The efficient synthesis of methanol and ethylene glycol via the chemoselective hydrogenation of ethylene carbonate(EC) is important for the sustainable utilization of CO_2 to produce commodity chemicals and fuels. I...The efficient synthesis of methanol and ethylene glycol via the chemoselective hydrogenation of ethylene carbonate(EC) is important for the sustainable utilization of CO_2 to produce commodity chemicals and fuels. In this work, a series of β-cyclodextrin-modified Cu/SiO_2 catalysts were prepared by ammonia evaporation method for the selective hydrogenation of EC to co-produce methanol and ethylene glycol. The structure and physicochemical properties of the catalysts were characterized in detail by N_2 physisorption, XRD, N_2O titration, H_2-TPR, TEM, and XPS/XAES. Compared with the unmodified 25 Cu/SiO_2 catalyst, the involvement of β-cyclodextrin in 5β-25 Cu/SiO_2 could remarkably increase the catalytic activity—excellent activity of 1178 mgEC g_(cat)^(–1) h^(–1) with 98.8%ethylene glycol selectivity, and 71.6% methanol selectivity could be achieved at 453 K. The remarkably improved recyclability was primarily attributed to the remaining proportion of Cu~+/(Cu^0+Cu~+). Furthermore, the DFT calculation results demonstrated that metallic Cu^0 dissociated adsorbed H_2, while Cu~+ activated the carbonyl group of EC and stabilized the intermediates. This study is a facile and efficient method to prepare highly dispersed Cu catalysts—this is also an effective and stable heterogeneous catalyst system for the sustainable synthesis of ethylene glycol and methanol via indirect chemical utilization of CO_2.展开更多
Carboxyl graphene modified CuxO/Cu electrode was fabricated. The bare copper electrode was firstly anodic polarized in 1.0 mol/L NaOH solution in order to get CuxO nanoparticles, then the carboxyl graphene (CG) was ...Carboxyl graphene modified CuxO/Cu electrode was fabricated. The bare copper electrode was firstly anodic polarized in 1.0 mol/L NaOH solution in order to get CuxO nanoparticles, then the carboxyl graphene (CG) was electrodeposited on the CuxO/Cu electrode by cyclic potential sweeping. The electrocatalytic oxidation behaviors of calcium folinate (CF) at the graphene modified CuxO/Cu electrode were investigated by cyclic voltammetry. A positive scan polarization reverse catalytic voltammetry was used to obtain the pure catalytic oxidation current. The graphene modified CuxO/Cu electrode was served as the electrochemical sensor of CF, a highly sensitivity of 22.0μA.(μmol/μL)^-1cm^-2 was achieved, and the current response was linear with increasing CF concentration in the range of 2.0×10^-7 mol/L to 2.0×10^-5 mol/L, which crossed three orders of magnitude, and the detection limit was found 7.6×10^-5 mol/L (S/N=3). In addition, the proposed sensor was successfully applied in determination of CF in drug sample.展开更多
Adsorptive desulfurization for removing propylmercaptan (PM) and dimethyl sulfide (DMS) over CuBr2 modi- fied bentonite was investigated under ambient conditions in this work. A saturated sulfur capacity as high a...Adsorptive desulfurization for removing propylmercaptan (PM) and dimethyl sulfide (DMS) over CuBr2 modi- fied bentonite was investigated under ambient conditions in this work. A saturated sulfur capacity as high as 196 mg of S per gram of adsorbent was demonstrated. The influence of loading amount of Cu (II) and calcination temperature on adsorptive desulfurization was investigated. Test results revealed that the optimum loading amount of Cu (II) was 15%, and the calcination temperature was 150 ℃. The pyridine-FTIR spectroscopy showed that a certain amount of Lewis acid could contribute to the increase of adsorption capacity. Spectral shifts of the v(C-S) and v(Cu-S) vibrations were detected from the Raman spectra of the Cu (II) complex which was a reaction product of CuBr2 with DMS. According to the hybrid orbital theory and the complex adsorption reaction, the desulfurization of PM and DMS over the CuBr2 modified bentonite is ascribed to the formation of S-M (σ) bonds.展开更多
The surface tensions and contact angles of Fe_(78)Si_9B_(13) and Fe_(73.5)Cu_1Nb_3Si_(13.5)B_9 alloy melts were studied as a function of temperature in various atmospheres(vacuum, Ar and N_2 gas) and on different subs...The surface tensions and contact angles of Fe_(78)Si_9B_(13) and Fe_(73.5)Cu_1Nb_3Si_(13.5)B_9 alloy melts were studied as a function of temperature in various atmospheres(vacuum, Ar and N_2 gas) and on different substrates(Si C, Al_2O_3 and BN). It is indicated that Si_3N_4, NbN, Fe_2 Al B and B_(13)C_2 are generated as new phases at the interface between the melt and substrate, and reactive wetting behaviour exists during the heating process. The surface tensions of two alloy melts on BN substrate both firstly decrease and then increase along with increasing temperature, leading to V-shaped surface tension versus temperature, which results from atomic diffusion effects in the surface layer during the oxidation of BN and formation of C-rich layer. Comparably, the surface tensions on Al_2O_3 and Si C substrates decrease with increasing temperature throughout the entire temperature range. Among three substrates, BN exhibits the mildest wetting behaviour. The vacuum environment has the strongest protective effect on melt stability among the tested atmospheres. These findings enrich our knowledge about the effects of the substrate and atmosphere on Fe-based alloy melts at a high temperature, and provide theoretical reference for designing jet nozzles in melt-spinning techniques.展开更多
Transmetalation of carborane-fused zirconacycles to Cu(II) induces the C-C coupling reaction to form four-membered rings. This serves as a new efficient and general methodology for the generation of a series of carb...Transmetalation of carborane-fused zirconacycles to Cu(II) induces the C-C coupling reaction to form four-membered rings. This serves as a new efficient and general methodology for the generation of a series of carborane-fused cyclobutenes and cyclobutanes. A reaction mechanism involving transmetalation to Cu(II) and reductive elimination is proposed.展开更多
Porous metal architectures are widely adopted as three-dimensional conducting scaffolds for constructing Li metal composite anodes,whereas their macropores hinder their practical application due to limited surface are...Porous metal architectures are widely adopted as three-dimensional conducting scaffolds for constructing Li metal composite anodes,whereas their macropores hinder their practical application due to limited surface area and large pore size of few hundred micrometers.In this work,a network of Li_(x)Cu solid solution alloy nanowires is in situ formed via infiltrating molten Li-Cu alloy into Ni foam and subsequent cooling treatment,whereby a three-component composite anode consisting of Li metal,Li_(x)Cu alloy,and Ni foam is fabricated.The Li_(x)Cu nanowires nested as secondary frame split the macropores into micropores,enlarging the active surface area and inducing uniform Li deposition significantly.The lithiophilicity of the alloy wires and the shrunken void size built by the hierarchical architecture can further tune the nucleation and growth behavior of Li.The multiscale synergetic effect between the primary and secondary scaffold guarantees the composite anode sheet with extraordinarily long-term cycling stability even under high current rates.展开更多
文摘The efficient synthesis of methanol and ethylene glycol via the chemoselective hydrogenation of ethylene carbonate(EC) is important for the sustainable utilization of CO_2 to produce commodity chemicals and fuels. In this work, a series of β-cyclodextrin-modified Cu/SiO_2 catalysts were prepared by ammonia evaporation method for the selective hydrogenation of EC to co-produce methanol and ethylene glycol. The structure and physicochemical properties of the catalysts were characterized in detail by N_2 physisorption, XRD, N_2O titration, H_2-TPR, TEM, and XPS/XAES. Compared with the unmodified 25 Cu/SiO_2 catalyst, the involvement of β-cyclodextrin in 5β-25 Cu/SiO_2 could remarkably increase the catalytic activity—excellent activity of 1178 mgEC g_(cat)^(–1) h^(–1) with 98.8%ethylene glycol selectivity, and 71.6% methanol selectivity could be achieved at 453 K. The remarkably improved recyclability was primarily attributed to the remaining proportion of Cu~+/(Cu^0+Cu~+). Furthermore, the DFT calculation results demonstrated that metallic Cu^0 dissociated adsorbed H_2, while Cu~+ activated the carbonyl group of EC and stabilized the intermediates. This study is a facile and efficient method to prepare highly dispersed Cu catalysts—this is also an effective and stable heterogeneous catalyst system for the sustainable synthesis of ethylene glycol and methanol via indirect chemical utilization of CO_2.
文摘Carboxyl graphene modified CuxO/Cu electrode was fabricated. The bare copper electrode was firstly anodic polarized in 1.0 mol/L NaOH solution in order to get CuxO nanoparticles, then the carboxyl graphene (CG) was electrodeposited on the CuxO/Cu electrode by cyclic potential sweeping. The electrocatalytic oxidation behaviors of calcium folinate (CF) at the graphene modified CuxO/Cu electrode were investigated by cyclic voltammetry. A positive scan polarization reverse catalytic voltammetry was used to obtain the pure catalytic oxidation current. The graphene modified CuxO/Cu electrode was served as the electrochemical sensor of CF, a highly sensitivity of 22.0μA.(μmol/μL)^-1cm^-2 was achieved, and the current response was linear with increasing CF concentration in the range of 2.0×10^-7 mol/L to 2.0×10^-5 mol/L, which crossed three orders of magnitude, and the detection limit was found 7.6×10^-5 mol/L (S/N=3). In addition, the proposed sensor was successfully applied in determination of CF in drug sample.
基金financially supported by the National Natural Science Foundation of China(No.21276086)
文摘Adsorptive desulfurization for removing propylmercaptan (PM) and dimethyl sulfide (DMS) over CuBr2 modi- fied bentonite was investigated under ambient conditions in this work. A saturated sulfur capacity as high as 196 mg of S per gram of adsorbent was demonstrated. The influence of loading amount of Cu (II) and calcination temperature on adsorptive desulfurization was investigated. Test results revealed that the optimum loading amount of Cu (II) was 15%, and the calcination temperature was 150 ℃. The pyridine-FTIR spectroscopy showed that a certain amount of Lewis acid could contribute to the increase of adsorption capacity. Spectral shifts of the v(C-S) and v(Cu-S) vibrations were detected from the Raman spectra of the Cu (II) complex which was a reaction product of CuBr2 with DMS. According to the hybrid orbital theory and the complex adsorption reaction, the desulfurization of PM and DMS over the CuBr2 modified bentonite is ascribed to the formation of S-M (σ) bonds.
基金supported by the National Natural Science Foundation of China(Grant No.51501043)National Scientific and Technological Support Projects(Grant No.2013BAE08B00)+1 种基金National Key Scientific Instrument and Equiment Development Project(Grant No.2014YQ120351)Science and Technology Program of Beijing(Grant No.Z141100003814007)
文摘The surface tensions and contact angles of Fe_(78)Si_9B_(13) and Fe_(73.5)Cu_1Nb_3Si_(13.5)B_9 alloy melts were studied as a function of temperature in various atmospheres(vacuum, Ar and N_2 gas) and on different substrates(Si C, Al_2O_3 and BN). It is indicated that Si_3N_4, NbN, Fe_2 Al B and B_(13)C_2 are generated as new phases at the interface between the melt and substrate, and reactive wetting behaviour exists during the heating process. The surface tensions of two alloy melts on BN substrate both firstly decrease and then increase along with increasing temperature, leading to V-shaped surface tension versus temperature, which results from atomic diffusion effects in the surface layer during the oxidation of BN and formation of C-rich layer. Comparably, the surface tensions on Al_2O_3 and Si C substrates decrease with increasing temperature throughout the entire temperature range. Among three substrates, BN exhibits the mildest wetting behaviour. The vacuum environment has the strongest protective effect on melt stability among the tested atmospheres. These findings enrich our knowledge about the effects of the substrate and atmosphere on Fe-based alloy melts at a high temperature, and provide theoretical reference for designing jet nozzles in melt-spinning techniques.
基金supported by the Research Grants Council of the Hong Kong Special Administration Region (404011)the National Natural Science Foundation of China (21372245 to QIU ZaoZao)
文摘Transmetalation of carborane-fused zirconacycles to Cu(II) induces the C-C coupling reaction to form four-membered rings. This serves as a new efficient and general methodology for the generation of a series of carborane-fused cyclobutenes and cyclobutanes. A reaction mechanism involving transmetalation to Cu(II) and reductive elimination is proposed.
基金partly supported by the National Natural Science Foundation of China(21673033)Sichuan Science and Technology Program(2020071)the Fundamental Research Founds for the Central Universities(ZYGX2019J024).
文摘Porous metal architectures are widely adopted as three-dimensional conducting scaffolds for constructing Li metal composite anodes,whereas their macropores hinder their practical application due to limited surface area and large pore size of few hundred micrometers.In this work,a network of Li_(x)Cu solid solution alloy nanowires is in situ formed via infiltrating molten Li-Cu alloy into Ni foam and subsequent cooling treatment,whereby a three-component composite anode consisting of Li metal,Li_(x)Cu alloy,and Ni foam is fabricated.The Li_(x)Cu nanowires nested as secondary frame split the macropores into micropores,enlarging the active surface area and inducing uniform Li deposition significantly.The lithiophilicity of the alloy wires and the shrunken void size built by the hierarchical architecture can further tune the nucleation and growth behavior of Li.The multiscale synergetic effect between the primary and secondary scaffold guarantees the composite anode sheet with extraordinarily long-term cycling stability even under high current rates.