A novel photocatalyst based on TiO2-PANI composite supported on small pieces of cork has been reported. It was prepared by simple impregnation method of the polyaniline（PANI）-modified TiO2 on cork. The TiO2-PANI/Cor...A novel photocatalyst based on TiO2-PANI composite supported on small pieces of cork has been reported. It was prepared by simple impregnation method of the polyaniline（PANI）-modified TiO2 on cork. The TiO2-PANI/Cork catalyst shows the unique feature of floating on the water surface. The as-synthesized catalyst was characterized by X-ray diffraction（XRD）,scanning electron micrograph（SEM）, transmission electron microscopy（TEM）, thermogravimetric analysis（TGA）, Fourier transform infrared spectroscopy（FT-IR）, UV-vis diffuse reflectance spectra（UV-vis DRS） and the Brunauer-Emmett-Teller（BET） surface area analysis. Characterization suggested the formation of anatase highly dispersed on the cork surface. The prepared floating photocatalyst showed high efficiency for the degradation of methyl orange dye and other organic pollutants under solar irradiation and constrained conditions, i.e., no-stirring and no-oxygenation. The TiO2-PANI/Cork floating photocatalyst can be reused for at least four consecutive times without significant decrease of the degradation efficiency.展开更多
Potassium promoted iron–zinc catalysts prepared by co-precipitation method(C–Fe–Zn/K),solvothermal method(S–Fe–Zn/K)and hydrothermal method(H–Fe–Zn/K)could selectively convert CO_2to light olefins,respectively....Potassium promoted iron–zinc catalysts prepared by co-precipitation method(C–Fe–Zn/K),solvothermal method(S–Fe–Zn/K)and hydrothermal method(H–Fe–Zn/K)could selectively convert CO_2to light olefins,respectively.The physicochemical properties of the obtained catalysts were determined by SEM,N_2physisorption,XRD,H_2-TPR,CO_2-TPD and XPS measurements.The results demonstrated that preparation methods had great influences on the morphology,phase structures,reduction and adsorption behavior,and hence the catalytic performance of the catalysts.The samples prepared by hydrothermal and co-precipitation method generated small uniform particles and led to lower specific surface area.In contrast,microspheres with larger specific surface area were formed by self-assembly of nanosheets using solvothermal method.ZnFe_2O_4was the only detectable phase in the fresh C–2Fe–1Zn/K,S–3Fe–1Zn/K and S–2Fe–1Zn/K samples.ZnFe_2O_4and ZnO co-existed with increasing Zncontent in S–1Fe–1Zn/K sample,while ZnO and Fe_2O_3could be observed over H–2Fe–1Zn/K sample.All the used samples contained Fe_3O_4,ZnO and Fe_5C_2.The peak intensity of ZnO was strong in the AR-H–2Fe–1Zn/K sample while it was the lowest in the AR-C–2Fe–1Zn/K sample after reaction.The formation of ZnFe_2O_4increased the interaction between iron and zinc for C–2Fe–1Zn/K and S–Fe–Zn/K samples,causing easier reduction of Fe_2O_3to Fe_3O_4.The surface basicity of the sample prepared by co-precipitation method was much more than that of the other two methods.During CO_2hydrogenation,all the catalysts showed good activity and olefin selectivity.The CO selectivity was increased with increasing Zncontent over S–Fe–Zn/K samples.H–2Fe–1Zn/K catalyst preferred to the production of C_5^+hydrocarbons.CO_2conversion of 54.76%and C_2~=–C_4~=contents of 57.38%were obtained on C–2Fe–1Zn/K sample,respectively.展开更多
A systematic study was carried out to investigate the promotion effect of manganese on the performance of a coprecipitated iron-manganese bimetallic catalyst for the light olefins synthesis from syngas. The catalyst s...A systematic study was carried out to investigate the promotion effect of manganese on the performance of a coprecipitated iron-manganese bimetallic catalyst for the light olefins synthesis from syngas. The catalyst samples were characterized by N2 physisorption, transmis- sion electron microscopy （TEM）, X-ray photoelectron spectroscopy （XPS）, powder X-ray diffraction （XRD）, Mossbauer spectroscopy, H2- differential thermogravimetric analysis （H2-DTG）, CO temperature-programmed reduction （CO-TPR） and CO2 temperature-programmed des- orption （CO2-TPD）. The Fischer-Tropsch synthesis （FTS） performance of the catalyst was measured at 1.5 MPa, 250 ℃ and syngas with H2/CO ratio of 2.0. The characterization results indicated that the addition of manganese decreases the catalyst crystallite size, and improves the catalyst BET surface area and pore volume. The presence of manganese suppresses the catalyst reduction and carburization in H2, CO and syngas, respectively. The addition of manganese improves the catalytic activity of water-gas shift reaction and suppresses the oxidation of iron carbides in the FTS reaction. The incorporation of manganese improves the catalyst surface basicity and results in a significant improvement in the selectivities to light olefins and heavy hydrocarbons （C5＋）, and furthermore an inhibition of methane formation in FTS. The pure iron catalyst （Mn-00） has the highest initial FTS catalytic activity （65%） and the lowest selectivity （17.35 wt%） to light olefins （C2=-C4=）. The addition of an appropriate amount of manganese can improve the catalyst FTS activity.展开更多
The isomerization of light paraffin over HZSM-5-Ni-Mo-F synthetic zeolite catalysts was studied, and the effects of reaction conditions on the isomerization were investigated. The results show that the optimum reactio...The isomerization of light paraffin over HZSM-5-Ni-Mo-F synthetic zeolite catalysts was studied, and the effects of reaction conditions on the isomerization were investigated. The results show that the optimum reaction condition can be obtained to enhance the research octane number (RON) of product and the liquid yield. The optimum experimental condition is: HZSM-5 catalyst with 1.5wt% of Ni, 2wt% of Mo and 0.4wt% of F, at a temperature of 345℃ and a reaction mass hourly space velocity (MHSV) of 0.2 h-1. The isomerization reaction of light paraffin from Tarim refinery was studied and the research octane number (RON) of gasoline product could be enhanced by 20 units under the condition of nonhydrogenization and optimum experimental status.展开更多
Visible-light responsive TiO2-V2O5 catalyst was prepared using a binary sol-gel and in-situ intercalation method. The TiO2 sol and V2O5 sol were mixed to disperse the V2O5 species in the TiO2 phase at molecular level....Visible-light responsive TiO2-V2O5 catalyst was prepared using a binary sol-gel and in-situ intercalation method. The TiO2 sol and V2O5 sol were mixed to disperse the V2O5 species in the TiO2 phase at molecular level. The binary sol was then intercalated into interspaces of polyaniline （PANI） by means of in-situ polymerization of aniline. Conglomeration of the TiO2-V2O5 dusters during the calcination process was avoided because of the wrap of polyaniline. The surface mor- phology, the crystal phases, the structure, and the absorption spectra of （PANI）,/TiO2-V2O5 and the composite catalyst were studied using SEM, XRD, FT-IR, and UV-Vis. The photoactivity of the prepared catalyst under UV and visible light irradiation were evaluated by decolorization of methylene blue （MB） solution. The results showed that the composite catalyst displayed a homogeneous anatase phase, and the vanadium pentoxide species was highly dispersed in the TiO2 phase. The composite catalyst responded to visible light because of the narrowed band gap. In this study, the catalyst with the sol volume ratio of TiO2： V2O5 = 10：1 presented the best photocatalytic activity.展开更多
Water oxidation, as a mandatory reaction of solar fuels conversion systems, requires the use of light absorbers with electronic properties that are well matched with those of the multi-electron catalyst in order to ac...Water oxidation, as a mandatory reaction of solar fuels conversion systems, requires the use of light absorbers with electronic properties that are well matched with those of the multi-electron catalyst in order to achieve high efficiency. Molecular light absorbers offer flexibility in fine tuning of orbital energetics,and metal oxide nanoparticles have emerged as robust oxygen evolving catalysts. Hence, these material choices offer a promising approach for the development of photocatalytic systems for water oxidation.However, efficient charge transfer coupling of molecular light absorbers and metal oxide nanoparticle catalysts has proven a challenge. Recent new approaches toward the efficient coupling of these components based on synthetic design improvements combined with direct spectroscopic observation and kinetic evaluation of charge transfer processes are discussed.展开更多
A new highly efficient, visible light active, silver vanadate/polymeric carbonitride “core/shell” photocatalyst was prepared mechano-chemically prepared by grinding mixtures of <i><span><span style=&q...A new highly efficient, visible light active, silver vanadate/polymeric carbonitride “core/shell” photocatalyst was prepared mechano-chemically prepared by grinding mixtures of <i><span><span style="white-space:nowrap;">β</span></span></i><span>-silver vanadate and mesoporous graphitic carbonitride. Besides the core/shell photocatalyst, </span><i><span><span style="white-space:nowrap;">β</span></span></i><span>-silver vanadate/mesoporous polymeric carbonitride composites and supported mpg-C</span><sub><span>3</span></sub><span>N</span><sub><span>4</span></sub><span><span style="white-space:nowrap;">@</span></span><i><span><span style="white-space:nowrap;">β</span></span></i><span>-silver vanadates were prepared. The materials were characterized by transmission elec</span><span>tron microscopy (TEM), X-ray diffraction (XRD), nitrogen ad- and</span><span> de-sorption, diffuse reflectance UV-Vis measurement (DRS), infrared spectroscopy, Raman microscopy, and time-resolved photoluminescence spectroscopy. The photocatalytic performance of the materials was investigated in the degradation of organics using pharmaceutical ibuprofen and 4-(isobutyl phenyl) propionic acid sodium salt as model compounds under batch conditions. Reaction intermediates were studied by electrospray ionization and time-of-flight mass spectrometry (ESI-TOF-MS). Additionally, the degree of mineralization was determined by total organic carbon TOC measurements. The core/shell photocatalyst has shown superior photocatalytic activity compared to the other prepared composites or supported photocatalysts as well as the single mpg-C</span><sub><span>3</span></sub><span>N</span><sub><span>4</span></sub><span>. Scavenger experiments showed that valence band holes and anio</span><span>nic superoxide radicals are the main active species in the photocatalytic</span><span> process. TOC measurement confirmed the mineralization of the organic compound, which was in line with ESI-TOF-MS experiments. Time-resolved photoluminescence measurements indicated that charges generated in carbonitride migrate via diffusive hopping and exhibit increased mobility in the case of the silver vanadate/polymeric carbonitride composite.</span>展开更多
文摘A novel photocatalyst based on TiO2-PANI composite supported on small pieces of cork has been reported. It was prepared by simple impregnation method of the polyaniline（PANI）-modified TiO2 on cork. The TiO2-PANI/Cork catalyst shows the unique feature of floating on the water surface. The as-synthesized catalyst was characterized by X-ray diffraction（XRD）,scanning electron micrograph（SEM）, transmission electron microscopy（TEM）, thermogravimetric analysis（TGA）, Fourier transform infrared spectroscopy（FT-IR）, UV-vis diffuse reflectance spectra（UV-vis DRS） and the Brunauer-Emmett-Teller（BET） surface area analysis. Characterization suggested the formation of anatase highly dispersed on the cork surface. The prepared floating photocatalyst showed high efficiency for the degradation of methyl orange dye and other organic pollutants under solar irradiation and constrained conditions, i.e., no-stirring and no-oxygenation. The TiO2-PANI/Cork floating photocatalyst can be reused for at least four consecutive times without significant decrease of the degradation efficiency.
基金Supports by the National Natural Science Foundation of China(21666030,21366025)National First-rate Discipline Construction Project of Ningxia(NXYLXK2017A04)
文摘Potassium promoted iron–zinc catalysts prepared by co-precipitation method(C–Fe–Zn/K),solvothermal method(S–Fe–Zn/K)and hydrothermal method(H–Fe–Zn/K)could selectively convert CO_2to light olefins,respectively.The physicochemical properties of the obtained catalysts were determined by SEM,N_2physisorption,XRD,H_2-TPR,CO_2-TPD and XPS measurements.The results demonstrated that preparation methods had great influences on the morphology,phase structures,reduction and adsorption behavior,and hence the catalytic performance of the catalysts.The samples prepared by hydrothermal and co-precipitation method generated small uniform particles and led to lower specific surface area.In contrast,microspheres with larger specific surface area were formed by self-assembly of nanosheets using solvothermal method.ZnFe_2O_4was the only detectable phase in the fresh C–2Fe–1Zn/K,S–3Fe–1Zn/K and S–2Fe–1Zn/K samples.ZnFe_2O_4and ZnO co-existed with increasing Zncontent in S–1Fe–1Zn/K sample,while ZnO and Fe_2O_3could be observed over H–2Fe–1Zn/K sample.All the used samples contained Fe_3O_4,ZnO and Fe_5C_2.The peak intensity of ZnO was strong in the AR-H–2Fe–1Zn/K sample while it was the lowest in the AR-C–2Fe–1Zn/K sample after reaction.The formation of ZnFe_2O_4increased the interaction between iron and zinc for C–2Fe–1Zn/K and S–Fe–Zn/K samples,causing easier reduction of Fe_2O_3to Fe_3O_4.The surface basicity of the sample prepared by co-precipitation method was much more than that of the other two methods.During CO_2hydrogenation,all the catalysts showed good activity and olefin selectivity.The CO selectivity was increased with increasing Zncontent over S–Fe–Zn/K samples.H–2Fe–1Zn/K catalyst preferred to the production of C_5^+hydrocarbons.CO_2conversion of 54.76%and C_2~=–C_4~=contents of 57.38%were obtained on C–2Fe–1Zn/K sample,respectively.
基金supported by Natural Science Foundation of Chongqing Three Gorges University (12ZD14)Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, Southeast University
文摘A systematic study was carried out to investigate the promotion effect of manganese on the performance of a coprecipitated iron-manganese bimetallic catalyst for the light olefins synthesis from syngas. The catalyst samples were characterized by N2 physisorption, transmis- sion electron microscopy （TEM）, X-ray photoelectron spectroscopy （XPS）, powder X-ray diffraction （XRD）, Mossbauer spectroscopy, H2- differential thermogravimetric analysis （H2-DTG）, CO temperature-programmed reduction （CO-TPR） and CO2 temperature-programmed des- orption （CO2-TPD）. The Fischer-Tropsch synthesis （FTS） performance of the catalyst was measured at 1.5 MPa, 250 ℃ and syngas with H2/CO ratio of 2.0. The characterization results indicated that the addition of manganese decreases the catalyst crystallite size, and improves the catalyst BET surface area and pore volume. The presence of manganese suppresses the catalyst reduction and carburization in H2, CO and syngas, respectively. The addition of manganese improves the catalytic activity of water-gas shift reaction and suppresses the oxidation of iron carbides in the FTS reaction. The incorporation of manganese improves the catalyst surface basicity and results in a significant improvement in the selectivities to light olefins and heavy hydrocarbons （C5＋）, and furthermore an inhibition of methane formation in FTS. The pure iron catalyst （Mn-00） has the highest initial FTS catalytic activity （65%） and the lowest selectivity （17.35 wt%） to light olefins （C2=-C4=）. The addition of an appropriate amount of manganese can improve the catalyst FTS activity.
文摘The isomerization of light paraffin over HZSM-5-Ni-Mo-F synthetic zeolite catalysts was studied, and the effects of reaction conditions on the isomerization were investigated. The results show that the optimum reaction condition can be obtained to enhance the research octane number (RON) of product and the liquid yield. The optimum experimental condition is: HZSM-5 catalyst with 1.5wt% of Ni, 2wt% of Mo and 0.4wt% of F, at a temperature of 345℃ and a reaction mass hourly space velocity (MHSV) of 0.2 h-1. The isomerization reaction of light paraffin from Tarim refinery was studied and the research octane number (RON) of gasoline product could be enhanced by 20 units under the condition of nonhydrogenization and optimum experimental status.
文摘Visible-light responsive TiO2-V2O5 catalyst was prepared using a binary sol-gel and in-situ intercalation method. The TiO2 sol and V2O5 sol were mixed to disperse the V2O5 species in the TiO2 phase at molecular level. The binary sol was then intercalated into interspaces of polyaniline （PANI） by means of in-situ polymerization of aniline. Conglomeration of the TiO2-V2O5 dusters during the calcination process was avoided because of the wrap of polyaniline. The surface mor- phology, the crystal phases, the structure, and the absorption spectra of （PANI）,/TiO2-V2O5 and the composite catalyst were studied using SEM, XRD, FT-IR, and UV-Vis. The photoactivity of the prepared catalyst under UV and visible light irradiation were evaluated by decolorization of methylene blue （MB） solution. The results showed that the composite catalyst displayed a homogeneous anatase phase, and the vanadium pentoxide species was highly dispersed in the TiO2 phase. The composite catalyst responded to visible light because of the narrowed band gap. In this study, the catalyst with the sol volume ratio of TiO2： V2O5 = 10：1 presented the best photocatalytic activity.
基金supported by the Director,Office of Science,Office of Basic Energy Sciences,Division of Chemical,Geological and Biosciences of the U.S.Department of Energy under Contract No.DE-AC02-05CH11231
文摘Water oxidation, as a mandatory reaction of solar fuels conversion systems, requires the use of light absorbers with electronic properties that are well matched with those of the multi-electron catalyst in order to achieve high efficiency. Molecular light absorbers offer flexibility in fine tuning of orbital energetics,and metal oxide nanoparticles have emerged as robust oxygen evolving catalysts. Hence, these material choices offer a promising approach for the development of photocatalytic systems for water oxidation.However, efficient charge transfer coupling of molecular light absorbers and metal oxide nanoparticle catalysts has proven a challenge. Recent new approaches toward the efficient coupling of these components based on synthetic design improvements combined with direct spectroscopic observation and kinetic evaluation of charge transfer processes are discussed.
文摘A new highly efficient, visible light active, silver vanadate/polymeric carbonitride “core/shell” photocatalyst was prepared mechano-chemically prepared by grinding mixtures of <i><span><span style="white-space:nowrap;">β</span></span></i><span>-silver vanadate and mesoporous graphitic carbonitride. Besides the core/shell photocatalyst, </span><i><span><span style="white-space:nowrap;">β</span></span></i><span>-silver vanadate/mesoporous polymeric carbonitride composites and supported mpg-C</span><sub><span>3</span></sub><span>N</span><sub><span>4</span></sub><span><span style="white-space:nowrap;">@</span></span><i><span><span style="white-space:nowrap;">β</span></span></i><span>-silver vanadates were prepared. The materials were characterized by transmission elec</span><span>tron microscopy (TEM), X-ray diffraction (XRD), nitrogen ad- and</span><span> de-sorption, diffuse reflectance UV-Vis measurement (DRS), infrared spectroscopy, Raman microscopy, and time-resolved photoluminescence spectroscopy. The photocatalytic performance of the materials was investigated in the degradation of organics using pharmaceutical ibuprofen and 4-(isobutyl phenyl) propionic acid sodium salt as model compounds under batch conditions. Reaction intermediates were studied by electrospray ionization and time-of-flight mass spectrometry (ESI-TOF-MS). Additionally, the degree of mineralization was determined by total organic carbon TOC measurements. The core/shell photocatalyst has shown superior photocatalytic activity compared to the other prepared composites or supported photocatalysts as well as the single mpg-C</span><sub><span>3</span></sub><span>N</span><sub><span>4</span></sub><span>. Scavenger experiments showed that valence band holes and anio</span><span>nic superoxide radicals are the main active species in the photocatalytic</span><span> process. TOC measurement confirmed the mineralization of the organic compound, which was in line with ESI-TOF-MS experiments. Time-resolved photoluminescence measurements indicated that charges generated in carbonitride migrate via diffusive hopping and exhibit increased mobility in the case of the silver vanadate/polymeric carbonitride composite.</span>
