The copper based catalysts, CuO/T-Al2O3, CuO/y-Al2O3-cordierite （Cord） and CuO/Cord, were prepared by impregnation method. The catalytic activity of the catalysts was tested in absence and presence of water vapor,an...The copper based catalysts, CuO/T-Al2O3, CuO/y-Al2O3-cordierite （Cord） and CuO/Cord, were prepared by impregnation method. The catalytic activity of the catalysts was tested in absence and presence of water vapor,and the catalysts were characterized. Temperature program desorption （TPD） experiments or toluene and water on the catalysts were carried out. The influence of water vapor on the activity of the catalysts was discussed. Results showed that addition of the water vapor has a significant negative effect on the catalytic activity of the catalysts.The higher the concentration of the Water vapor in feed steam was, the lower the catalytic activity of the copper based catalysts became, which could be mainly ascribed to the competition of water molecules with toluene molecules for adsorption on the catalyst surfaces. TPD experiments showed that the strength of the interaction between water molecules and three catalysts followed the order： CuO/γ-Al2O3〉CuO/γ-Al2O3-Cord〉CuO/Cord. As a consequence of that, the degree of degradation in the catalytic activity of these three catalysts by the water vapor followed the order： CuO/γ-Al2O3〉CuO/y-Al2O3-Cord〉CuO/Cord. However, the negative effect of the water vapor was reversible.展开更多
The catalytic activity for the synthesis of methanol from carbon dioxide and hydrogen was measured on various binary and ternary catalysts containing copper oxide under a pressure of 10 atm. Among these samples the ca...The catalytic activity for the synthesis of methanol from carbon dioxide and hydrogen was measured on various binary and ternary catalysts containing copper oxide under a pressure of 10 atm. Among these samples the catalysts, CuO/ZnO/γ-Al_2O_3, demonstrated the highest activity and selectivity to methanol; MnO, as third component, had no promotional effect on the activity of meth- anol formation. Based on a simple power rate law the apparent activation energy estimation and par- tial pressure dependence measurement were accomplished over eight catalysts. The activation energies varied from 40 to 120 kJ / mol depending on the composition of catalysts. The rates of methanol for- mation to be 0.3 -- 0.9 order in H_2 and about 0.1 -- 0.2 order in CO_2 were reported.展开更多
Effects of nickel component,thiourea,glue and chloride ions and their interactions on the passivation of copper–nickel based alloy scrap anodes were investigated by combining conventional electrochemical techniques.R...Effects of nickel component,thiourea,glue and chloride ions and their interactions on the passivation of copper–nickel based alloy scrap anodes were investigated by combining conventional electrochemical techniques.Results obtained from chronopotentiometry and linear voltammetry curves showed that the Ni component made electrochemical stability of the anode strong and difficult to be corroded,caused by the adsorption of generated Cu2O,NiO or copper powder to the anode surface.The Ni2+reducing Cu2+to Cu+or copper powder aggravated the anode passivation.In a certain range of the glue concentration≤8×10–6 or thiourea concentration≤4×10–6,the increase of glue or thiourea concentration increases the anode passivation time.Over this range,glue and thiourea played an adverse effect.The increase of chloride ions concentration led to the increase in passivation time.展开更多
Electrotherapy (ET) effectively ablates solid tumors,inhibiting their growth.However,poor electrical conductivity limits ET efficacy for tumors.Herein,we have developed a novel copper-based inorganic nanozyme that enh...Electrotherapy (ET) effectively ablates solid tumors,inhibiting their growth.However,poor electrical conductivity limits ET efficacy for tumors.Herein,we have developed a novel copper-based inorganic nanozyme that enhances the electrical ablation of tumors.Our approach involves liposome-encapsulated copper oxide (CuO) embedded with potassium chloride nanoclusters (LCuPC).When LCuPCs enter cancer cells,they quickly dissolve due to the weakly acidic tumor microenvironment,releasing an abundance of salt ions,including Cu^(2+),K^(+),and Cl^(-).The release of salt ions significantly improves the tumor electroconductivity,thereby enhancing the ET efficiency for tumors.Furthermore,these salt ions also upregulate the expression of cleaved caspase-1 and GSDMD,activating the pyroptosis of cancer cells.Additionally,the released Cu^(2+) ions catalyze the conversion of cellular overexpressed H_(2)O_(2) into highly toxic ˙OH through a Fenton-like reaction.This process causes damage to the mitochondria,leading to the induction of apoptosis and ferroptosis in cancer cells.Moreover,the electrical stimulation transforms chloride ions into hypochlorite radicals,further enhancing the oxidative stress levels in cancer cells and promoting ROS-mediated cancer cell death.In an in vivo experiment,we demonstrated that LCuPC dramatically inhibit tumor growth through the pathways of pyroptosis,ferroptosis,and apoptosis.This innovative strategy provides a promising approach for enhancing ET efficiency for tumors.展开更多
Crystallization of[CuI(CNXyl)_(3)](1)with I_(2)(exhibiting strong halogen bond donor properties),at different molar ratios between the reactants,resulted in a series of(XylNC)Cu^(Ⅰ) crystal polyiodides formed along w...Crystallization of[CuI(CNXyl)_(3)](1)with I_(2)(exhibiting strong halogen bond donor properties),at different molar ratios between the reactants,resulted in a series of(XylNC)Cu^(Ⅰ) crystal polyiodides formed along with gradual accumulation of iodine,namely[Cu(I_(3))(CNXyl)_(3)](two crystalline polymorphs 2^(Ⅰ) and 2^(Ⅱ)),[Cu(I_(3))(CNXyl)_(3)]·1/2I_(2)(2·1/2 I_(2))and[Cu(CNXyl)_(3)](I_(5))(3);all these compounds were studied by X-ray diffractometry.Molecular electrostatic potential(MEP)surface plots were also calculated using density functional theory(DFT)for isolated molecules of 2 and I_(2),showing electrophilic and nucleophilic sites.Halogen bonding in 2·1/2 I_(2) was additionally elucidated for both crystal and cluster models,including combined quantum theory of atoms-in-molecules(QTAIM)and one-electron potential(OEP)projections.For model clusters,DFT energetic analysis,quantum theory of atoms-in-molecules,combined with the noncovalent interaction index plot(QTAIM/NCIplot),natural bond orbital(NBO)donor–acceptor charge transfer analysis,and Wiberg bond index(WBI)analysis were used.In the structure of 2·1/2I_(2),the presence of an I_(2)…I_(3)_(−)halogen bonded linkage gives a key toward the understanding of the precise mechanism for the generation of I_(5)^(−)(and then I_(8)^(2−))ligands from I_(2) and metal-coordinated I_(3)_(−).展开更多
Purifying ethylene from an acetylene/ethylene mixture is feasible but challenging because of their similar physical properties.Herein,we synthesized a copper-based metal–organic framework(MOF),namely complex 1,that c...Purifying ethylene from an acetylene/ethylene mixture is feasible but challenging because of their similar physical properties.Herein,we synthesized a copper-based metal–organic framework(MOF),namely complex 1,that can preferentially adsorb more C_(2)H_(2) than C_(2)H_(4).Breakthrough experiments show that complex 1 can purify the acetylene/ethylene mixture into high-purity ethylene(99.99%)and the productivity is 0.48 mmol g^(−1).This work shows that a suitable pore environment will greatly enhance the host–vip interaction,to realize the separation of a similar mixture.展开更多
Luminescent Cu-doped semiconductor nanocrystals have long played a pivotal role in the advancement of lighting and display technologies.The luminescence observed in colloidal copper-based I-III-VI nanocrystals is attr...Luminescent Cu-doped semiconductor nanocrystals have long played a pivotal role in the advancement of lighting and display technologies.The luminescence observed in colloidal copper-based I-III-VI nanocrystals is attributed to defect emission arising from donor-acceptor pair recombination of excited charge carriers.However,a detailed atomic-level exploration of how distinct chemical components precisely influence the defect position has remained challenging,primarily due to inherent local structural imprecision of the traditional Ⅰ-Ⅲ-Ⅵ nanocrystals.In this study,we have prepared a set of copper-containing Ⅰ-Ⅲ-Ⅵ metal chalcogenide nanoclusters,1-CuInS,1-CuGaS,and 2-CuGaS,serving as unique models to address the aforementioned issues.Interestingly,despite possessing an identical crystalline structure,1-CuInS and 1-CuGaS exhibit significantly different photoluminescence behaviors.For comparsion,1-CuGaS and 2-CuGaS,which share the same second building units but differ in structural configuration,demonstrate similar luminescence performance.More importantly,we found that the green emission observed in 1-CuInS likely stems from the radiative recombination of electrons migrating from shallow delocalized traps to copper-localized holes.In contrast,the red emission observed in both 1-CuGaS and 2-CuGaS is presumably due to the recombination of electrons originating from deeply localized traps with copper-localized holes.This disparity in trap sites appears to be highly dependent on the presence of trivalent metal ions(In^(3+)and Ga^(3+))within the clusters,and the hypothesis is further substantiated through photoluminescence characterization of 1-CuInGaS containing both In^(3+)and Ga^(3+)ions simultaneously.Furthermore,we have explored the impact of introducing Cd ions into 1-CuInS,which can alter the position of shallow delocalized traps and thereby fine-tune the luminescence properties.Our findings shed light on the intricate interplay of chemical composition and defect states in coppercontaining Ⅰ-Ⅲ-Ⅵ nanoclusters,offering valuable insights into the optoelectronic properties of copperbased semiconductor nanocrystals.展开更多
Copper base alloy was overlaid onto 35CrMnSiA steel plate by tungsten inert gas （TIG） welding method. The heat transfer process was simulated, the microstructures of the copper base overlay were analyzed by scanning...Copper base alloy was overlaid onto 35CrMnSiA steel plate by tungsten inert gas （TIG） welding method. The heat transfer process was simulated, the microstructures of the copper base overlay were analyzed by scanning electron microscopy （SEM） and energy dispersive spectrometer （EDS）, and the friction and abrasion properties of the overlay were measured. The results show that the Fe content increases in the overlay with increasing the welding current. And with the increase of Fe content in the overlay, the friction coefficient increases and the wear mechanism changes from oxidation wear to abrasive wear and plough wear, which is related to the size and quantity of Fe grains in the overlay. While with the increase of Fe content in the overlay, the protection of oxidation layer against the oxidation wear on the melted metal decreases.展开更多
A copper（Ⅱ） complex [LCu2Cl4]n was synthesized by a new bis-Schiff base ligand containing quinoline unit, 1,4-bis[2-（4-fluorophenyl）iminomethyl-8-quinolinoxy]butane（L）. X-ray crystal structure shows that it is ...A copper（Ⅱ） complex [LCu2Cl4]n was synthesized by a new bis-Schiff base ligand containing quinoline unit, 1,4-bis[2-（4-fluorophenyl）iminomethyl-8-quinolinoxy]butane（L）. X-ray crystal structure shows that it is a binuclear complex, and the crystal belongs to the triclinic system, space group P1, with a = 9.387（2）, b = 9.968（2）, c = 10.291（2） ？, α = 87.532（3）, β = 63.762（2）, γ = 86.628（3）o, V = 862.1（3） ？^3, Z = 1, Dc = 1.640 Mg/m^3, F（000） = 428, R = 0.0416 and wR = 0.1141. Each Cu（Ⅱ） metal ion coordinates with a quinoline N atom, an imine N atom, an ether oxygen atom and three chlorides, forming a distorted six-coordinated octahedronal structure. Each copper（Ⅱ） complexation unit links with one of the adjacent ligand copper complexation units through the chlorido bridging groups, thus generating an infinite one-dimensional chain structure. Such 1D chains further construct a 2D network structure by π-π stacking interactions.展开更多
A new chain-like coordination polymer, namely, [CuL]n （1, Na2L = 2-[（2-hydroxy- benzylidene）-amino]-benzenesulfonic acid sodium salt）, has been synthesized and characterized by single-crystal X-ray diffraction, IR...A new chain-like coordination polymer, namely, [CuL]n （1, Na2L = 2-[（2-hydroxy- benzylidene）-amino]-benzenesulfonic acid sodium salt）, has been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy and elemental analysis. Complex 1 crystallizes in monoclinic system, space group P21/c with a = 9.2296（16）, b = 10.4754（18）, c = 12.200（2） A, β = 102.392（2）°, V = 1152.0（3）A3, CI3H9CuNOaN, Mr = 338.83, Dc = 1.953 g/cm3, Z = 4, F（000） = 684, p = 2.089 mm-1, the final R = 0.0376 and wR = 0.0956. X-ray diffraction analyses indicate that 1 displays a square-pyramidal metal center with NO4 donor sets. The sulfonate-derived Schiff base serves as a common N,O,O＇-tridentate and a unique O-bridged ligand connecting the metals. Dinuclear copper complexes serve as secondary building blocks （SBUs） to construct an unusual 2D coordination network. In the crystal, the components form a stable 3D supramolecular architecture by C-H...O interactions and to-stacking展开更多
A calculation formula of ln γ i 0 for solute element i in liquid alloys was derived by use of free volume theory and Miedema formation enthalpy model. The values of ln γ i 0 of solute elements in liqui...A calculation formula of ln γ i 0 for solute element i in liquid alloys was derived by use of free volume theory and Miedema formation enthalpy model. The values of ln γ i 0 of solute elements in liquid copper at 1273 K were obtained. The results obtained show that the coincidence rate of sign (positive or negative) was 90% for the calculated and experimental values, which were basically in the same magnitude.展开更多
The copper complex Cu（C12H9N2O3）2 has been synthesized by the reaction of furaldehyde salicylylhydrazone （Hfs） and copper acetylacetonate and characterized by X-ray crystal diffraction and spectroscopic studies. T...The copper complex Cu（C12H9N2O3）2 has been synthesized by the reaction of furaldehyde salicylylhydrazone （Hfs） and copper acetylacetonate and characterized by X-ray crystal diffraction and spectroscopic studies. The crystal crystallizes in space group P211n with a = 5.9765（3）, b = 15.7196（9）, c = 12.0514（6）A,β= 101.618（3）^o, V = 1109.0（1）A^3, C24H18CuN4O6, Mr = 521.96, Z = 2, Dc = 1.563 g/cm^3, μ = 1.035 mm^-1, F（000） = 534, R = 0.0373 and wR = 0.1058 for 2283 observed reflections （I 〉 2σ（I））. The copper atom has a square-planar CuN2O2 coordination and should be in an octahedral coordination if considering Cu-O （phenol） with distances of 2.796（2）A as weak bonds. The neighboring copper complex molecules are linked together by these weak Cu-O （phenol） bonds, resulting in an extended 1D chain. The title compound exhibits paramagnetic property and fluorescence behavior at room temperature supported by the EPR and fluorescence spectra.展开更多
A new Schiff base (LK) obtained from 2, 4, -dihydroxybenzaldehyde and glycly-DL- phenylalanine reacted with Cu(II), Zn(II), Ni(II) and Co(II) to yield new complexes. The complexes were characterized by elemental an...A new Schiff base (LK) obtained from 2, 4, -dihydroxybenzaldehyde and glycly-DL- phenylalanine reacted with Cu(II), Zn(II), Ni(II) and Co(II) to yield new complexes. The complexes were characterized by elemental analyses, molar conductance, 1H NMR DTA, TG, IR and UV spectroscopy. In these complexes the ligand is coordinated to the metal through its phenolic oxygen, carboxyl oxygen, imino nitrogen and amide nitrogen. All complexes are non-electrolytes and four coordinated with 1:1(metal; ligand) stoichiometry. The probable structure of the complexes is suggested展开更多
Two new Cu（Ⅱ） complexes have been synthesized with two different bidentate N2O2 donor Schiffbase ligands HL1 （2-（（E）-（4-chlorophenylimino）methyl）-6-bromo-4-chlorophenol） and HL2 （2-（（E）-（2-chlorophenyl...Two new Cu（Ⅱ） complexes have been synthesized with two different bidentate N2O2 donor Schiffbase ligands HL1 （2-（（E）-（4-chlorophenylimino）methyl）-6-bromo-4-chlorophenol） and HL2 （2-（（E）-（2-chlorophenylimino）methyl）-6-bromo-4-chlorophenol）, respectively. Both complexes 1 and 2 have been characterized by elemental analysis and single-crystal X-ray diffraction studies. Structural studies reveal that in both complexes the metal centers are four-coordinated with N202 donor set of Schiff base ligands. Complex 1 belongs to the tetragonal system, space group P4（3）2（1）2 with a = 10.2379（2）, b = 10.2379（2）, c = 24.9623（90） A, V = 2616.41（12） A^3, Z = 4, Dc = 1.908 g/cm^3,μ（MoKa） = 4.3327 mm^-1, F（000） = 1468, S = 0.999, the final R = 0.0345 and wR = 0.0835 for 3506 unique reflections （Rint= 0.0428） with 3249 observed ones （I 〉 2σ（I））. Complex 2 is of monoclinic system, space group P21/c with a = 11.064（3）, b = 9.437（2）, c = 13.277（4） A, fl = 108.997（3）°, V = 1310.8（6） A^3, Z = 2, Dc= 1.904 g/cm^3,μ（MoKa） = 4.319 mm^-1, F（000） = 734, S = 0.997, the final R = 0.0282 and wR = 0.0619 for 3491 unique reflections （Rint = 0.0428） with 2777 observed ones （I 〉 20（I））. The units of the complex are linked via weak interactions, such as C-H…Br hydrogen bonds together with Cl…C1 and Cu…Cl interactions, leading to the formation of one-dimensional chain and two-dimensional network and stabilizing the crystal structure.展开更多
To systematically study the effect of Lewis acid sites(LASs)and Lewis base sites(LBSs)in MOF materials for the CO_(2)cycloaddition reaction,four isomorphous copper polyhedron-based MOFs(Cu-PMOFs),JLU-Liu20,JLU-Liu21,J...To systematically study the effect of Lewis acid sites(LASs)and Lewis base sites(LBSs)in MOF materials for the CO_(2)cycloaddition reaction,four isomorphous copper polyhedron-based MOFs(Cu-PMOFs),JLU-Liu20,JLU-Liu21,JLU-Liu22 and JLU-Liu46 with different amounts of LASs and LBSs were selected to investigate their CO_(2)fixation catalytic performance.It is commendable that the catalytic capabilities of the four Cu-PMOFs exceed that of most reported MOF-based catalysts.展开更多
It is highly desirable yet challenging to incorporate open micropores with mass transportation and open active metal sites into metal-organic frameworks(MOFs)for developing novel highly efficient catalysts.Herein,we r...It is highly desirable yet challenging to incorporate open micropores with mass transportation and open active metal sites into metal-organic frameworks(MOFs)for developing novel highly efficient catalysts.Herein,we report a catalyst of low-nuclearity copper-cluster-based micropore MOF,namely H-1e,incor-porated with unsaturated Cu(Ⅱ)centres as open active sites obtained via a highly efficient electrochemical synthesis within 20 minutes.The catalyst H-1e shows potential porosity with 1D open functionalized hexagonal channels for size-selective air oxidation as well as high stability.The electrochemically pre-pared H-1e exhibits excellent catalytic aerobic oxidation activity for the conversion of alcohols(mini-size)to aldehydes with over 99%selectivity and 99%yield under air conditions,showing excellent reusability and stability.The selective catalytic performances are found to be closely dependent on the suitable aperture size of the 1D channels in H-1e,which provided better beds for the oxidation transformations(confirmed by the computational DFT study).In this study,it offers a simple and potential strategy to con-struct microporous materials with open active metal sites to promote the catalytic efficiency of MOFs by electrochemical synthesis.展开更多
Two novel porous MOFs,[Cu_(2)Cl(TZI)(H_(2)O)_(3)]·4DMA(compound 1)and[Cu_(2)(TZI)(OH)(DMF)]·DMF·H_(2)O(compound 2)(H_(3)TZI=5-(tetrazol-5-yl)isophthalic acid,DMA=N,N-dimethylacetamide,and DMF=N,N-dimeth...Two novel porous MOFs,[Cu_(2)Cl(TZI)(H_(2)O)_(3)]·4DMA(compound 1)and[Cu_(2)(TZI)(OH)(DMF)]·DMF·H_(2)O(compound 2)(H_(3)TZI=5-(tetrazol-5-yl)isophthalic acid,DMA=N,N-dimethylacetamide,and DMF=N,N-dimethylformamide),have been successfully synthesized using the same ligand consisting of isophthalate and tetrazolate groups and CuCl_(2)·2H_(2)O through the secondary building unit(SBU)strategy.Both compounds are constructed from copper cluster-based SBUs.Compound 1 is made up of two different cages based on a Cu paddlewheel and rare-reported double-crown like hexanuclear Cu cluster.In this SBU,the Cu atom adopts a five-coordination in a trigonal bipyramidal configuration,which is very rare in reported MOFs.Moreover,compound 1 with dual functionalities of open metal sites(OMSs)and N-rich Lewis basic sites(LBSs)exhibits good CO_(2) adsorption(92 cm^(3) g^(-1) at 273 K)and high-effect separation ability(9.6 for CO_(2)/CH_(4)=0.5/0.5 under 1 bar at 298 K).展开更多
Nitrogen is essential for life and ecosystems.The nitrogen cycle is fundamental to all life on earth and has been implicated in his-torical mass extinction events,where disruptions to its stability have played a criti...Nitrogen is essential for life and ecosystems.The nitrogen cycle is fundamental to all life on earth and has been implicated in his-torical mass extinction events,where disruptions to its stability have played a critical role[1].Moreover,the nitrogen cycle's response to climate change could critically influence atmo-spheric CO_(2) levels and the trajectory of global warming[2].However,improper management of anthropogenic nitrogen-containing wastewater,including domestic sewage,agricultural runoff,and industrial effluents,has pushed the nitrogen cycle to the brink of imbalance[1].展开更多
Many regions across the globe are grappling with water scarcity issues,prompting the exploration of innovative water harvesting techniques.While the development of high-performance water harvesting materials has been ...Many regions across the globe are grappling with water scarcity issues,prompting the exploration of innovative water harvesting techniques.While the development of high-performance water harvesting materials has been widely documented,these technologies often rely on a singular source with limited efficiency.This study presents a dual-functional copper Janus system that facilitates continuous freshwater harvesting by integrating seawater desalination powered by solar energy during daylight hours and fog collection during night and morning time.The Janus system consists of a copper sheet and copper foam substrate,featuring superhydrophilic pores arranged on the superhydrophobic surface,as well as superhydrophilic flake-like structures made of soot-carbon particles,which are deposited on the framework of the copper foam.The fog collection rate of this system has been measured at 210.65 kg m^(−2) h^(−1),while the solar-driven evaporation rate of seawater under 1-sun conditions is reported at 1.44 kg m^(−2) h^(−1).The fog collection and evaporation efficiency have been enhanced by 28.72% and 183.27%,respectively.Furthermore,the system demonstrates strong and consistent performance even after repeated use,ensuring sustained water collection over prolonged periods.Therefore,this study presents a promising avenue for water collection technologies and offers valuable insights for the advancement of sustainable freshwater production methods.展开更多
Herein,by using pillaring ligands with different lengths,two copper-based metal–organic frameworks,compounds 1 (Cu_(2)(bada)_(2)(dabco)) and 2 (Cu_(2)(bada)_(2)(bipy)) (bada=4,4′-carbonylbis(azanediyl)dibenzoic acid...Herein,by using pillaring ligands with different lengths,two copper-based metal–organic frameworks,compounds 1 (Cu_(2)(bada)_(2)(dabco)) and 2 (Cu_(2)(bada)_(2)(bipy)) (bada=4,4′-carbonylbis(azanediyl)dibenzoic acid,dabco=1,4-diazabicyclo[2.2.2]octane,bipy=4,4′-bipyridine) with the urea-functionalized ligand bada,have been successfully synthesized using a pillared-layer strategy.Both 1 and 2 exhibit two-dimensional square lattice (sql) layers pillared by dabco and bipy,respectively,and feature pcu topology.Different to dabco in 1,the pillaring ligand 4,4′-bipyridine with longer length forms a doubly interpenetrated structure of 2.Both compounds display good thermal stabilities and permanent porosities.1 exhibits good performance for CO_(2)(32 cm^(3) g^(-1)),C_(2)H_(6) (58 cm^(3) g^(-1)),and C_(3)H_(8) (105 cm^(3) g^(-1)) capture among MOFs without open metal sites.In particular,1 possesses high Q_st for CO_(2)(32.8 kJ mol^(-1)),C_(2)H_(6) (37.2 kJ mol^(-1)),and C_(3)H_(8) (40.3 kJ mol^(-1)) adsorption and outstanding selectivities for CO_(2)(5.7),C_(2)H_(6) (28),and C_(3)H_(8) (224) over CH_(4) at 298 K.Density functional theory (DFT)-based calculations further prove the hydrogen-bond interactions and σ–π interactions between gas molecules and urea-based ligands.2 exhibits a gate-opening behavior for N_(2),Ar and CO_(2).Compound 1 could be seen as a significant potential material for gas storage and separation.展开更多
基金Supported by the National-Natural Science Foundation of China （20936001）, the Natural Science Foundation of Guangdong Province, and the State Key Lab of Subtropical Building Science, South China University of Technology （x2yj C709028Z）.
文摘The copper based catalysts, CuO/T-Al2O3, CuO/y-Al2O3-cordierite （Cord） and CuO/Cord, were prepared by impregnation method. The catalytic activity of the catalysts was tested in absence and presence of water vapor,and the catalysts were characterized. Temperature program desorption （TPD） experiments or toluene and water on the catalysts were carried out. The influence of water vapor on the activity of the catalysts was discussed. Results showed that addition of the water vapor has a significant negative effect on the catalytic activity of the catalysts.The higher the concentration of the Water vapor in feed steam was, the lower the catalytic activity of the copper based catalysts became, which could be mainly ascribed to the competition of water molecules with toluene molecules for adsorption on the catalyst surfaces. TPD experiments showed that the strength of the interaction between water molecules and three catalysts followed the order： CuO/γ-Al2O3〉CuO/γ-Al2O3-Cord〉CuO/Cord. As a consequence of that, the degree of degradation in the catalytic activity of these three catalysts by the water vapor followed the order： CuO/γ-Al2O3〉CuO/y-Al2O3-Cord〉CuO/Cord. However, the negative effect of the water vapor was reversible.
基金Work financially supported by the National Natural Science Foundation of China.
文摘The catalytic activity for the synthesis of methanol from carbon dioxide and hydrogen was measured on various binary and ternary catalysts containing copper oxide under a pressure of 10 atm. Among these samples the catalysts, CuO/ZnO/γ-Al_2O_3, demonstrated the highest activity and selectivity to methanol; MnO, as third component, had no promotional effect on the activity of meth- anol formation. Based on a simple power rate law the apparent activation energy estimation and par- tial pressure dependence measurement were accomplished over eight catalysts. The activation energies varied from 40 to 120 kJ / mol depending on the composition of catalysts. The rates of methanol for- mation to be 0.3 -- 0.9 order in H_2 and about 0.1 -- 0.2 order in CO_2 were reported.
基金Project(51574135)supported by the National Natural Science Foundation of ChinaProject(KKPT201563022)supported by the Collaborative Innovation Center of Kunming University of Science and Technology,China
文摘Effects of nickel component,thiourea,glue and chloride ions and their interactions on the passivation of copper–nickel based alloy scrap anodes were investigated by combining conventional electrochemical techniques.Results obtained from chronopotentiometry and linear voltammetry curves showed that the Ni component made electrochemical stability of the anode strong and difficult to be corroded,caused by the adsorption of generated Cu2O,NiO or copper powder to the anode surface.The Ni2+reducing Cu2+to Cu+or copper powder aggravated the anode passivation.In a certain range of the glue concentration≤8×10–6 or thiourea concentration≤4×10–6,the increase of glue or thiourea concentration increases the anode passivation time.Over this range,glue and thiourea played an adverse effect.The increase of chloride ions concentration led to the increase in passivation time.
基金supported by the Key R&D Program of Shandong Province,China(No.2023CXPT012)the National Natural Science Foundation of China(No.22007006)+2 种基金the Taishan Scholars Construction Engineering(No.tsqn201909144)the Natural Science Foundation of Shandong Province(No.ZR2020QB102 and ZR2021QH315)the School Foundation of Anhui Medical University(No.2020xkj022).
文摘Electrotherapy (ET) effectively ablates solid tumors,inhibiting their growth.However,poor electrical conductivity limits ET efficacy for tumors.Herein,we have developed a novel copper-based inorganic nanozyme that enhances the electrical ablation of tumors.Our approach involves liposome-encapsulated copper oxide (CuO) embedded with potassium chloride nanoclusters (LCuPC).When LCuPCs enter cancer cells,they quickly dissolve due to the weakly acidic tumor microenvironment,releasing an abundance of salt ions,including Cu^(2+),K^(+),and Cl^(-).The release of salt ions significantly improves the tumor electroconductivity,thereby enhancing the ET efficiency for tumors.Furthermore,these salt ions also upregulate the expression of cleaved caspase-1 and GSDMD,activating the pyroptosis of cancer cells.Additionally,the released Cu^(2+) ions catalyze the conversion of cellular overexpressed H_(2)O_(2) into highly toxic ˙OH through a Fenton-like reaction.This process causes damage to the mitochondria,leading to the induction of apoptosis and ferroptosis in cancer cells.Moreover,the electrical stimulation transforms chloride ions into hypochlorite radicals,further enhancing the oxidative stress levels in cancer cells and promoting ROS-mediated cancer cell death.In an in vivo experiment,we demonstrated that LCuPC dramatically inhibit tumor growth through the pathways of pyroptosis,ferroptosis,and apoptosis.This innovative strategy provides a promising approach for enhancing ET efficiency for tumors.
基金supported by the Russian Science Foundation projects 22-13-00078(experimental part and XRD analysis)22-73-00021(theoretical calculations under periodic conditions and for cluster mode)The QTAIM/NCIPlot calculations were funded by the MICIU/AEI of Spain(project PID2020-115637GB-I00 FEDER funds)。
文摘Crystallization of[CuI(CNXyl)_(3)](1)with I_(2)(exhibiting strong halogen bond donor properties),at different molar ratios between the reactants,resulted in a series of(XylNC)Cu^(Ⅰ) crystal polyiodides formed along with gradual accumulation of iodine,namely[Cu(I_(3))(CNXyl)_(3)](two crystalline polymorphs 2^(Ⅰ) and 2^(Ⅱ)),[Cu(I_(3))(CNXyl)_(3)]·1/2I_(2)(2·1/2 I_(2))and[Cu(CNXyl)_(3)](I_(5))(3);all these compounds were studied by X-ray diffractometry.Molecular electrostatic potential(MEP)surface plots were also calculated using density functional theory(DFT)for isolated molecules of 2 and I_(2),showing electrophilic and nucleophilic sites.Halogen bonding in 2·1/2 I_(2) was additionally elucidated for both crystal and cluster models,including combined quantum theory of atoms-in-molecules(QTAIM)and one-electron potential(OEP)projections.For model clusters,DFT energetic analysis,quantum theory of atoms-in-molecules,combined with the noncovalent interaction index plot(QTAIM/NCIplot),natural bond orbital(NBO)donor–acceptor charge transfer analysis,and Wiberg bond index(WBI)analysis were used.In the structure of 2·1/2I_(2),the presence of an I_(2)…I_(3)_(−)halogen bonded linkage gives a key toward the understanding of the precise mechanism for the generation of I_(5)^(−)(and then I_(8)^(2−))ligands from I_(2) and metal-coordinated I_(3)_(−).
基金financially supported by the Shandong Provincial Key Research and Development Program(Project No.2020CXGC010403&No.2019JZZY010513)the Key Projects of New and Old Kinetic Energy Conversion under Grant(Project No.[2020]1220).
文摘Purifying ethylene from an acetylene/ethylene mixture is feasible but challenging because of their similar physical properties.Herein,we synthesized a copper-based metal–organic framework(MOF),namely complex 1,that can preferentially adsorb more C_(2)H_(2) than C_(2)H_(4).Breakthrough experiments show that complex 1 can purify the acetylene/ethylene mixture into high-purity ethylene(99.99%)and the productivity is 0.48 mmol g^(−1).This work shows that a suitable pore environment will greatly enhance the host–vip interaction,to realize the separation of a similar mixture.
基金National Natural Science Foundation of China(22071165,92261205,22201103,and U22A20432)the 111 Project(D20015).
文摘Luminescent Cu-doped semiconductor nanocrystals have long played a pivotal role in the advancement of lighting and display technologies.The luminescence observed in colloidal copper-based I-III-VI nanocrystals is attributed to defect emission arising from donor-acceptor pair recombination of excited charge carriers.However,a detailed atomic-level exploration of how distinct chemical components precisely influence the defect position has remained challenging,primarily due to inherent local structural imprecision of the traditional Ⅰ-Ⅲ-Ⅵ nanocrystals.In this study,we have prepared a set of copper-containing Ⅰ-Ⅲ-Ⅵ metal chalcogenide nanoclusters,1-CuInS,1-CuGaS,and 2-CuGaS,serving as unique models to address the aforementioned issues.Interestingly,despite possessing an identical crystalline structure,1-CuInS and 1-CuGaS exhibit significantly different photoluminescence behaviors.For comparsion,1-CuGaS and 2-CuGaS,which share the same second building units but differ in structural configuration,demonstrate similar luminescence performance.More importantly,we found that the green emission observed in 1-CuInS likely stems from the radiative recombination of electrons migrating from shallow delocalized traps to copper-localized holes.In contrast,the red emission observed in both 1-CuGaS and 2-CuGaS is presumably due to the recombination of electrons originating from deeply localized traps with copper-localized holes.This disparity in trap sites appears to be highly dependent on the presence of trivalent metal ions(In^(3+)and Ga^(3+))within the clusters,and the hypothesis is further substantiated through photoluminescence characterization of 1-CuInGaS containing both In^(3+)and Ga^(3+)ions simultaneously.Furthermore,we have explored the impact of introducing Cd ions into 1-CuInS,which can alter the position of shallow delocalized traps and thereby fine-tune the luminescence properties.Our findings shed light on the intricate interplay of chemical composition and defect states in coppercontaining Ⅰ-Ⅲ-Ⅵ nanoclusters,offering valuable insights into the optoelectronic properties of copperbased semiconductor nanocrystals.
文摘Copper base alloy was overlaid onto 35CrMnSiA steel plate by tungsten inert gas （TIG） welding method. The heat transfer process was simulated, the microstructures of the copper base overlay were analyzed by scanning electron microscopy （SEM） and energy dispersive spectrometer （EDS）, and the friction and abrasion properties of the overlay were measured. The results show that the Fe content increases in the overlay with increasing the welding current. And with the increase of Fe content in the overlay, the friction coefficient increases and the wear mechanism changes from oxidation wear to abrasive wear and plough wear, which is related to the size and quantity of Fe grains in the overlay. While with the increase of Fe content in the overlay, the protection of oxidation layer against the oxidation wear on the melted metal decreases.
文摘A copper（Ⅱ） complex [LCu2Cl4]n was synthesized by a new bis-Schiff base ligand containing quinoline unit, 1,4-bis[2-（4-fluorophenyl）iminomethyl-8-quinolinoxy]butane（L）. X-ray crystal structure shows that it is a binuclear complex, and the crystal belongs to the triclinic system, space group P1, with a = 9.387（2）, b = 9.968（2）, c = 10.291（2） ？, α = 87.532（3）, β = 63.762（2）, γ = 86.628（3）o, V = 862.1（3） ？^3, Z = 1, Dc = 1.640 Mg/m^3, F（000） = 428, R = 0.0416 and wR = 0.1141. Each Cu（Ⅱ） metal ion coordinates with a quinoline N atom, an imine N atom, an ether oxygen atom and three chlorides, forming a distorted six-coordinated octahedronal structure. Each copper（Ⅱ） complexation unit links with one of the adjacent ligand copper complexation units through the chlorido bridging groups, thus generating an infinite one-dimensional chain structure. Such 1D chains further construct a 2D network structure by π-π stacking interactions.
基金Supported by Guangxi Provincial Department of Education(No.YB2014333)the Scientific research and technological development project of Guilin(No.20110330)+2 种基金the Project of Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources(Guangxi Normal University)Ministry of Education of China(CMEMR2011-13)Key Subjects of Universities in Guangxi Province Applied Chemistry(2007<20>)
文摘A new chain-like coordination polymer, namely, [CuL]n （1, Na2L = 2-[（2-hydroxy- benzylidene）-amino]-benzenesulfonic acid sodium salt）, has been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy and elemental analysis. Complex 1 crystallizes in monoclinic system, space group P21/c with a = 9.2296（16）, b = 10.4754（18）, c = 12.200（2） A, β = 102.392（2）°, V = 1152.0（3）A3, CI3H9CuNOaN, Mr = 338.83, Dc = 1.953 g/cm3, Z = 4, F（000） = 684, p = 2.089 mm-1, the final R = 0.0376 and wR = 0.0956. X-ray diffraction analyses indicate that 1 displays a square-pyramidal metal center with NO4 donor sets. The sulfonate-derived Schiff base serves as a common N,O,O＇-tridentate and a unique O-bridged ligand connecting the metals. Dinuclear copper complexes serve as secondary building blocks （SBUs） to construct an unusual 2D coordination network. In the crystal, the components form a stable 3D supramolecular architecture by C-H...O interactions and to-stacking
文摘A calculation formula of ln γ i 0 for solute element i in liquid alloys was derived by use of free volume theory and Miedema formation enthalpy model. The values of ln γ i 0 of solute elements in liquid copper at 1273 K were obtained. The results obtained show that the coincidence rate of sign (positive or negative) was 90% for the calculated and experimental values, which were basically in the same magnitude.
基金This work was financially supported by the NNSFC (No. 20431010 and 20171012)
文摘The copper complex Cu（C12H9N2O3）2 has been synthesized by the reaction of furaldehyde salicylylhydrazone （Hfs） and copper acetylacetonate and characterized by X-ray crystal diffraction and spectroscopic studies. The crystal crystallizes in space group P211n with a = 5.9765（3）, b = 15.7196（9）, c = 12.0514（6）A,β= 101.618（3）^o, V = 1109.0（1）A^3, C24H18CuN4O6, Mr = 521.96, Z = 2, Dc = 1.563 g/cm^3, μ = 1.035 mm^-1, F（000） = 534, R = 0.0373 and wR = 0.1058 for 2283 observed reflections （I 〉 2σ（I））. The copper atom has a square-planar CuN2O2 coordination and should be in an octahedral coordination if considering Cu-O （phenol） with distances of 2.796（2）A as weak bonds. The neighboring copper complex molecules are linked together by these weak Cu-O （phenol） bonds, resulting in an extended 1D chain. The title compound exhibits paramagnetic property and fluorescence behavior at room temperature supported by the EPR and fluorescence spectra.
文摘A new Schiff base (LK) obtained from 2, 4, -dihydroxybenzaldehyde and glycly-DL- phenylalanine reacted with Cu(II), Zn(II), Ni(II) and Co(II) to yield new complexes. The complexes were characterized by elemental analyses, molar conductance, 1H NMR DTA, TG, IR and UV spectroscopy. In these complexes the ligand is coordinated to the metal through its phenolic oxygen, carboxyl oxygen, imino nitrogen and amide nitrogen. All complexes are non-electrolytes and four coordinated with 1:1(metal; ligand) stoichiometry. The probable structure of the complexes is suggested
基金Project supported by the research grant of Phytochemistry Key Laboratory of Shaanxi Province (No. 12JS007)
文摘Two new Cu（Ⅱ） complexes have been synthesized with two different bidentate N2O2 donor Schiffbase ligands HL1 （2-（（E）-（4-chlorophenylimino）methyl）-6-bromo-4-chlorophenol） and HL2 （2-（（E）-（2-chlorophenylimino）methyl）-6-bromo-4-chlorophenol）, respectively. Both complexes 1 and 2 have been characterized by elemental analysis and single-crystal X-ray diffraction studies. Structural studies reveal that in both complexes the metal centers are four-coordinated with N202 donor set of Schiff base ligands. Complex 1 belongs to the tetragonal system, space group P4（3）2（1）2 with a = 10.2379（2）, b = 10.2379（2）, c = 24.9623（90） A, V = 2616.41（12） A^3, Z = 4, Dc = 1.908 g/cm^3,μ（MoKa） = 4.3327 mm^-1, F（000） = 1468, S = 0.999, the final R = 0.0345 and wR = 0.0835 for 3506 unique reflections （Rint= 0.0428） with 3249 observed ones （I 〉 2σ（I））. Complex 2 is of monoclinic system, space group P21/c with a = 11.064（3）, b = 9.437（2）, c = 13.277（4） A, fl = 108.997（3）°, V = 1310.8（6） A^3, Z = 2, Dc= 1.904 g/cm^3,μ（MoKa） = 4.319 mm^-1, F（000） = 734, S = 0.997, the final R = 0.0282 and wR = 0.0619 for 3491 unique reflections （Rint = 0.0428） with 2777 observed ones （I 〉 20（I））. The units of the complex are linked via weak interactions, such as C-H…Br hydrogen bonds together with Cl…C1 and Cu…Cl interactions, leading to the formation of one-dimensional chain and two-dimensional network and stabilizing the crystal structure.
基金supported by the National Natural Science Foundation of China(No.21771078 and 21621001)the 111 Project(B17020)the National Key Research and Development Program of China(2016YFB0701100).
文摘To systematically study the effect of Lewis acid sites(LASs)and Lewis base sites(LBSs)in MOF materials for the CO_(2)cycloaddition reaction,four isomorphous copper polyhedron-based MOFs(Cu-PMOFs),JLU-Liu20,JLU-Liu21,JLU-Liu22 and JLU-Liu46 with different amounts of LASs and LBSs were selected to investigate their CO_(2)fixation catalytic performance.It is commendable that the catalytic capabilities of the four Cu-PMOFs exceed that of most reported MOF-based catalysts.
基金supported by the International Scientific and Technological Cooperation Foundation of Science and Technology Department of Jilin province(No.20200801041GH)Science and Technology Department of Changchun(21ZGM02),P.R.China.
文摘It is highly desirable yet challenging to incorporate open micropores with mass transportation and open active metal sites into metal-organic frameworks(MOFs)for developing novel highly efficient catalysts.Herein,we report a catalyst of low-nuclearity copper-cluster-based micropore MOF,namely H-1e,incor-porated with unsaturated Cu(Ⅱ)centres as open active sites obtained via a highly efficient electrochemical synthesis within 20 minutes.The catalyst H-1e shows potential porosity with 1D open functionalized hexagonal channels for size-selective air oxidation as well as high stability.The electrochemically pre-pared H-1e exhibits excellent catalytic aerobic oxidation activity for the conversion of alcohols(mini-size)to aldehydes with over 99%selectivity and 99%yield under air conditions,showing excellent reusability and stability.The selective catalytic performances are found to be closely dependent on the suitable aperture size of the 1D channels in H-1e,which provided better beds for the oxidation transformations(confirmed by the computational DFT study).In this study,it offers a simple and potential strategy to con-struct microporous materials with open active metal sites to promote the catalytic efficiency of MOFs by electrochemical synthesis.
基金supported by the National Natural Science Foundation of China(No.21771078,21671074,and 21621001)the 111 Project(B17020)the National Key Research and Development Program of China(2016YFB0701100).
文摘Two novel porous MOFs,[Cu_(2)Cl(TZI)(H_(2)O)_(3)]·4DMA(compound 1)and[Cu_(2)(TZI)(OH)(DMF)]·DMF·H_(2)O(compound 2)(H_(3)TZI=5-(tetrazol-5-yl)isophthalic acid,DMA=N,N-dimethylacetamide,and DMF=N,N-dimethylformamide),have been successfully synthesized using the same ligand consisting of isophthalate and tetrazolate groups and CuCl_(2)·2H_(2)O through the secondary building unit(SBU)strategy.Both compounds are constructed from copper cluster-based SBUs.Compound 1 is made up of two different cages based on a Cu paddlewheel and rare-reported double-crown like hexanuclear Cu cluster.In this SBU,the Cu atom adopts a five-coordination in a trigonal bipyramidal configuration,which is very rare in reported MOFs.Moreover,compound 1 with dual functionalities of open metal sites(OMSs)and N-rich Lewis basic sites(LBSs)exhibits good CO_(2) adsorption(92 cm^(3) g^(-1) at 273 K)and high-effect separation ability(9.6 for CO_(2)/CH_(4)=0.5/0.5 under 1 bar at 298 K).
基金supported by the National Natural Science Foundation of China(Nos.52172291,52122312 and 52473294)the“Shuguang Program”supported by Shanghai Education Development Foundation and Shanghai Municipal Education Commission(No.22SG31).
文摘Nitrogen is essential for life and ecosystems.The nitrogen cycle is fundamental to all life on earth and has been implicated in his-torical mass extinction events,where disruptions to its stability have played a critical role[1].Moreover,the nitrogen cycle's response to climate change could critically influence atmo-spheric CO_(2) levels and the trajectory of global warming[2].However,improper management of anthropogenic nitrogen-containing wastewater,including domestic sewage,agricultural runoff,and industrial effluents,has pushed the nitrogen cycle to the brink of imbalance[1].
基金National Natural Science Foundation of China,Grant/Award Number:12205226Hubei Provincial Department of Education,Grant/Award Number:Q20221508。
文摘Many regions across the globe are grappling with water scarcity issues,prompting the exploration of innovative water harvesting techniques.While the development of high-performance water harvesting materials has been widely documented,these technologies often rely on a singular source with limited efficiency.This study presents a dual-functional copper Janus system that facilitates continuous freshwater harvesting by integrating seawater desalination powered by solar energy during daylight hours and fog collection during night and morning time.The Janus system consists of a copper sheet and copper foam substrate,featuring superhydrophilic pores arranged on the superhydrophobic surface,as well as superhydrophilic flake-like structures made of soot-carbon particles,which are deposited on the framework of the copper foam.The fog collection rate of this system has been measured at 210.65 kg m^(−2) h^(−1),while the solar-driven evaporation rate of seawater under 1-sun conditions is reported at 1.44 kg m^(−2) h^(−1).The fog collection and evaporation efficiency have been enhanced by 28.72% and 183.27%,respectively.Furthermore,the system demonstrates strong and consistent performance even after repeated use,ensuring sustained water collection over prolonged periods.Therefore,this study presents a promising avenue for water collection technologies and offers valuable insights for the advancement of sustainable freshwater production methods.
基金supported by the National Natural Science Foundation of China(No.21771078,21671074,and 21621001)the 111 Project(B17020)the National Key Research and Development Program of China(2016YFB0701100)。
文摘Herein,by using pillaring ligands with different lengths,two copper-based metal–organic frameworks,compounds 1 (Cu_(2)(bada)_(2)(dabco)) and 2 (Cu_(2)(bada)_(2)(bipy)) (bada=4,4′-carbonylbis(azanediyl)dibenzoic acid,dabco=1,4-diazabicyclo[2.2.2]octane,bipy=4,4′-bipyridine) with the urea-functionalized ligand bada,have been successfully synthesized using a pillared-layer strategy.Both 1 and 2 exhibit two-dimensional square lattice (sql) layers pillared by dabco and bipy,respectively,and feature pcu topology.Different to dabco in 1,the pillaring ligand 4,4′-bipyridine with longer length forms a doubly interpenetrated structure of 2.Both compounds display good thermal stabilities and permanent porosities.1 exhibits good performance for CO_(2)(32 cm^(3) g^(-1)),C_(2)H_(6) (58 cm^(3) g^(-1)),and C_(3)H_(8) (105 cm^(3) g^(-1)) capture among MOFs without open metal sites.In particular,1 possesses high Q_st for CO_(2)(32.8 kJ mol^(-1)),C_(2)H_(6) (37.2 kJ mol^(-1)),and C_(3)H_(8) (40.3 kJ mol^(-1)) adsorption and outstanding selectivities for CO_(2)(5.7),C_(2)H_(6) (28),and C_(3)H_(8) (224) over CH_(4) at 298 K.Density functional theory (DFT)-based calculations further prove the hydrogen-bond interactions and σ–π interactions between gas molecules and urea-based ligands.2 exhibits a gate-opening behavior for N_(2),Ar and CO_(2).Compound 1 could be seen as a significant potential material for gas storage and separation.
