Despite of extensive attention on the copper-based heterogeneous oxidative homocoupling of alkynes(OHA)to 1,3-diynes,the photocatalytic OHA is scarcely investigated.By screening copper-containing spinel catalysts,we d...Despite of extensive attention on the copper-based heterogeneous oxidative homocoupling of alkynes(OHA)to 1,3-diynes,the photocatalytic OHA is scarcely investigated.By screening copper-containing spinel catalysts,we discovered that a prereduced copper ferrite(CuFe2O4)not only can catalyze the thermocatalytic OHA but also is efficient for the photocatalytic OHA under visible light irradiation.It is found that the sol-gel combustion(SG)method and the partial reduction at 250 ℃ can result in the optimal CuFe2O4-SG-250 catalyst showing high activity and stability.Surface oxidized Cu2O is evidenced to be the active species for the thermocatalytic OHA,whereas metallic copper nanopaticles(CuNPs)are identified as the active sites for the photocatalytic OHA.The efficiency of photocatalytic OHA at ambient temperature is comparable to that of thermocatalytic OHA at 120 ℃,and the CuFe2O4-SG-250 catalyst can be magnetically separated and reused at least five times.The localized surface plasmon resonance effect of CuNPs contributes to visible light-induced photocatalytic OHA.展开更多
We have performed the first-principles calculations onto the structural,electronic and magnetic properties of seven 3d transition-metal(TM=V,Cr,Mn,Fe,Co,Ni and Cu) atom substituting cation Zn in both zigzag(10,0) and ...We have performed the first-principles calculations onto the structural,electronic and magnetic properties of seven 3d transition-metal(TM=V,Cr,Mn,Fe,Co,Ni and Cu) atom substituting cation Zn in both zigzag(10,0) and armchair(6,6) zinc oxide nanotubes(ZnONTs).The results show that there exists a structural distortion around 3d TM impurities with respect to the pristine ZnONTs.The magnetic moment increases for V-,Cr-doped ZnONTs and reaches maximum for Mn-doped ZnONTs,and then decreases for Fe-,Co-,Ni-and Cu-doped ZnONTs successively,which is consistent with the predicted trend of Hund's rule for maximizing the magnetic moments of the doped TM ions.However,the values of the magnetic moments are smaller than the predicted values of Hund's rule due to strong hybridization between p orbitals of the nearest neighbor O atoms of ZnONTs and d orbitals of the TM atoms.Furthermore,the Mn-,Fe-,Co-,Cu-doped(10,0) and(6,6) ZnONTs with half-metal and thus 100% spin polarization characters seem to be good candidates for spintronic applications.展开更多
基金supported by the National Natural Science Foundation of China (21673088)~~
文摘Despite of extensive attention on the copper-based heterogeneous oxidative homocoupling of alkynes(OHA)to 1,3-diynes,the photocatalytic OHA is scarcely investigated.By screening copper-containing spinel catalysts,we discovered that a prereduced copper ferrite(CuFe2O4)not only can catalyze the thermocatalytic OHA but also is efficient for the photocatalytic OHA under visible light irradiation.It is found that the sol-gel combustion(SG)method and the partial reduction at 250 ℃ can result in the optimal CuFe2O4-SG-250 catalyst showing high activity and stability.Surface oxidized Cu2O is evidenced to be the active species for the thermocatalytic OHA,whereas metallic copper nanopaticles(CuNPs)are identified as the active sites for the photocatalytic OHA.The efficiency of photocatalytic OHA at ambient temperature is comparable to that of thermocatalytic OHA at 120 ℃,and the CuFe2O4-SG-250 catalyst can be magnetically separated and reused at least five times.The localized surface plasmon resonance effect of CuNPs contributes to visible light-induced photocatalytic OHA.
基金supported by the National Natural Science Foundation of China (Grant No. 51071098)the State Key Development for Basic Research of China (Grant No. 2010CB631002)
文摘We have performed the first-principles calculations onto the structural,electronic and magnetic properties of seven 3d transition-metal(TM=V,Cr,Mn,Fe,Co,Ni and Cu) atom substituting cation Zn in both zigzag(10,0) and armchair(6,6) zinc oxide nanotubes(ZnONTs).The results show that there exists a structural distortion around 3d TM impurities with respect to the pristine ZnONTs.The magnetic moment increases for V-,Cr-doped ZnONTs and reaches maximum for Mn-doped ZnONTs,and then decreases for Fe-,Co-,Ni-and Cu-doped ZnONTs successively,which is consistent with the predicted trend of Hund's rule for maximizing the magnetic moments of the doped TM ions.However,the values of the magnetic moments are smaller than the predicted values of Hund's rule due to strong hybridization between p orbitals of the nearest neighbor O atoms of ZnONTs and d orbitals of the TM atoms.Furthermore,the Mn-,Fe-,Co-,Cu-doped(10,0) and(6,6) ZnONTs with half-metal and thus 100% spin polarization characters seem to be good candidates for spintronic applications.
