-tetracyanoquinodimethane(CuTCNQ),an organic charge-transfer complex is evaluated as a zinc-ion battery cathode owing to the good electron acceptation ability in the cyano groups that improves the voltage output.Through electrochemical activation,electrolyte optimization,and adoption of graphene-based separator,CuTCNQ-based aqueous zinc-ion batteries deliver much improved rate performance and cycling stability with anti-self-discharge properties.The structural evolution of CuTCNQ during discharge/charge are investigated by ex situ Fourier transform infra-red(FT-IR)spectra,ex situ X-ray photoelectron spectroscopy(XPS),and in situ ultraviolet visible spectroscopy(UV-vis),revealing reversible redox reactions in both cuprous cations(Cu^(+))and organic anions(TCNQ^(x-1)),thus delivering a high voltage output of 1.0 V and excellent discharge capacity of 158 mAh g^(-1).The remarkable electrochemical performance in Zn//CuTCNQ is ascribed to the strong inductive effect of cyano groups in CuTCNQ that elevated the voltage output and the graphene-modified separator that inhibited CuTCNQ dissolution and shuttle effect in aqueous electrolytes.展开更多
In this paper,three new polyoxometalates(POM)-based metal–organic complexes constructed from a new semi-rigid organic ligand N,N'-bis(4-pyrimidinecarboxamido)-1,2-cyclohexane(4-bpmah)H_(2)[Cu(4-bpmah)_(2)(SiMo_(1...In this paper,three new polyoxometalates(POM)-based metal–organic complexes constructed from a new semi-rigid organic ligand N,N'-bis(4-pyrimidinecarboxamido)-1,2-cyclohexane(4-bpmah)H_(2)[Cu(4-bpmah)_(2)(SiMo_(12)O_(40))(H_(2)O)_(2)]·2H_(2)O(1),H[Cu(4-bpmah)_(2)(PMo_(12)O_(4)0)(H_(2)O)_(2)]·2H_(2)O(2)and[Cu(4-bpmah)(H_(2)O)_(2)]·[Cu_(2)(TeMo_(6)O_(24))(H_(2)O)_(10)]·4H_(2)O(3)were synthesized by hydrothermal method.Single crystal X-ray analyses showed that complexes 1 and 2 were isostructural,in which the isolated Keggin-type[SiMo1_(2)O_(40)]^(4–)/[PMo_(12)O_(40)]^(3–)anions and[Cu(4-bpmah)_(2)(H_(2)O)2]^(2n+)units were expanded into 3D supramolecular structures through hydrogen bond interactions.In complex 3,the 1D[Cu(4-bpmah)(H_(2)O)_(2)]^(2n+)metal–organic chains and isolated[Cu_(2)(TeMo_(6)O_(24))(H_(2)O)_(10)]^(2n–)units were expanded into a 3D supramolecular framework by the hydrogen bond interactions.In this paper,carbon cloth working electrodes composited by the title complexes(1/CC,2/CC and 3/CC)were prepared and used as electrodes for supercapacitors.The performance of supercapacitors as well as the influence of electrolyte solution and title complexes quality load on the performance of supercapacitors were studied.Furthermore,the electrochemistry and electrocatalytic behaviors of complexes 1–3 bulk-modified carbon paste electrodes(1-CPE,2-CPE and 3-CPE)toward the reduction of KBrO_(3),KNO_(2),Cr(Ⅵ),as well as their sensing behaviors on Cr(Ⅵ)were investigated.展开更多
Both silica and boron-silica glass materials doped with terbium organic complex were prepared by in situ sol-gel method respectively. XRD and SEM measurements were performed to verify the non-crystalline structure of ...Both silica and boron-silica glass materials doped with terbium organic complex were prepared by in situ sol-gel method respectively. XRD and SEM measurements were performed to verify the non-crystalline structure of the glass. The influence of the glass contents on the structure of the glass and the erwrgy level of the doped Tb （Ⅲ） ions was analyzed by the emission spectra and IR spectra. The effect of B2O3 on the photolumirwscence properties of rare earth organic complex in silica- based glass was investigated. The IR spectra indicate that the in situ sylthesized rare earth complex molecule was confined to the micropores of the bost and the vibration of the ligands was frozen. When B2O3 was added into the silica host gel, B2O3 had little influence on the noncrystallirw structure of the glass, and BO3 triangle, which had a layer structure different from the silica framework, could form. So the silica network became more inhomogenous, and the luminescence of terbium complexes was quenched with the increase of the B2O23 amount.展开更多
Hole-transporting material(HTM)plays a paramount role in enhancing the photovltaic performance of perovskite solar cells(PSCs).Currently,the vast majority of these HTMs employed in PSCs are organic small molecules and...Hole-transporting material(HTM)plays a paramount role in enhancing the photovltaic performance of perovskite solar cells(PSCs).Currently,the vast majority of these HTMs employed in PSCs are organic small molecules and polymers,yet the use of organic metal complexes in PSCs applications remains less explored.To date,most of reported HTMs require additional chemical additives(e.g.Li-TFSI,t-TBP)towards high performance,however,the introduction of additives decrease the PSCs device stability.Herein,an organic metal complex(Ni-TPA)is first developed as a dopant-free HTM applied in PSCs for its facile synthesis and efficient hole extract/transfer ability.Consequently,the dopant-free Ni-TPAbased device achieves a champion efficiency of 17.89%,which is superior to that of pristine Spiro-OMeTAD(14.25%).Furthermore,we introduce a double HTM layer with a graded energy bandgap containing a Ni-TPA layer and a CuSCN layer into PSCs,the non-encapsulated PSCs based on the Ni-TPA/CuSCN layers affords impressive efficiency up to 20.39%and maintains 96%of the initial PCE after 1000 h at a relative humidity around 40%.The results have demonstrated that metal organic complexes represent a great promise for designing new dopant-free HTMs towards highly stable PSCs.展开更多
The recovery of neptunium(Np)from nuclear waste is of paramount importance for mitigating long-term environmental radiotoxicity.However,this endeavor is significantly hindered by the intricate redox chemistry of Np,wh...The recovery of neptunium(Np)from nuclear waste is of paramount importance for mitigating long-term environmental radiotoxicity.However,this endeavor is significantly hindered by the intricate redox chemistry of Np,which necessitates precise control over its oxidation states.Here we present a straightforward and efficient methodology for the quantitative conversion of Np(V)to Np(IV)under catalysis-free and mild conditions,leveraging organic complexation with an array of widely employed tridentate O-donor ligands:N,N,N′,N′-tetramethyl diglycolamide(TMDGA),N,N-dimethyl diglycolamide(DMDGA),and diglycol acid(DGA).Compared to the“free”Np ion,the reduction efficiency of Np(V)unprecedentedly boosts more than 300times in the case of complexing with TMDGA,thereby opening up a new path to control the oxidation state of Np and supporting the crucial task of Np recovering in spent nuclear fuel reprocessing.展开更多
Tin-based metal organic complexes with breakable coordination bonds,multiple active sites,and high theoretical capacity have attracted wide attentiorials for lithium-ion batteries(LIBs).However,the inferior electrical...Tin-based metal organic complexes with breakable coordination bonds,multiple active sites,and high theoretical capacity have attracted wide attentiorials for lithium-ion batteries(LIBs).However,the inferior electrical conductivity and significant volume changes have limited their electrochemical stability and practical application performance.This work proposes a universal doping strategy for the preparation of tin-phthalic acid complexes(Sn-MOF)doped with metal atoms(Al,Cr,Mn,Fe,Co,Ni,Cu,Zn).Metal atoms are uniformly dispersed within Sn-MOF for enhancing electrical conductivity and accommodating appropriate volume expansion,resulting in improved rate capability and cycling stability.Additionally,compared to a series of doped Sn-MOF,Zn-doped Sn-MOF exhibits the most exceptional electrochemical performance with a high reversible capacity of 1131 mAh·g^(-1)and stable cycling performance at a current density of 0.5 A·g^(-1),delivering a capacity of 1065 mAh·g^(-1)after 500 cycles.Zn-doping catalyzes the lithiation reaction between Sn-MOF and Li^(+),promoting their reaction kinetics during the first cycle.Furthermore,the Zn-doped Sn-MOF is inclined to form a thin and stable solid electrolyte interface film to maintain cyclic stability.展开更多
Organoboron compounds have become important intermediates for the construction of new compounds in synthetic chemistry and pharmaceutical chemistry,and it has been found that pinacol biborate(B_(2)pin_(2))as the boron...Organoboron compounds have become important intermediates for the construction of new compounds in synthetic chemistry and pharmaceutical chemistry,and it has been found that pinacol biborate(B_(2)pin_(2))as the boron source and Cu^(Ⅱ) organophosphorus complex(L)as the catalyst can effectively realize the hydrogen-reduced borylation products and dehydrohydrated borylation products of aryl olefins.The reaction regioselectivity involvingβ-C positions of aryl olefins can be controlled by regulating the ligand and additive types.The formation mechanism of the product is conducted at LCu^(Ⅰ)Bpin formed from Cu^(Ⅱ),L and B_(2)pin_(2).Subsequently the substrate aryl olefins undergo addition reaction to form the active intermediate PhCH(LCu^(Ⅰ))CH_(2)Bpin.Followed by the metathesis of the active intermediate with water to form hydrogen reduction products,the same active intermediate can be oxidized with 2,2,6,6-tetramethylpiperidoxyl(TEMPO)to form trans dehydrogenation products.展开更多
Taking the shale oil of the first member of the Cretaceous Qingshankou Formation of Changling Sag in southern Songliao Basin as an example,this paper establishes a saturation model of lacustrine shale oil considering ...Taking the shale oil of the first member of the Cretaceous Qingshankou Formation of Changling Sag in southern Songliao Basin as an example,this paper establishes a saturation model of lacustrine shale oil considering the influence of organic matter on clay-bound water conductivity.Based on the fluid characterization results of sealed samples and two-dimensional nuclear magnetic resonance,the differential influence of organic matter on clay-bound water conductivity was quantitatively revealed,and the conductivity mechanism and rock-electrical relationships of lacustrine shale were systematically analyzed.The results show that there are two conductive networks for lacustrine shales,i.e.the matrix free water and the clay-bound water.The bound water cementation index msh was introduced to reflect the impact of organic matter on clay-bound water conductivity,and it is positively correlated with the effective porosity.When there is sufficient rigid framework support and well-developed pores,organic matter is more likely to fill or adsorb onto clay interlayers.This reduces the ion exchange capacity of the electrical double layer,leading to an increase in msh and a decrease in the conductivity of clay-bound water.The overall conductivity of shale is controlled by the clay-bound water conductivity,and the relative contributions of the mentioned two conductive networks to formation conductivity are affected by the effective porosity and msh.The larger the effective porosity and msh,the more the contribution of the matrix free water to formation conductivity.According to the experimental results,the proposed saturation model yields a significantly higher interpretation accuracy in oil saturation than the Archie model and the Total-shale model.展开更多
The phosphorus（P） fraction distribution and formation mechanism in the supernatant after P adsorption onto iron oxides and iron oxide-humic acid（HA） complexes were analyzed using the ultrafiltration method in this...The phosphorus（P） fraction distribution and formation mechanism in the supernatant after P adsorption onto iron oxides and iron oxide-humic acid（HA） complexes were analyzed using the ultrafiltration method in this study.With an initial P concentration of 20 mg/L（I =0.01 mol/L and pH = 7）,it was shown that the colloid（1 kDa-0.45 μm） component of P accounted for 10.6%,11.6%,6.5%,and 4.0%of remaining total P concentration in the supernatant after P adsorption onto ferrihydrite（FH）,goethite（GE）,ferrihydrite-humic acid complex（FH-HA）,goethite-humic acid complex（GE-HA）,respectively.The 〈1 kDa component of P was still the predominant fraction in the supernatant,and underestimated colloidal P accounted for 2.2%,55.1%,45.5%,and 38.7%of P adsorption onto the solid surface of FH,FH-HA,GE and GE-HA,respectively.Thus,the colloid P could not be neglected.Notably,it could be interpreted that Fe3＋ hydrolysis from the adsorbents followed by the formation of colloidal hydrous ferric oxide aggregates was the main mechanism for the formation of the colloid P in the supernatant.And colloidal adsorbent particles co-existing in the supernatant were another important reason for it.Additionally,dissolve organic matter dissolved from iron oxide-HA complexes could occupy large adsorption sites of colloidal iron causing less colloid P in the supernatant.Ultimately,we believe that the findings can provide a new way to deeply interpret the geochemical cycling of P,even when considering other contaminants such as organic pollutants,heavy metal ions,and arsenate at the sediment/soil-water interface in the real environment.展开更多
Elementary information theory is used to model cybersecurity complexity, where the model assumes that security risk management is a binomial stochastic process. Complexity is shown to increase exponentially with the n...Elementary information theory is used to model cybersecurity complexity, where the model assumes that security risk management is a binomial stochastic process. Complexity is shown to increase exponentially with the number of vulnerabilities in combination with security risk management entropy. However, vulnerabilities can be either local or non-local, where the former is confined to networked elements and the latter results from interactions between elements. Furthermore, interactions involve multiple methods of communication, where each method can contain vulnerabilities specific to that method. Importantly, the number of possible interactions scales quadratically with the number of elements in standard network topologies. Minimizing these interactions can significantly reduce the number of vulnerabilities and the accompanying complexity. Two network configurations that yield sub-quadratic and linear scaling relations are presented.展开更多
The most simple method for solventless synthesis of supramolecular complex of CMCR·2BPY·BZP, [CMCR = C-methylcalix[4]resorcinarene, BPY = 4,4'-bipyridine, BZP = benzophenone], is proposed. Although CMCR ...The most simple method for solventless synthesis of supramolecular complex of CMCR·2BPY·BZP, [CMCR = C-methylcalix[4]resorcinarene, BPY = 4,4'-bipyridine, BZP = benzophenone], is proposed. Although CMCR by itself is high melting point compound (above 300°C), CMCR was found to be dissolved in melt mixture of BPY and BZPeven below 120°C. In the mixture of the three components, the reaction occurs to form CMCR·2BPY·BZP supramolecular complex.展开更多
A novel Fe/Co metal organic complex nanosheet modified by 1,4-dicarboxybenzene(BDC),i.e.,FeCo@BDC,was prepared,and highly efficient removal performance for trace lead(Ⅱ)(Pb^(2+))was demonstrated in the neutral aqueou...A novel Fe/Co metal organic complex nanosheet modified by 1,4-dicarboxybenzene(BDC),i.e.,FeCo@BDC,was prepared,and highly efficient removal performance for trace lead(Ⅱ)(Pb^(2+))was demonstrated in the neutral aqueous solutions.The removal rates were higher than 95%and the adsorption was equilibrated in 15 min.The isotherms and kinetics for the adsorption Pb^(2+)by the FeCo@BDC adsorbents followed Langmuir model and pseudo-second-order model,respectively.The maximum adsorption capacity was 220.48 mg g^(-1).The FeCo@BDC adsorbents also own a prominent regeneration performance.The prominent performance of in the removal of trace Pb^(2+)makes FeCo@BDC an ideal candidate as commercial adsorbent materials.展开更多
A novel europium complex, bi(dibenzamide) benzoate europium(Ⅲ) (Eu-DBA-B), was synthesized. The composition and photoluminescence properties of Eu-DBA-B were investigated. The results show that the europium complex i...A novel europium complex, bi(dibenzamide) benzoate europium(Ⅲ) (Eu-DBA-B), was synthesized. The composition and photoluminescence properties of Eu-DBA-B were investigated. The results show that the europium complex is an electroneutral complex, and it emits very strong red luminescence from (()~5D_1→()~7F_j) (j=0, 1, 2, 3, 4) transitions.展开更多
The reaction of MeCpLnCl·2LiCl·nTHF with 2 equivalent of LiNPh_2 in THF,hexane and toluene mixture solution gives the new complex[Li(DME)_2][(η~5-MeCp)Ln(NPh_2)_3](Ln=La,Pr,Nd)by extraction with DME.They ha...The reaction of MeCpLnCl·2LiCl·nTHF with 2 equivalent of LiNPh_2 in THF,hexane and toluene mixture solution gives the new complex[Li(DME)_2][(η~5-MeCp)Ln(NPh_2)_3](Ln=La,Pr,Nd)by extraction with DME.They have been characterized by elemental analysis,IR and NMR.The La complex crystallizes in the monoclinic space group P2_1/c with α=1.8335(6)nm,b=1.6576(5)nm,c=1.7461(6)nm, β=96.04°,V=5.277 nm^2,Z=4,D_c=1.26g·cm^(-3),R=0.057 and R_w=0.048(1≥2.5σ(I_o))for 3378 reflec- tions.The complex consists of a pair of a cation and an anion.La^(3+) is coordinated by one methylcyclopentadienyl and three diphenylamidos to form six-coordinate pseudotetrahedron with the mean Ln-N and La-C(ring)distances of 0.2459(8)and 0.2843(11)nm,respectively.展开更多
[Pb（HL）（phen）]n （1） and [Cd3L2（phen）]n （2）, where phen = 1,10-phenanthroline and L = 4,4＇-（2-carboxylatopropane-1,3-diyl）dibenzoate, were hydrothermally prepared and fully characterized by X-ray single-cr...[Pb（HL）（phen）]n （1） and [Cd3L2（phen）]n （2）, where phen = 1,10-phenanthroline and L = 4,4＇-（2-carboxylatopropane-1,3-diyl）dibenzoate, were hydrothermally prepared and fully characterized by X-ray single-crystal diffraction, infrared spectroscopy and thermogravimetric analyses. The decomposition temperature of 1 and 2 was measured to be ca. 304 and 416 ℃, respectively. The charge transfer transition based absorption of 1 and 2 was also verified by the powder scattering spectra and theoretical analyses.展开更多
Multi-organ-on-a-chip(MOOC)technology represents a pivotal direction in the organ-on-a-chip field,seeking to emulate the complex interactions of multiple human organs in vitro through microfluidic systems.This technol...Multi-organ-on-a-chip(MOOC)technology represents a pivotal direction in the organ-on-a-chip field,seeking to emulate the complex interactions of multiple human organs in vitro through microfluidic systems.This technology overcomes the limitations of traditional single-organ models,providing a novel platform for investigating complex disease mechanisms and evaluating drug efficacy and toxicity.Although it demonstrates broad application prospects,its development still faces critical bottlenecks,including inadequate physiological coupling between organs,short functional maintenance durations,and limited real-time monitoring capabilities.Contemporary research is advancing along three key directions,including functional coupling,sensor integration,and full-process automation systems,to propel the technology toward enhanced levels of physiological relevance and predictive accuracy.展开更多
To examine the activation of organic acids on the leaching process of ion-adsorption type rare earth ore（IRE-ore）, the leaching behavior of rare earth（RE） and zeta potential of IRE-ore were investigated in the abs...To examine the activation of organic acids on the leaching process of ion-adsorption type rare earth ore（IRE-ore）, the leaching behavior of rare earth（RE） and zeta potential of IRE-ore were investigated in the absence and presence of carboxylic acids. The results show that all the tested organic acids（acetic acid,malonic acid, citric acid, tartaric acid, succinic acid, and malic acid） can promote RE extraction. At relatively high concentrations of organic acids, the activation efficiency of organic acids on RE extraction is generally consistent with their complexation ability; whereas at their low concentrations, the change of zeta potential on the IRE-ore surface with organic acid concentration and p H has a close association with RE extraction, which indicates that organic acids can impact the surface electrical property of IREore via their adsorption/desorption, and thereby increase/decrease the affinity of RE ions to IRE-ore.Therefore the influence of organic acids on the IRE-ore surface electrical property also plays an important role in RE extraction in addition to their complexation with RE ions.展开更多
This paper presents the results of the search of biologically active uranium compounds such as amino acids. We first received and examined X-ray and IR （infrared radiation） spectroscopy of uranium complexes with α-...This paper presents the results of the search of biologically active uranium compounds such as amino acids. We first received and examined X-ray and IR （infrared radiation） spectroscopy of uranium complexes with α- and β-amino acids in aqueous and organic solution. We proposed a method for direct synthesis of complex organic compounds of uranium chloride UO2Cl2 with α- andβ-amino acids for the synthesis of drugs for the treatment of cancer.展开更多
文摘In this article the affiliation of Jin-Ke Shen,Nai-Teng Wu,Li-Yuan Wang,Gang Jiang,Jin Li,Gui-Long Liu,Xian-Ming Liu were incorrectly given as:State Key Laboratory of Chemistry and Utilization of Carbon Based Energy Resources,School of Chemical Engineering and Technology,Xinjiang University,Urumqi 830046,China.
基金financially supported by the Program for Science&Technology Innovation Talents in Universities of Henan Province(No.24HASTIT006)the Natural Science Foundations of China(No.42002040)+2 种基金Natural Science Foundations of Henan Province(No.222300420502)Key Science and Technology Program of Henan Province(No.222102240044)Key Scientific Research Projects in Colleges and Universities of Henan Province(No.21B610010)。
文摘Sn-based metal organic complexes with coordination bonds,multi-active sites,and high theoretical capacity have attracted much attention as promising anodes for lithium ion batteries.However,the low electrical conductivity and huge volume changes restricted their electrochemical stability and practical utilization.Herein,Snbased anode with superior electrochemical performance,including a high reversible capacity of 1050.1 mAh·g^(-1)at 2 A·g^(-1)and a stable capacity of 1105.5 mAh·g^(-1)after 500 cycles at 1 A·g^(-1),was fabricated via a low-temperature calcination strategy from Sn metal organic complexes.The low-temperature calcination process regulates Sn-O bond and prevents the agglomeration of SnO_(2),generating highly dispersed SnO_(2) decorated metal organic complexes and providing sufficient active sites for ion storage.Ex situ characterizations expound that the undecomposed Sn-based metal organic complexes could be transformed into SnO_(2) during lithiation and delithiation,which enhances the electrical conductivity and induces a strong pseudo-capacitive behavior,accelerating the electrochemical kinetics;the multiple solid electrolyte interface with inflexible LiF and flexible ROCO_(2)Li buffers the volume variation of the electrode,resulting in its high electrochemical stability.This work provides a simple strategy for preparing excellent Sn-based anodes from metal organic complexes and reveals the lithium storage mechanism of the prepared Snbased anode.
基金financially supported by the National Natural Science Foundation of China(Nos.52102117,51173170,and 21773216)the joint project from the Henan-Provincial and the China-National Natural Science Foundations(No.U2004208)Key Science and Technology Program of Henan Province(No.202102310212)
文摘Organic redox compounds are attractive cathode materials in aqueous zinc-ion batteries owing to their low cost,environmental friendliness,multiple-electron-transfer reactions,and resource sustainability.However,the realized energy density is constrained by the limited capacity and low voltage.Herein,copper-tetracyanoquinodimethane(CuTCNQ),an organic charge-transfer complex is evaluated as a zinc-ion battery cathode owing to the good electron acceptation ability in the cyano groups that improves the voltage output.Through electrochemical activation,electrolyte optimization,and adoption of graphene-based separator,CuTCNQ-based aqueous zinc-ion batteries deliver much improved rate performance and cycling stability with anti-self-discharge properties.The structural evolution of CuTCNQ during discharge/charge are investigated by ex situ Fourier transform infra-red(FT-IR)spectra,ex situ X-ray photoelectron spectroscopy(XPS),and in situ ultraviolet visible spectroscopy(UV-vis),revealing reversible redox reactions in both cuprous cations(Cu^(+))and organic anions(TCNQ^(x-1)),thus delivering a high voltage output of 1.0 V and excellent discharge capacity of 158 mAh g^(-1).The remarkable electrochemical performance in Zn//CuTCNQ is ascribed to the strong inductive effect of cyano groups in CuTCNQ that elevated the voltage output and the graphene-modified separator that inhibited CuTCNQ dissolution and shuttle effect in aqueous electrolytes.
基金financially supported by the National Natural Science Foundation of China (Nos. 21971024, 21671025)Liaoning Revitalization Talents Program (No. XLYC1902011)
文摘In this paper,three new polyoxometalates(POM)-based metal–organic complexes constructed from a new semi-rigid organic ligand N,N'-bis(4-pyrimidinecarboxamido)-1,2-cyclohexane(4-bpmah)H_(2)[Cu(4-bpmah)_(2)(SiMo_(12)O_(40))(H_(2)O)_(2)]·2H_(2)O(1),H[Cu(4-bpmah)_(2)(PMo_(12)O_(4)0)(H_(2)O)_(2)]·2H_(2)O(2)and[Cu(4-bpmah)(H_(2)O)_(2)]·[Cu_(2)(TeMo_(6)O_(24))(H_(2)O)_(10)]·4H_(2)O(3)were synthesized by hydrothermal method.Single crystal X-ray analyses showed that complexes 1 and 2 were isostructural,in which the isolated Keggin-type[SiMo1_(2)O_(40)]^(4–)/[PMo_(12)O_(40)]^(3–)anions and[Cu(4-bpmah)_(2)(H_(2)O)2]^(2n+)units were expanded into 3D supramolecular structures through hydrogen bond interactions.In complex 3,the 1D[Cu(4-bpmah)(H_(2)O)_(2)]^(2n+)metal–organic chains and isolated[Cu_(2)(TeMo_(6)O_(24))(H_(2)O)_(10)]^(2n–)units were expanded into a 3D supramolecular framework by the hydrogen bond interactions.In this paper,carbon cloth working electrodes composited by the title complexes(1/CC,2/CC and 3/CC)were prepared and used as electrodes for supercapacitors.The performance of supercapacitors as well as the influence of electrolyte solution and title complexes quality load on the performance of supercapacitors were studied.Furthermore,the electrochemistry and electrocatalytic behaviors of complexes 1–3 bulk-modified carbon paste electrodes(1-CPE,2-CPE and 3-CPE)toward the reduction of KBrO_(3),KNO_(2),Cr(Ⅵ),as well as their sensing behaviors on Cr(Ⅵ)were investigated.
基金Funded bythe National Natural Science Fundation of China(No.90206047)
文摘Both silica and boron-silica glass materials doped with terbium organic complex were prepared by in situ sol-gel method respectively. XRD and SEM measurements were performed to verify the non-crystalline structure of the glass. The influence of the glass contents on the structure of the glass and the erwrgy level of the doped Tb （Ⅲ） ions was analyzed by the emission spectra and IR spectra. The effect of B2O3 on the photolumirwscence properties of rare earth organic complex in silica- based glass was investigated. The IR spectra indicate that the in situ sylthesized rare earth complex molecule was confined to the micropores of the bost and the vibration of the ligands was frozen. When B2O3 was added into the silica host gel, B2O3 had little influence on the noncrystallirw structure of the glass, and BO3 triangle, which had a layer structure different from the silica framework, could form. So the silica network became more inhomogenous, and the luminescence of terbium complexes was quenched with the increase of the B2O23 amount.
基金the National Natural Science Foundation of China(22065038)the Key Project of Natural Science Foundation of Yunnan(KC10110419)+4 种基金the High-Level Talents Introduction in Yunnan Province(C619300A010)the Fund for Excellent Young Scholars of Yunnan(K264202006820)the Program for Excellent Young Talents of Yunnan University and Major Science(C176220200)the International Joint Research Center for Advanced Energy Materials of Yunnan Province(202003AE140001)the Technology Project of Precious Metal Materials Genetic Engineering in Yunnan Province(No.2019Z E001-1202002AB080001)for financial support。
文摘Hole-transporting material(HTM)plays a paramount role in enhancing the photovltaic performance of perovskite solar cells(PSCs).Currently,the vast majority of these HTMs employed in PSCs are organic small molecules and polymers,yet the use of organic metal complexes in PSCs applications remains less explored.To date,most of reported HTMs require additional chemical additives(e.g.Li-TFSI,t-TBP)towards high performance,however,the introduction of additives decrease the PSCs device stability.Herein,an organic metal complex(Ni-TPA)is first developed as a dopant-free HTM applied in PSCs for its facile synthesis and efficient hole extract/transfer ability.Consequently,the dopant-free Ni-TPAbased device achieves a champion efficiency of 17.89%,which is superior to that of pristine Spiro-OMeTAD(14.25%).Furthermore,we introduce a double HTM layer with a graded energy bandgap containing a Ni-TPA layer and a CuSCN layer into PSCs,the non-encapsulated PSCs based on the Ni-TPA/CuSCN layers affords impressive efficiency up to 20.39%and maintains 96%of the initial PCE after 1000 h at a relative humidity around 40%.The results have demonstrated that metal organic complexes represent a great promise for designing new dopant-free HTMs towards highly stable PSCs.
基金financial support from the National Natural Science Foundation of China(22376116)the Young Elite Scientists Sponsorship Program by China Association for Science and Technology(2023QNRC001)+2 种基金the Ling Chuang Research Project of China National Nuclear Corporation(CNNC-LCKY-2024-014)the Outstanding Young Engineer Program by Beijing Association for Science and Technologythe financial support from the National Natural Science Foundation of China(22406104)。
文摘The recovery of neptunium(Np)from nuclear waste is of paramount importance for mitigating long-term environmental radiotoxicity.However,this endeavor is significantly hindered by the intricate redox chemistry of Np,which necessitates precise control over its oxidation states.Here we present a straightforward and efficient methodology for the quantitative conversion of Np(V)to Np(IV)under catalysis-free and mild conditions,leveraging organic complexation with an array of widely employed tridentate O-donor ligands:N,N,N′,N′-tetramethyl diglycolamide(TMDGA),N,N-dimethyl diglycolamide(DMDGA),and diglycol acid(DGA).Compared to the“free”Np ion,the reduction efficiency of Np(V)unprecedentedly boosts more than 300times in the case of complexing with TMDGA,thereby opening up a new path to control the oxidation state of Np and supporting the crucial task of Np recovering in spent nuclear fuel reprocessing.
基金support from Natural Science Foundations of Henan Province(Nos.222300420502 and 232300420093)the Program for Science and Technology Innovation Talents in Universities of Henan Province(No.24HASTIT006)the Key Science and Technology Program of Henan Province(No.222102240044)。
文摘Tin-based metal organic complexes with breakable coordination bonds,multiple active sites,and high theoretical capacity have attracted wide attentiorials for lithium-ion batteries(LIBs).However,the inferior electrical conductivity and significant volume changes have limited their electrochemical stability and practical application performance.This work proposes a universal doping strategy for the preparation of tin-phthalic acid complexes(Sn-MOF)doped with metal atoms(Al,Cr,Mn,Fe,Co,Ni,Cu,Zn).Metal atoms are uniformly dispersed within Sn-MOF for enhancing electrical conductivity and accommodating appropriate volume expansion,resulting in improved rate capability and cycling stability.Additionally,compared to a series of doped Sn-MOF,Zn-doped Sn-MOF exhibits the most exceptional electrochemical performance with a high reversible capacity of 1131 mAh·g^(-1)and stable cycling performance at a current density of 0.5 A·g^(-1),delivering a capacity of 1065 mAh·g^(-1)after 500 cycles.Zn-doping catalyzes the lithiation reaction between Sn-MOF and Li^(+),promoting their reaction kinetics during the first cycle.Furthermore,the Zn-doped Sn-MOF is inclined to form a thin and stable solid electrolyte interface film to maintain cyclic stability.
文摘Organoboron compounds have become important intermediates for the construction of new compounds in synthetic chemistry and pharmaceutical chemistry,and it has been found that pinacol biborate(B_(2)pin_(2))as the boron source and Cu^(Ⅱ) organophosphorus complex(L)as the catalyst can effectively realize the hydrogen-reduced borylation products and dehydrohydrated borylation products of aryl olefins.The reaction regioselectivity involvingβ-C positions of aryl olefins can be controlled by regulating the ligand and additive types.The formation mechanism of the product is conducted at LCu^(Ⅰ)Bpin formed from Cu^(Ⅱ),L and B_(2)pin_(2).Subsequently the substrate aryl olefins undergo addition reaction to form the active intermediate PhCH(LCu^(Ⅰ))CH_(2)Bpin.Followed by the metathesis of the active intermediate with water to form hydrogen reduction products,the same active intermediate can be oxidized with 2,2,6,6-tetramethylpiperidoxyl(TEMPO)to form trans dehydrogenation products.
基金Supported by National Natural Science Foundation of China(42472217).
文摘Taking the shale oil of the first member of the Cretaceous Qingshankou Formation of Changling Sag in southern Songliao Basin as an example,this paper establishes a saturation model of lacustrine shale oil considering the influence of organic matter on clay-bound water conductivity.Based on the fluid characterization results of sealed samples and two-dimensional nuclear magnetic resonance,the differential influence of organic matter on clay-bound water conductivity was quantitatively revealed,and the conductivity mechanism and rock-electrical relationships of lacustrine shale were systematically analyzed.The results show that there are two conductive networks for lacustrine shales,i.e.the matrix free water and the clay-bound water.The bound water cementation index msh was introduced to reflect the impact of organic matter on clay-bound water conductivity,and it is positively correlated with the effective porosity.When there is sufficient rigid framework support and well-developed pores,organic matter is more likely to fill or adsorb onto clay interlayers.This reduces the ion exchange capacity of the electrical double layer,leading to an increase in msh and a decrease in the conductivity of clay-bound water.The overall conductivity of shale is controlled by the clay-bound water conductivity,and the relative contributions of the mentioned two conductive networks to formation conductivity are affected by the effective porosity and msh.The larger the effective porosity and msh,the more the contribution of the matrix free water to formation conductivity.According to the experimental results,the proposed saturation model yields a significantly higher interpretation accuracy in oil saturation than the Archie model and the Total-shale model.
基金supported by the National Natural Science Foundation of China(nos.41171198,41403079)the Chongqing Research Program of Basic Research and Frontier Technology(no.cstc2015jcyj A20021)the Fundamental Research Funds for the Central Universities of Ministry of Education of China(no.XDJK2015B035)
文摘The phosphorus（P） fraction distribution and formation mechanism in the supernatant after P adsorption onto iron oxides and iron oxide-humic acid（HA） complexes were analyzed using the ultrafiltration method in this study.With an initial P concentration of 20 mg/L（I =0.01 mol/L and pH = 7）,it was shown that the colloid（1 kDa-0.45 μm） component of P accounted for 10.6%,11.6%,6.5%,and 4.0%of remaining total P concentration in the supernatant after P adsorption onto ferrihydrite（FH）,goethite（GE）,ferrihydrite-humic acid complex（FH-HA）,goethite-humic acid complex（GE-HA）,respectively.The 〈1 kDa component of P was still the predominant fraction in the supernatant,and underestimated colloidal P accounted for 2.2%,55.1%,45.5%,and 38.7%of P adsorption onto the solid surface of FH,FH-HA,GE and GE-HA,respectively.Thus,the colloid P could not be neglected.Notably,it could be interpreted that Fe3＋ hydrolysis from the adsorbents followed by the formation of colloidal hydrous ferric oxide aggregates was the main mechanism for the formation of the colloid P in the supernatant.And colloidal adsorbent particles co-existing in the supernatant were another important reason for it.Additionally,dissolve organic matter dissolved from iron oxide-HA complexes could occupy large adsorption sites of colloidal iron causing less colloid P in the supernatant.Ultimately,we believe that the findings can provide a new way to deeply interpret the geochemical cycling of P,even when considering other contaminants such as organic pollutants,heavy metal ions,and arsenate at the sediment/soil-water interface in the real environment.
文摘Elementary information theory is used to model cybersecurity complexity, where the model assumes that security risk management is a binomial stochastic process. Complexity is shown to increase exponentially with the number of vulnerabilities in combination with security risk management entropy. However, vulnerabilities can be either local or non-local, where the former is confined to networked elements and the latter results from interactions between elements. Furthermore, interactions involve multiple methods of communication, where each method can contain vulnerabilities specific to that method. Importantly, the number of possible interactions scales quadratically with the number of elements in standard network topologies. Minimizing these interactions can significantly reduce the number of vulnerabilities and the accompanying complexity. Two network configurations that yield sub-quadratic and linear scaling relations are presented.
文摘The most simple method for solventless synthesis of supramolecular complex of CMCR·2BPY·BZP, [CMCR = C-methylcalix[4]resorcinarene, BPY = 4,4'-bipyridine, BZP = benzophenone], is proposed. Although CMCR by itself is high melting point compound (above 300°C), CMCR was found to be dissolved in melt mixture of BPY and BZPeven below 120°C. In the mixture of the three components, the reaction occurs to form CMCR·2BPY·BZP supramolecular complex.
文摘A novel Fe/Co metal organic complex nanosheet modified by 1,4-dicarboxybenzene(BDC),i.e.,FeCo@BDC,was prepared,and highly efficient removal performance for trace lead(Ⅱ)(Pb^(2+))was demonstrated in the neutral aqueous solutions.The removal rates were higher than 95%and the adsorption was equilibrated in 15 min.The isotherms and kinetics for the adsorption Pb^(2+)by the FeCo@BDC adsorbents followed Langmuir model and pseudo-second-order model,respectively.The maximum adsorption capacity was 220.48 mg g^(-1).The FeCo@BDC adsorbents also own a prominent regeneration performance.The prominent performance of in the removal of trace Pb^(2+)makes FeCo@BDC an ideal candidate as commercial adsorbent materials.
文摘A novel europium complex, bi(dibenzamide) benzoate europium(Ⅲ) (Eu-DBA-B), was synthesized. The composition and photoluminescence properties of Eu-DBA-B were investigated. The results show that the europium complex is an electroneutral complex, and it emits very strong red luminescence from (()~5D_1→()~7F_j) (j=0, 1, 2, 3, 4) transitions.
文摘The reaction of MeCpLnCl·2LiCl·nTHF with 2 equivalent of LiNPh_2 in THF,hexane and toluene mixture solution gives the new complex[Li(DME)_2][(η~5-MeCp)Ln(NPh_2)_3](Ln=La,Pr,Nd)by extraction with DME.They have been characterized by elemental analysis,IR and NMR.The La complex crystallizes in the monoclinic space group P2_1/c with α=1.8335(6)nm,b=1.6576(5)nm,c=1.7461(6)nm, β=96.04°,V=5.277 nm^2,Z=4,D_c=1.26g·cm^(-3),R=0.057 and R_w=0.048(1≥2.5σ(I_o))for 3378 reflec- tions.The complex consists of a pair of a cation and an anion.La^(3+) is coordinated by one methylcyclopentadienyl and three diphenylamidos to form six-coordinate pseudotetrahedron with the mean Ln-N and La-C(ring)distances of 0.2459(8)and 0.2843(11)nm,respectively.
基金supported by the National Natural Science Foundation of China(No.21271033)
文摘[Pb（HL）（phen）]n （1） and [Cd3L2（phen）]n （2）, where phen = 1,10-phenanthroline and L = 4,4＇-（2-carboxylatopropane-1,3-diyl）dibenzoate, were hydrothermally prepared and fully characterized by X-ray single-crystal diffraction, infrared spectroscopy and thermogravimetric analyses. The decomposition temperature of 1 and 2 was measured to be ca. 304 and 416 ℃, respectively. The charge transfer transition based absorption of 1 and 2 was also verified by the powder scattering spectra and theoretical analyses.
基金supported by the Shenzhen Medical Research Fund(Grant No.A2303049)Guangdong Basic and Applied Basic Research(Grant No.2023A1515010647)+1 种基金National Natural Science Foundation of China(Grant No.22004135)Shenzhen Science and Technology Program(Grant No.RCBS20210706092409020,GXWD20201231165807008,20200824162253002).
文摘Multi-organ-on-a-chip(MOOC)technology represents a pivotal direction in the organ-on-a-chip field,seeking to emulate the complex interactions of multiple human organs in vitro through microfluidic systems.This technology overcomes the limitations of traditional single-organ models,providing a novel platform for investigating complex disease mechanisms and evaluating drug efficacy and toxicity.Although it demonstrates broad application prospects,its development still faces critical bottlenecks,including inadequate physiological coupling between organs,short functional maintenance durations,and limited real-time monitoring capabilities.Contemporary research is advancing along three key directions,including functional coupling,sensor integration,and full-process automation systems,to propel the technology toward enhanced levels of physiological relevance and predictive accuracy.
基金Project supported by National Natural Science Foundation of China(51604128)
文摘To examine the activation of organic acids on the leaching process of ion-adsorption type rare earth ore（IRE-ore）, the leaching behavior of rare earth（RE） and zeta potential of IRE-ore were investigated in the absence and presence of carboxylic acids. The results show that all the tested organic acids（acetic acid,malonic acid, citric acid, tartaric acid, succinic acid, and malic acid） can promote RE extraction. At relatively high concentrations of organic acids, the activation efficiency of organic acids on RE extraction is generally consistent with their complexation ability; whereas at their low concentrations, the change of zeta potential on the IRE-ore surface with organic acid concentration and p H has a close association with RE extraction, which indicates that organic acids can impact the surface electrical property of IREore via their adsorption/desorption, and thereby increase/decrease the affinity of RE ions to IRE-ore.Therefore the influence of organic acids on the IRE-ore surface electrical property also plays an important role in RE extraction in addition to their complexation with RE ions.
文摘This paper presents the results of the search of biologically active uranium compounds such as amino acids. We first received and examined X-ray and IR （infrared radiation） spectroscopy of uranium complexes with α- and β-amino acids in aqueous and organic solution. We proposed a method for direct synthesis of complex organic compounds of uranium chloride UO2Cl2 with α- andβ-amino acids for the synthesis of drugs for the treatment of cancer.
