A novel solid superacid catalyst S2O8^2-/ZrO2-CeO2 was prepared by a coprecipitation method and characterized by means of XRD FTIR, BET, TEM and DSC/TG analysis methods. The results indicated that incorporation of app...A novel solid superacid catalyst S2O8^2-/ZrO2-CeO2 was prepared by a coprecipitation method and characterized by means of XRD FTIR, BET, TEM and DSC/TG analysis methods. The results indicated that incorporation of appropriate amounts of Ce into the catalyst was beneficial to the formation of sole tetragonal ZrO2 and effectively prevented from the formation of monoclinic ZrO〉 and restrained the loss of sulfated species. XRD revealed the presence of tetragonal Ce0.16Zr0.84O2phase in the case of S2O8^2-/ZrO2-CeO2 calcined above 500 ℃. Catalytic activities of S2O8^2-/ZrO2-CeO2 for the esterification of lactic acid with n-butanol was studied. The results showed that the optimum conditions were as follows： calcination temperature of the catalyst 600 ℃, n（lactic acid）：n（n-butyl alcohol）=1.0：3.0, w（S2O8^2-/ZrO2- CeO2）=12.0%, reaction temperature 145 ℃, and reaction time 2 h. The esterification efficiency of lactic acid was about 96.6%.展开更多
SO4^2- / TiO2-La2O3, a novel solid superacid, was prepared and its catalytic activities at different synthetic conditions are discussed with esterification of n-butanoic acid and n-butyl alcohol as probing reaction. T...SO4^2- / TiO2-La2O3, a novel solid superacid, was prepared and its catalytic activities at different synthetic conditions are discussed with esterification of n-butanoic acid and n-butyl alcohol as probing reaction. The optimum conditions have also been found, mole ratio of n（La^3＋）：n（Ti^4＋） is 1：34, the soaked consistency of H2SO4 is 0.8 tool/L, the soaked time of HESO4 is 24 h, the calcining temperature is 480 ℃, the calcining time is 3 h. Then it was applied in the catalytic synthesis often important ketals and acetals as catalyst and revealed high catalytic activity. Under these conditions on which the molar ratio of aldehyde/ketone to glycol is l： 1.5, the mass ratio of the catalyst used in the reactants is 0.5%, and the reaction time is 1.0 h, the yields of ketals and acetals can reach 41.4%-95.8%.展开更多
Rare earth complexes Eu(Phen)_2(TTA)(Bipy)(NO_3)_3 and Eu(L)_x(TTA)_(4-x)(NO_3)_3 (L=Phen or Bipy; x=4, 3, 2, 1, 0) solutions (1×10^(-3) mol·L^(-1)) were prepared in EtOH. The luminescent experimental result...Rare earth complexes Eu(Phen)_2(TTA)(Bipy)(NO_3)_3 and Eu(L)_x(TTA)_(4-x)(NO_3)_3 (L=Phen or Bipy; x=4, 3, 2, 1, 0) solutions (1×10^(-3) mol·L^(-1)) were prepared in EtOH. The luminescent experimental results show that the synergy effect of Phen and TTA exists in Eu^(3+) complexes. But when the ligands of Bipy and TTA coexist in europium complex, the synergy effect does not exist. If a solution of a europium complex has a specific electron configuration of excited state, the solution of the complex has an intensity of fluorescence and a quantum yield. 2.5×10^(-5) mol·L^(-1) Eu(Phen)_2(TTA)_2(NO_3)_3 solution (λ_(ex)=347.0 nm) possesses a maximal quantum yield (0.25) and the strongest fluorescent intensity. The nanosized mesoporous molecular sieves possess spherical cage structure that is fit for preparation of composite materials with encapsulation method. The research results of XRD and IR show that the guest molecule is encapsulated into the channels of the host. The thermostability of the guest molecule in the channels of the host (CH_3)_3Si-MCM-41 is enhanced. The fluorescent intensity and the half-life of nanosized composites of (CH_3)_3Si-MCM-41 and Eu^(3+) complexes are stronger and longer than those of encapsulation products of MCM-41 and Eu^(3+) complexes. Supramolecular encapsulation products emit characteristic radiation of Eu^(3+) ion, vesting in the transitions of (()~5D_0→()~7F_J) (J=0, 1, 2, 3, 4), respectively; each excitation peak of fluorescent spectra of the composites is assigned to an excited electron configuration of Eu^(3+) ion. The host with lipophilic channels is more favourable to fluorescence of the rare earth complex than hydrophilic mesoporous molecular sieve; The fluorescent intensity of (CH_3)_3Si-MCM-41-Eu(Phen)(TTA)_3(NO_3)_3 can match with that of Eu(Phen)(TTA)_3(NO_3)_3 powder sample. These results could be assumed to result from strong radiation absorption of the guest complex molecule (blue shift of maximum excitation wavelength), greatly reducing of silanol group vibration relaxation of the host (CH_3)_3Si-MCM-41, energy transfer from host to guest, and presence of discrete luminescent center associated with nanosized material structures. The selectivity of host to guest and the interaction between the host and the guest influence greatly the luminescent properties of supramolecular system.展开更多
The research of poly(ethylene oxide)(PEO)-based solid composite electrolyte with high ionic conductivity and excellent interfacial stability is the key to the development of all-solid-state lithium-ion batteries(ASSLI...The research of poly(ethylene oxide)(PEO)-based solid composite electrolyte with high ionic conductivity and excellent interfacial stability is the key to the development of all-solid-state lithium-ion batteries(ASSLIBs). Herein, uniform nanorod structured CeO_(2) fillers were controllably synthesized by electrospinning, which were subsequently filled into PEO polymer to prepare CeO_(2)/PEO solid composite electrolyte. The addition of CeO_(2) nanorods can reduce both the glass transition temperature and the melting point of PEO polymer, and also interact with PEO and lithium bis(trifluoromethanesulphonyl)imide(LITFSI) by Lewis acid—base reaction. Therefore, the solid composite electrolyte exhibits a high ionic conductivity of 4.52 × 10^(-4)S/cm, a wide electrochemical stability window of about 4.8 V, and a good interfacial stability with Li at 55℃. Moreover, the LiFePO_4/Li ASSLIB divulges the discharging specific capacity of 165, 162, 156 and 146 mA,h/g at 0.2, 0.5, 1 and 2 C, respectively, and achieves the capacity retention of 90.3% after 150 cycles at 0.5 C. Consequently, one dimensional CeO_(2) nanorods can be considered as an alternative filler for polymeric solid electrolyte.展开更多
To promote the electrocatalytic activity and stability of traditional(a_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)(LSCF)oxygen electrodes in reversible solid oxide cells(RSOCs),conventional physical mixed method was used t...To promote the electrocatalytic activity and stability of traditional(a_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)(LSCF)oxygen electrodes in reversible solid oxide cells(RSOCs),conventional physical mixed method was used to prepare the Pd-LSCF composite oxygen electrode.The cell with Pd-LSCF|GDC|YSZ|Ni-YSZ configuration shows perfect electrochemical performance in both solid oxide fuel cell(SOFC)mode and solid oxide electrolysis cell(SOEC)mode.In the SOFC mode,the cell achieves a power density of 1.73 W/cm^(2)at800℃higher than that of the LSCF oxygen electrode with 1.38 W/cm^(2).In the SOEC mode,the current density at 1.5 V is 1.67 A/cm^(2)at 800℃under 50 vol%steam concentration.Moreover,the reversibility and stability of the RSOCs were tested during 192 h long-term reversible operation.The degradation rate of the cell is only 2.2%/100 h and 2.5%/100 h in the SOEC and the SOFC modes,respectively.These results confirm that compositing Pd with the LSCF oxygen electrode can considerably boost the electrochemical performance of LSCF electrode in RSOCs field.展开更多
The synthesis of isoamyl butyrate with isoamyl alcohol and butyric acid as reactants and rare-earth solid superacid SO42-/TiO2/La3+ as catalyst had been studied. The influent actors of reaction were investigated. The ...The synthesis of isoamyl butyrate with isoamyl alcohol and butyric acid as reactants and rare-earth solid superacid SO42-/TiO2/La3+ as catalyst had been studied. The influent actors of reaction were investigated. The results showed that the appropriate conditions should be: Weight of catalyst was 0. 5g (weight of butyric acid if 0. 2mol); molar ratio of isoamyl alcohol to butyric acid was 1. 8: 1; reaction time was 2. 0 h; the taking water reagent (Toluene) was 15mL. The yield of isoamyl butyrate was about 99. 0%.展开更多
基金supported by the Science and Technique Foundation of Shaaxi Province of China (2008K07-32)the Foundation of Shaanxi Educa- tional Committee of China (08JK228)the Graduate Innovation Fund of Shaanxi University of Science and Technology
文摘A novel solid superacid catalyst S2O8^2-/ZrO2-CeO2 was prepared by a coprecipitation method and characterized by means of XRD FTIR, BET, TEM and DSC/TG analysis methods. The results indicated that incorporation of appropriate amounts of Ce into the catalyst was beneficial to the formation of sole tetragonal ZrO2 and effectively prevented from the formation of monoclinic ZrO〉 and restrained the loss of sulfated species. XRD revealed the presence of tetragonal Ce0.16Zr0.84O2phase in the case of S2O8^2-/ZrO2-CeO2 calcined above 500 ℃. Catalytic activities of S2O8^2-/ZrO2-CeO2 for the esterification of lactic acid with n-butanol was studied. The results showed that the optimum conditions were as follows： calcination temperature of the catalyst 600 ℃, n（lactic acid）：n（n-butyl alcohol）=1.0：3.0, w（S2O8^2-/ZrO2- CeO2）=12.0%, reaction temperature 145 ℃, and reaction time 2 h. The esterification efficiency of lactic acid was about 96.6%.
基金Project supported by the National Natural Science Foundation of China (No. 20471044), and the Natural Science Foundation of Hubei Province (No. 2005ABA053), China
文摘SO4^2- / TiO2-La2O3, a novel solid superacid, was prepared and its catalytic activities at different synthetic conditions are discussed with esterification of n-butanoic acid and n-butyl alcohol as probing reaction. The optimum conditions have also been found, mole ratio of n（La^3＋）：n（Ti^4＋） is 1：34, the soaked consistency of H2SO4 is 0.8 tool/L, the soaked time of HESO4 is 24 h, the calcining temperature is 480 ℃, the calcining time is 3 h. Then it was applied in the catalytic synthesis often important ketals and acetals as catalyst and revealed high catalytic activity. Under these conditions on which the molar ratio of aldehyde/ketone to glycol is l： 1.5, the mass ratio of the catalyst used in the reactants is 0.5%, and the reaction time is 1.0 h, the yields of ketals and acetals can reach 41.4%-95.8%.
文摘Rare earth complexes Eu(Phen)_2(TTA)(Bipy)(NO_3)_3 and Eu(L)_x(TTA)_(4-x)(NO_3)_3 (L=Phen or Bipy; x=4, 3, 2, 1, 0) solutions (1×10^(-3) mol·L^(-1)) were prepared in EtOH. The luminescent experimental results show that the synergy effect of Phen and TTA exists in Eu^(3+) complexes. But when the ligands of Bipy and TTA coexist in europium complex, the synergy effect does not exist. If a solution of a europium complex has a specific electron configuration of excited state, the solution of the complex has an intensity of fluorescence and a quantum yield. 2.5×10^(-5) mol·L^(-1) Eu(Phen)_2(TTA)_2(NO_3)_3 solution (λ_(ex)=347.0 nm) possesses a maximal quantum yield (0.25) and the strongest fluorescent intensity. The nanosized mesoporous molecular sieves possess spherical cage structure that is fit for preparation of composite materials with encapsulation method. The research results of XRD and IR show that the guest molecule is encapsulated into the channels of the host. The thermostability of the guest molecule in the channels of the host (CH_3)_3Si-MCM-41 is enhanced. The fluorescent intensity and the half-life of nanosized composites of (CH_3)_3Si-MCM-41 and Eu^(3+) complexes are stronger and longer than those of encapsulation products of MCM-41 and Eu^(3+) complexes. Supramolecular encapsulation products emit characteristic radiation of Eu^(3+) ion, vesting in the transitions of (()~5D_0→()~7F_J) (J=0, 1, 2, 3, 4), respectively; each excitation peak of fluorescent spectra of the composites is assigned to an excited electron configuration of Eu^(3+) ion. The host with lipophilic channels is more favourable to fluorescence of the rare earth complex than hydrophilic mesoporous molecular sieve; The fluorescent intensity of (CH_3)_3Si-MCM-41-Eu(Phen)(TTA)_3(NO_3)_3 can match with that of Eu(Phen)(TTA)_3(NO_3)_3 powder sample. These results could be assumed to result from strong radiation absorption of the guest complex molecule (blue shift of maximum excitation wavelength), greatly reducing of silanol group vibration relaxation of the host (CH_3)_3Si-MCM-41, energy transfer from host to guest, and presence of discrete luminescent center associated with nanosized material structures. The selectivity of host to guest and the interaction between the host and the guest influence greatly the luminescent properties of supramolecular system.
基金Project supported by the Education Department of Henan Province(22A170017)the Science and Technology Department of Henan Province(232102240011)+1 种基金Henan Institute of Science and Technology(2016034)National College Students'Innovation and Entrepreneurship Training Program(202211071012)。
文摘The research of poly(ethylene oxide)(PEO)-based solid composite electrolyte with high ionic conductivity and excellent interfacial stability is the key to the development of all-solid-state lithium-ion batteries(ASSLIBs). Herein, uniform nanorod structured CeO_(2) fillers were controllably synthesized by electrospinning, which were subsequently filled into PEO polymer to prepare CeO_(2)/PEO solid composite electrolyte. The addition of CeO_(2) nanorods can reduce both the glass transition temperature and the melting point of PEO polymer, and also interact with PEO and lithium bis(trifluoromethanesulphonyl)imide(LITFSI) by Lewis acid—base reaction. Therefore, the solid composite electrolyte exhibits a high ionic conductivity of 4.52 × 10^(-4)S/cm, a wide electrochemical stability window of about 4.8 V, and a good interfacial stability with Li at 55℃. Moreover, the LiFePO_4/Li ASSLIB divulges the discharging specific capacity of 165, 162, 156 and 146 mA,h/g at 0.2, 0.5, 1 and 2 C, respectively, and achieves the capacity retention of 90.3% after 150 cycles at 0.5 C. Consequently, one dimensional CeO_(2) nanorods can be considered as an alternative filler for polymeric solid electrolyte.
基金Project supported by the National Key Research&Development Project(2020YFB1506304)the National Natural Science Foundation of China(52172199,52072135,52002121)。
文摘To promote the electrocatalytic activity and stability of traditional(a_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O_(3-δ)(LSCF)oxygen electrodes in reversible solid oxide cells(RSOCs),conventional physical mixed method was used to prepare the Pd-LSCF composite oxygen electrode.The cell with Pd-LSCF|GDC|YSZ|Ni-YSZ configuration shows perfect electrochemical performance in both solid oxide fuel cell(SOFC)mode and solid oxide electrolysis cell(SOEC)mode.In the SOFC mode,the cell achieves a power density of 1.73 W/cm^(2)at800℃higher than that of the LSCF oxygen electrode with 1.38 W/cm^(2).In the SOEC mode,the current density at 1.5 V is 1.67 A/cm^(2)at 800℃under 50 vol%steam concentration.Moreover,the reversibility and stability of the RSOCs were tested during 192 h long-term reversible operation.The degradation rate of the cell is only 2.2%/100 h and 2.5%/100 h in the SOEC and the SOFC modes,respectively.These results confirm that compositing Pd with the LSCF oxygen electrode can considerably boost the electrochemical performance of LSCF electrode in RSOCs field.
文摘The synthesis of isoamyl butyrate with isoamyl alcohol and butyric acid as reactants and rare-earth solid superacid SO42-/TiO2/La3+ as catalyst had been studied. The influent actors of reaction were investigated. The results showed that the appropriate conditions should be: Weight of catalyst was 0. 5g (weight of butyric acid if 0. 2mol); molar ratio of isoamyl alcohol to butyric acid was 1. 8: 1; reaction time was 2. 0 h; the taking water reagent (Toluene) was 15mL. The yield of isoamyl butyrate was about 99. 0%.
