Gold stabilized on reducible oxide （CeO2 and FeOx） and irreducible oxide （γ‐Al2O3, SiO2, and HZSM‐5） were prepared by deposition precipitation method and tested for catalytic oxidation of formaldehyde （HCHO） ...Gold stabilized on reducible oxide （CeO2 and FeOx） and irreducible oxide （γ‐Al2O3, SiO2, and HZSM‐5） were prepared by deposition precipitation method and tested for catalytic oxidation of formaldehyde （HCHO） at room temperature under high GHSV of 600000 ml/（g＆#183;s）. Au/γ‐Al2O3 cata‐lyst showed distinctive catalytic performance, presenting the highest initial HCHO conversion and stability. Correlating the reaction rate with Au particle size, there is a linear relationship, suggesting that the smaller Au particle size with higher dispersion possesses high reactivity for HCHO oxida‐tion. All the catalysts deactivated at high GHSV （600000 ml/（g＆#183;s））, but in a quite different rate. Re‐ducible oxide （CeO2 and FeOx） could stabilize gold through O linkage and therefore exhibits a better stability for HCHO oxidation reaction. However, the aggregation of gold particles occurred over Au/SiO2 and Au/HZSM‐5 catalysts, which result in the fast deactivation. Therefore, our results sug‐gest that the reducibility of the supports for Au catalysis has no direct influence on the activity, but affects the catalytic stability.展开更多
Low optical absorption and photocorrosion are two crucial issues limiting the practical applications of zinc oxide(ZnO)-based photocatalysts.In this paper,we report the fabrication of graphitic-carbon-mediated ZnO nan...Low optical absorption and photocorrosion are two crucial issues limiting the practical applications of zinc oxide(ZnO)-based photocatalysts.In this paper,we report the fabrication of graphitic-carbon-mediated ZnO nanorod arrays(NRAs)with enhanced photocatalytic activity and photostability for CO2 reduction under visible light irradiation.ZnO NRA/C-x(x=005,01,02,and 03)nanohybrids are prepared by calcining pre-synthesized ZnO NRAs with different amounts of glucose(0.05,0.1,0.2,and 0.3 g)as a carbon source via a hydrothermal method.X-ray photoelectron spectroscopy reveals that the obtained ZnO NRA/C-x nanohybrids are imparted with the effects of both carbon doping and carbon coating,as evidenced by the detected C-O-Zn bond and the C-C,C-O and C=O bonds,respectively.While the basic structure of ZnO remains unchanged,the UV-Vis absorption spectra show increased absorbance owing to the carbon doping effect in the ZnO NRA/C-x nanohybrids.The photoluminescence(PL)intensities of ZnO NRA/C-x nanohybrids are lower than that of bare ZnO NRA,indicating that the graphitic carbon layer coated on the surface of the ZnO NRA significantly enhances the charge carrier separation and transport,which in turn enhances the photoelectrochemical property and photocatalytic activity of the ZnO NRA/C-x nanohybrids for CO2 reduction.More importantly,a long-term reaction of photocatalytic CO2 reduction demonstrates that the photostability of ZnO NRA/C-x nanohybrids is significantly increased in comparison with the bare ZnO NRA.展开更多
The present work establishes a systematic approach based on the application of in-situ Fourier transform infrared spectroscopy （FTIR） for the investigation of the crystal structure, thermal stability, redox behavior...The present work establishes a systematic approach based on the application of in-situ Fourier transform infrared spectroscopy （FTIR） for the investigation of the crystal structure, thermal stability, redox behavior （temperature-programmed reduction/temperatureprogrammed re-oxidation） as well as the catalytic properties of Co3O4 thin films. The syntheses of Co3O4 were achieved by chemical vapor deposition in the temperature range of 400-500℃. The structure analysis of the as-prepared material revealed the presence of two prominent IR bands peaking at 544 cm-1 （υ1） and 650 cm-1 （υ2） respectively, which originate from the stretching vibrations of the Co-O bond, characteristic of the Co3O4 spinel. The lattice stability limit of Co3O4 was estimated to be above 650℃. The redox properties of the spinel structure were determined by integrating the area under the emission bands υ1 and υ2 as a function of the temperature. Moreover, Co3O4 has been successfully tested as a catalyst towards complete oxidation of dimethyl ether below 340 ℃. The exhaust gas analysis during the catalytic process by in situ absorption FTIR revealed that only CO2 and H2O were detected as the final products in the catalytic reaction. The redox behavior suggests that the oxidation of dimethyl ether over Co3O4 follows a Mars-van Krevelen type mechanism. The comprehensive application of in situ FTIR provides a novel diagnostic tool in characterization and performance test of catalysts.展开更多
Tocopherol is the most active vitamin and natural antioxidant existing in the nature known as vitamin E. Lacking of this vitamin makes drastic exchanges on the health of the living organisms. Their active chemical for...Tocopherol is the most active vitamin and natural antioxidant existing in the nature known as vitamin E. Lacking of this vitamin makes drastic exchanges on the health of the living organisms. Their active chemical form is l-α-tocopherol substance. In this article, α-thiotocopherol a tocopherol derivative was synthesized via a precursor like dl-α-tocopherol, which has better antioxidant than natural α-tocopherol. And the last compound after separation and purification via TLC and PC procedures was analyzed by FTIR, GC-MS and elemental analysis, oxidative stability is tested with TGA method in air showing roughly antioxidant effect. Another approach is measurment of redox potential against a reference electrode under inert nitrogen atmosphere.展开更多
Modulating the oxidation states of transition metal species has been regarded as a promising strategy to tune the redox activity and achieve more active sites in electrode materials.In this work,a unique three-dimensi...Modulating the oxidation states of transition metal species has been regarded as a promising strategy to tune the redox activity and achieve more active sites in electrode materials.In this work,a unique three-dimensional(3D)honeycomb-like cobalt sulfide(Co_(x)S_(y))network organized by cross-linked nanosheets(Co_(x)S_(y)-T NSs)was prepared via a simple triethanolamine(TEOA)-assisted self-templating strategy.Interestingly,it has been found for the first time that the introduction of TEOA in the reaction effectively increases the ratio of high-valence Co^(3+)in the final product.Benefiting from the synergetic effect of the tailored high-valence Co^(3+)with the 3D network structure,the Co_(x)S_(y)-T NS electrode exhibits a maximum specific capacity of 351 mA h g^(-1)(2635 F g^(-1))at 5 A g^(-1)as well as excellent cycling stability.Furthermore,with the solid-state asymmetric supercapacitor(ASC)constructed based on the Co_(x)S_(y)-T NSs and activated carbon(AC)electrodes,a high energy density up to 81.62 W h kg^(-1)has been achieved at the power density of 0.81 kW kg^(-1)and 96.2%capacitance is preserved after 7000 cycles,indicating robust cycling stability.This result highlights the simple approach of simultaneously tailoring highvalence metal species and constructing 3D network structure toward high-performance electrode materials for energy storage and conversion.展开更多
Transition metal catalysts have been considerably used for NH3 decomposition because of the potential application in COx-free H2 generation for fuel cells. However, most transition metal catalysts prepared via traditi...Transition metal catalysts have been considerably used for NH3 decomposition because of the potential application in COx-free H2 generation for fuel cells. However, most transition metal catalysts prepared via traditional synthetic approaches performed the inferior stability due to the agglomeration of active components. Here, we adopted an efficient method, aerosol-assisted self- assembly approach （AASA）, to prepare the optimized cobalt-alumina （C0304-A1203） catalysts. The C0304-A1203 catalysts exhibited excellent catalytic performance in the NH3 decomposition reaction, which can reach 100% conversion at 600 ℃and maintain stable for 72 h at a gaseous hourly space velocity （GHSV） of 18000 cm3 gcat-1 h-1. The catalysts were characterized by various techniques including transmission electron microscope （TEM）, scanning electron microscope （SEM）, nitrogen sorption, temperature-programmed reduction by hydrogen （H2-TPR）, ex-situ/in-situ Raman and ex-situ/in-situ X-ray diffraction （XRD） to obtain the information about the structure and property of the catalysts. H2-TPR and in-situ XRD results show that there is strong interaction between the cobalt and alumina species, which influences the redox properties of the catalysts. It is found that even a low content of alumina （10 at%） is able to stabilize the catalysts due to the adequate dispersion and rational interaction between different components, which ensures the high activity and superior stability of the cobalt-alumina catalysts.展开更多
Water electrolysis is one of the most promising approaches for producing hydrogen.However,it has been hindered by the sluggishness of the anodic oxygen evolution reaction.In this work,we fabricated Ru-Co-Mn trimetalli...Water electrolysis is one of the most promising approaches for producing hydrogen.However,it has been hindered by the sluggishness of the anodic oxygen evolution reaction.In this work,we fabricated Ru-Co-Mn trimetallic alloy nanoparticles on N-doped carbon support(RuCoMn@NC)via the pyrolysis-adsorption-pyrolysis process using ZIF-67 as a precursor.The RuCoMn@NC catalyst exhibited excellent electrocatalytic performance for the hydrogen evolution reaction(HER)over a wide range of pH and glucose oxidation reaction in alkaline media.It showed exceptional HER activity in alkaline medium,superior to that of the commercial Pt/C catalyst(20 wt%),and good electrochemical stability.Further,a two-electrode alkaline electrolyzer pairing RuCoMn@NC as both cathode and anode was employed,and only a cell voltage of 1.63 V was required to attain a current density of 10 mA cm^(-2)in glucose electrolysis,which is about 270 mV lower than that in the overall water-splitting electrolyzer.This paper provides a promising method for developing efficiently bifunctional electrocatalysts driving redox electrocatalysis,and it would be beneficial to energy-saving electrolytic H_(2) production.展开更多
基金supported by the National Natural Science Foundation of China(21373037,21577013)China Postdoctoral Science Foundation(2014M560201)the Fundamental Research Funds for the Central Universities(DUT15TD49,DUT16ZD224)~~
文摘Gold stabilized on reducible oxide （CeO2 and FeOx） and irreducible oxide （γ‐Al2O3, SiO2, and HZSM‐5） were prepared by deposition precipitation method and tested for catalytic oxidation of formaldehyde （HCHO） at room temperature under high GHSV of 600000 ml/（g＆#183;s）. Au/γ‐Al2O3 cata‐lyst showed distinctive catalytic performance, presenting the highest initial HCHO conversion and stability. Correlating the reaction rate with Au particle size, there is a linear relationship, suggesting that the smaller Au particle size with higher dispersion possesses high reactivity for HCHO oxida‐tion. All the catalysts deactivated at high GHSV （600000 ml/（g＆#183;s））, but in a quite different rate. Re‐ducible oxide （CeO2 and FeOx） could stabilize gold through O linkage and therefore exhibits a better stability for HCHO oxidation reaction. However, the aggregation of gold particles occurred over Au/SiO2 and Au/HZSM‐5 catalysts, which result in the fast deactivation. Therefore, our results sug‐gest that the reducibility of the supports for Au catalysis has no direct influence on the activity, but affects the catalytic stability.
文摘Low optical absorption and photocorrosion are two crucial issues limiting the practical applications of zinc oxide(ZnO)-based photocatalysts.In this paper,we report the fabrication of graphitic-carbon-mediated ZnO nanorod arrays(NRAs)with enhanced photocatalytic activity and photostability for CO2 reduction under visible light irradiation.ZnO NRA/C-x(x=005,01,02,and 03)nanohybrids are prepared by calcining pre-synthesized ZnO NRAs with different amounts of glucose(0.05,0.1,0.2,and 0.3 g)as a carbon source via a hydrothermal method.X-ray photoelectron spectroscopy reveals that the obtained ZnO NRA/C-x nanohybrids are imparted with the effects of both carbon doping and carbon coating,as evidenced by the detected C-O-Zn bond and the C-C,C-O and C=O bonds,respectively.While the basic structure of ZnO remains unchanged,the UV-Vis absorption spectra show increased absorbance owing to the carbon doping effect in the ZnO NRA/C-x nanohybrids.The photoluminescence(PL)intensities of ZnO NRA/C-x nanohybrids are lower than that of bare ZnO NRA,indicating that the graphitic carbon layer coated on the surface of the ZnO NRA significantly enhances the charge carrier separation and transport,which in turn enhances the photoelectrochemical property and photocatalytic activity of the ZnO NRA/C-x nanohybrids for CO2 reduction.More importantly,a long-term reaction of photocatalytic CO2 reduction demonstrates that the photostability of ZnO NRA/C-x nanohybrids is significantly increased in comparison with the bare ZnO NRA.
文摘The present work establishes a systematic approach based on the application of in-situ Fourier transform infrared spectroscopy （FTIR） for the investigation of the crystal structure, thermal stability, redox behavior （temperature-programmed reduction/temperatureprogrammed re-oxidation） as well as the catalytic properties of Co3O4 thin films. The syntheses of Co3O4 were achieved by chemical vapor deposition in the temperature range of 400-500℃. The structure analysis of the as-prepared material revealed the presence of two prominent IR bands peaking at 544 cm-1 （υ1） and 650 cm-1 （υ2） respectively, which originate from the stretching vibrations of the Co-O bond, characteristic of the Co3O4 spinel. The lattice stability limit of Co3O4 was estimated to be above 650℃. The redox properties of the spinel structure were determined by integrating the area under the emission bands υ1 and υ2 as a function of the temperature. Moreover, Co3O4 has been successfully tested as a catalyst towards complete oxidation of dimethyl ether below 340 ℃. The exhaust gas analysis during the catalytic process by in situ absorption FTIR revealed that only CO2 and H2O were detected as the final products in the catalytic reaction. The redox behavior suggests that the oxidation of dimethyl ether over Co3O4 follows a Mars-van Krevelen type mechanism. The comprehensive application of in situ FTIR provides a novel diagnostic tool in characterization and performance test of catalysts.
文摘Tocopherol is the most active vitamin and natural antioxidant existing in the nature known as vitamin E. Lacking of this vitamin makes drastic exchanges on the health of the living organisms. Their active chemical form is l-α-tocopherol substance. In this article, α-thiotocopherol a tocopherol derivative was synthesized via a precursor like dl-α-tocopherol, which has better antioxidant than natural α-tocopherol. And the last compound after separation and purification via TLC and PC procedures was analyzed by FTIR, GC-MS and elemental analysis, oxidative stability is tested with TGA method in air showing roughly antioxidant effect. Another approach is measurment of redox potential against a reference electrode under inert nitrogen atmosphere.
基金the National Natural Science Foundation of China(21671173)Zhejiang Provincial Ten Thousand Talent Program(2017R52043)。
文摘Modulating the oxidation states of transition metal species has been regarded as a promising strategy to tune the redox activity and achieve more active sites in electrode materials.In this work,a unique three-dimensional(3D)honeycomb-like cobalt sulfide(Co_(x)S_(y))network organized by cross-linked nanosheets(Co_(x)S_(y)-T NSs)was prepared via a simple triethanolamine(TEOA)-assisted self-templating strategy.Interestingly,it has been found for the first time that the introduction of TEOA in the reaction effectively increases the ratio of high-valence Co^(3+)in the final product.Benefiting from the synergetic effect of the tailored high-valence Co^(3+)with the 3D network structure,the Co_(x)S_(y)-T NS electrode exhibits a maximum specific capacity of 351 mA h g^(-1)(2635 F g^(-1))at 5 A g^(-1)as well as excellent cycling stability.Furthermore,with the solid-state asymmetric supercapacitor(ASC)constructed based on the Co_(x)S_(y)-T NSs and activated carbon(AC)electrodes,a high energy density up to 81.62 W h kg^(-1)has been achieved at the power density of 0.81 kW kg^(-1)and 96.2%capacitance is preserved after 7000 cycles,indicating robust cycling stability.This result highlights the simple approach of simultaneously tailoring highvalence metal species and constructing 3D network structure toward high-performance electrode materials for energy storage and conversion.
基金supported by the National Natural Science Foundation of China (21622106, 21501109, 21771117)the Outstanding Scholar Fund from the Science Foundation of Shandong Province of China (JQ201703)the Taishan Scholar Project of Shandong Province of China
文摘Transition metal catalysts have been considerably used for NH3 decomposition because of the potential application in COx-free H2 generation for fuel cells. However, most transition metal catalysts prepared via traditional synthetic approaches performed the inferior stability due to the agglomeration of active components. Here, we adopted an efficient method, aerosol-assisted self- assembly approach （AASA）, to prepare the optimized cobalt-alumina （C0304-A1203） catalysts. The C0304-A1203 catalysts exhibited excellent catalytic performance in the NH3 decomposition reaction, which can reach 100% conversion at 600 ℃and maintain stable for 72 h at a gaseous hourly space velocity （GHSV） of 18000 cm3 gcat-1 h-1. The catalysts were characterized by various techniques including transmission electron microscope （TEM）, scanning electron microscope （SEM）, nitrogen sorption, temperature-programmed reduction by hydrogen （H2-TPR）, ex-situ/in-situ Raman and ex-situ/in-situ X-ray diffraction （XRD） to obtain the information about the structure and property of the catalysts. H2-TPR and in-situ XRD results show that there is strong interaction between the cobalt and alumina species, which influences the redox properties of the catalysts. It is found that even a low content of alumina （10 at%） is able to stabilize the catalysts due to the adequate dispersion and rational interaction between different components, which ensures the high activity and superior stability of the cobalt-alumina catalysts.
基金supported by the National Natural Science Foundation of China(52072035,51631001,21801015,51902023 and 51872030)the Fundamental Research Funds for the Central Universities(2017CX01003)+1 种基金Beijing Institute of Technology Research Fund Program for Young Scholarsthe Joint R&D Plan of Hong Kong,Macao,Taiwan,and Beijing(Z191100001619002).
文摘Water electrolysis is one of the most promising approaches for producing hydrogen.However,it has been hindered by the sluggishness of the anodic oxygen evolution reaction.In this work,we fabricated Ru-Co-Mn trimetallic alloy nanoparticles on N-doped carbon support(RuCoMn@NC)via the pyrolysis-adsorption-pyrolysis process using ZIF-67 as a precursor.The RuCoMn@NC catalyst exhibited excellent electrocatalytic performance for the hydrogen evolution reaction(HER)over a wide range of pH and glucose oxidation reaction in alkaline media.It showed exceptional HER activity in alkaline medium,superior to that of the commercial Pt/C catalyst(20 wt%),and good electrochemical stability.Further,a two-electrode alkaline electrolyzer pairing RuCoMn@NC as both cathode and anode was employed,and only a cell voltage of 1.63 V was required to attain a current density of 10 mA cm^(-2)in glucose electrolysis,which is about 270 mV lower than that in the overall water-splitting electrolyzer.This paper provides a promising method for developing efficiently bifunctional electrocatalysts driving redox electrocatalysis,and it would be beneficial to energy-saving electrolytic H_(2) production.
