TiO2-SnO2-SiO2 nanocomposite photocatalysts were prepared with Na2SiO3·9H2O, SnCl4·5H2O and TiCl4 as precursors by chemistry coating processes and supercritical fluid drying (SCFD) method. Characterizations ...TiO2-SnO2-SiO2 nanocomposite photocatalysts were prepared with Na2SiO3·9H2O, SnCl4·5H2O and TiCl4 as precursors by chemistry coating processes and supercritical fluid drying (SCFD) method. Characterizations with XRD, TEM, NMR and FTIR showed that in addition to anatase type TiO2, a new active phase(Ti,Sn)O2 was also formed in the range of the studied doping concentration, The catalytic activity was evaluated by photocatalytic degradation of phenol as model reaction. SiO2 remained amphorous at all samples. It could prevent from growth of the size of nanopaticle and transformation from anatase to rutile. Compared with pure TiO2, or TiO2-SnO2 catalyst prepared by Sol-gel method, Nano-composite photo-catalyst showed significant improvement in catalytic activity, the photo-catalytic degradation rate of phenol in 7 h reached 88.7%. Application of the composite catalysts for the photocatalytic decomposition of phenol not only gave the same activity relative to pure ultrafine TiO2, but also reduced cost. The experimental results also proved that the thermal stability of TiO2 was greatly enhanced after mixing with small amount of SiO2. The optimized doping of SiO2 was 20.3%. The photo-catalyst prepared by SCFD combination technology was characterized with smaller particle size, larger surface area and higher activity.展开更多
A kind of solar thermochemical cycle based on methanothermal reduction of SnO2 is proposed for H2 and CO production. We find that the oxygen release capacity and thermodynamic driven force for methanothermal reduction...A kind of solar thermochemical cycle based on methanothermal reduction of SnO2 is proposed for H2 and CO production. We find that the oxygen release capacity and thermodynamic driven force for methanothermal reduction of SnO2 are large, and suggest CH4 :SnO2 = 2:1 as the feasible reduction condition for achieving high purities of syngas and avoiding vaporization of produced Sn. Subsequently, the amount of H2 and energetic upgrade factors under different oxidation conditions are compared, in which excess water vapor is found beneficial for hydrogen production and fuel energetic upgradation. Moreover, the effect of incom plete recovery of SnO2 on the subsequent cycle is underscored and explained. After accounting for factors such as isothermal operation and cycle stability, CH4 :SnO2 = 2:1 and H2O:Sn = 4:1 are suggested for highest solar-to-fuel efficiency of 46.1% at nonisothermal condition, where the reduction and oxidation temperature are 1400 and 600 K, respectively.展开更多
A series of three‐dimensionally ordered macroporous(3DOM)SnO2‐based catalysts modified by the cations Ce4+,Mn3+,and Cu2+have been prepared by using a colloidal crystal templating method and tested for soot combustio...A series of three‐dimensionally ordered macroporous(3DOM)SnO2‐based catalysts modified by the cations Ce4+,Mn3+,and Cu2+have been prepared by using a colloidal crystal templating method and tested for soot combustion under loose contact condition.XRD and STEM mapping results confirm that all the secondary metal cations have entered the lattice matrix of tetragonal rutile SnO2 to form non‐continuous solid solutions,thus impeding crystallization and improving the surface areas and pore volumes of the modified catalysts.In comparison with regular SnO2 nanoparticles,the 3DOM SnO2 displays evidently improved activity,testifying that the formation of the 3DOM structure can anchor the soot particulates in the macro‐pores,which ensures that the contact of the soot particles with the active sites on the 3DOM skeleton is more easily formed,thus benefiting the target reaction.With the incorporation of the secondary metal cations,the activity of the catalyst can be further improved due to the formation of more abundant mobile oxygen species.In summary,these effects are believed to be the major factors responsible for the activity of the catalyst.展开更多
With the objective to investigate the structure-reactivity relationship of CuO/SnO2 and eventually design more applicable catalysts for soot combustion,catalysts with different CuO loadings have been prepared by impre...With the objective to investigate the structure-reactivity relationship of CuO/SnO2 and eventually design more applicable catalysts for soot combustion,catalysts with different CuO loadings have been prepared by impregnation method.By using X-ray diffraction and X-ray photoelectron spectroscopy extrapolation methods,it is disclosed that CuO disperses finely on the SnO2 support to form a monolayer with a capacity of 2.09 mmol 100 m^-2,which equals 4.8 wt%CuO loading.When the CuO loading is below the capacity,it is in a sub-monolayer state.However,when the loading is above the capacity,CuO micro-crystallites will be formed that coexist with the CuO monolayer.The soot combustion activity of the catalyst increases with the CuO loading until it reaches the monolayer dispersion capacity.A further increase in the CuO loading has no evident influence on the activity.Raman results have testified that with the addition of CuO onto the SnO2 support,a surface-active oxygen species can be formed,the amount of which also increases significantly with the increase in the CuO loading until it reaches the monolayer dispersion capacity.Increasing the CuO loading further has no evident impact on the amount of surface oxygen.Therefore,an apparent monolayer dispersion threshold effect is observed for soot combustion over CuO/SnO2 catalysts.It is concluded that the amount of surface-active oxygen sites is the major factor determining the activity of the catalyst.展开更多
Synergistic interplays involving multiple active centers originating from TiO2 nanotube layers(TNT)and ruthenium(Ru)species comprising of both single atoms(SAs)and nanoparticles(NPs)augment the alkaline hydrogen evolu...Synergistic interplays involving multiple active centers originating from TiO2 nanotube layers(TNT)and ruthenium(Ru)species comprising of both single atoms(SAs)and nanoparticles(NPs)augment the alkaline hydrogen evolution reaction(HER)by enhancing Volmer kinetics from rapid water dissociation and improving Tafel kinetics from efficient H*desorption.Atomic layer deposition of Ru with 50 process cycles results in a mixture of Ru SAs and 2.8-0.4 nm NPs present on TNT layers,and it emerges with the highest HER activity among all the electrodes synthesized.A detailed study of the Ti and Ru species using different high-resolution techniques confirmed the presence of Ti3+states and the coexistence of Ru SAs and NPs.With insights from literature,the role of Ti3+,appropriate work functions of TNT layers and Ru,and the synergistic effect of Ru SAs and Ru NPs in improving the performance of alkaline HER were elaborated and justified.The aforementioned characteristics led to a remarkable performance by having 9mV onset potentials and 33 mV dec-1 of Tafel slopes and a higher turnover frequency of 1.72 H2 s-1 at 30 mV.Besides,a notable stability from 28 h staircase chronopotentiometric measurements for TNT@Ru surpasses TNT@Pt in comparison.展开更多
摘要TiO2-SnO2-SiO2 nanocomposite photocatalysts were prepared with Na2SiO3·9H2O, SnCl4·5H2O and TiCl4 as precursors by chemistry coating processes and supercritical fluid drying (SCFD) method. Characterizations with XRD, TEM, NMR and FTIR showed that in addition to anatase type TiO2, a new active phase(Ti,Sn)O2 was also formed in the range of the studied doping concentration, The catalytic activity was evaluated by photocatalytic degradation of phenol as model reaction. SiO2 remained amphorous at all samples. It could prevent from growth of the size of nanopaticle and transformation from anatase to rutile. Compared with pure TiO2, or TiO2-SnO2 catalyst prepared by Sol-gel method, Nano-composite photo-catalyst showed significant improvement in catalytic activity, the photo-catalytic degradation rate of phenol in 7 h reached 88.7%. Application of the composite catalysts for the photocatalytic decomposition of phenol not only gave the same activity relative to pure ultrafine TiO2, but also reduced cost. The experimental results also proved that the thermal stability of TiO2 was greatly enhanced after mixing with small amount of SiO2. The optimized doping of SiO2 was 20.3%. The photo-catalyst prepared by SCFD combination technology was characterized with smaller particle size, larger surface area and higher activity.
基金supported by the National Key R&D Program of China (Grant no. 2018YFB1502005)the National Natural Science Foundation of China (Grant nos. 51476163 , 51806209 and 81801768)Institute of Electrical Engineering, Chinese Academy of Sciences (No.Y770111CSC)
摘要A kind of solar thermochemical cycle based on methanothermal reduction of SnO2 is proposed for H2 and CO production. We find that the oxygen release capacity and thermodynamic driven force for methanothermal reduction of SnO2 are large, and suggest CH4 :SnO2 = 2:1 as the feasible reduction condition for achieving high purities of syngas and avoiding vaporization of produced Sn. Subsequently, the amount of H2 and energetic upgrade factors under different oxidation conditions are compared, in which excess water vapor is found beneficial for hydrogen production and fuel energetic upgradation. Moreover, the effect of incom plete recovery of SnO2 on the subsequent cycle is underscored and explained. After accounting for factors such as isothermal operation and cycle stability, CH4 :SnO2 = 2:1 and H2O:Sn = 4:1 are suggested for highest solar-to-fuel efficiency of 46.1% at nonisothermal condition, where the reduction and oxidation temperature are 1400 and 600 K, respectively.
基金the Natural Science Foundation of China(21567016,21503106)the Natural Science Foundation of Jiangxi Province(20171BAB213013)+3 种基金the Education Department Foundation of Jiangxi Province(KJLD14005)National Key Research and Development Program of China(2016YFC0209302)the Innovation Fund Designated for Graduate Students of Jiangxi Province(YC2015-B017)the Innovation Fund Designated for Undergraduate Students of China(201701035)~~
摘要A series of three‐dimensionally ordered macroporous(3DOM)SnO2‐based catalysts modified by the cations Ce4+,Mn3+,and Cu2+have been prepared by using a colloidal crystal templating method and tested for soot combustion under loose contact condition.XRD and STEM mapping results confirm that all the secondary metal cations have entered the lattice matrix of tetragonal rutile SnO2 to form non‐continuous solid solutions,thus impeding crystallization and improving the surface areas and pore volumes of the modified catalysts.In comparison with regular SnO2 nanoparticles,the 3DOM SnO2 displays evidently improved activity,testifying that the formation of the 3DOM structure can anchor the soot particulates in the macro‐pores,which ensures that the contact of the soot particles with the active sites on the 3DOM skeleton is more easily formed,thus benefiting the target reaction.With the incorporation of the secondary metal cations,the activity of the catalyst can be further improved due to the formation of more abundant mobile oxygen species.In summary,these effects are believed to be the major factors responsible for the activity of the catalyst.
基金supported by the National Natural Science Foundation of China(21567016,21666020)the Natural Science Foundation of Jiangxi Province(20181ACB20005,20171BAB213013,20181BCD40004,20181BAB203017)+2 种基金the Innovation Fund Designated for Graduate Students of Jiangxi Province(YC2018-B015)the Education Department Foundation of Jiangxi Province(KJLD14005)the Opening Fund of Key Laboratory of Process Analysis and Control of Sichuan Universities(2017002)~~
摘要With the objective to investigate the structure-reactivity relationship of CuO/SnO2 and eventually design more applicable catalysts for soot combustion,catalysts with different CuO loadings have been prepared by impregnation method.By using X-ray diffraction and X-ray photoelectron spectroscopy extrapolation methods,it is disclosed that CuO disperses finely on the SnO2 support to form a monolayer with a capacity of 2.09 mmol 100 m^-2,which equals 4.8 wt%CuO loading.When the CuO loading is below the capacity,it is in a sub-monolayer state.However,when the loading is above the capacity,CuO micro-crystallites will be formed that coexist with the CuO monolayer.The soot combustion activity of the catalyst increases with the CuO loading until it reaches the monolayer dispersion capacity.A further increase in the CuO loading has no evident influence on the activity.Raman results have testified that with the addition of CuO onto the SnO2 support,a surface-active oxygen species can be formed,the amount of which also increases significantly with the increase in the CuO loading until it reaches the monolayer dispersion capacity.Increasing the CuO loading further has no evident impact on the amount of surface oxygen.Therefore,an apparent monolayer dispersion threshold effect is observed for soot combustion over CuO/SnO2 catalysts.It is concluded that the amount of surface-active oxygen sites is the major factor determining the activity of the catalyst.
基金support from the European Union Horizon 2020 program(project HERMES,nr.952184)the Ministry of Education,Youth and Sports of the Czech Republic for supporting CEMNAT(LM2023037)+1 种基金Czech-NanoLab(LM2023051)infrastructures for providing ALD,SEM,EDX,XPS,TEM,and XRDCzech Science Foundation(project 23-08019X,EXPRO).
摘要Synergistic interplays involving multiple active centers originating from TiO2 nanotube layers(TNT)and ruthenium(Ru)species comprising of both single atoms(SAs)and nanoparticles(NPs)augment the alkaline hydrogen evolution reaction(HER)by enhancing Volmer kinetics from rapid water dissociation and improving Tafel kinetics from efficient H*desorption.Atomic layer deposition of Ru with 50 process cycles results in a mixture of Ru SAs and 2.8-0.4 nm NPs present on TNT layers,and it emerges with the highest HER activity among all the electrodes synthesized.A detailed study of the Ti and Ru species using different high-resolution techniques confirmed the presence of Ti3+states and the coexistence of Ru SAs and NPs.With insights from literature,the role of Ti3+,appropriate work functions of TNT layers and Ru,and the synergistic effect of Ru SAs and Ru NPs in improving the performance of alkaline HER were elaborated and justified.The aforementioned characteristics led to a remarkable performance by having 9mV onset potentials and 33 mV dec-1 of Tafel slopes and a higher turnover frequency of 1.72 H2 s-1 at 30 mV.Besides,a notable stability from 28 h staircase chronopotentiometric measurements for TNT@Ru surpasses TNT@Pt in comparison.