The development of bifunctional electrocatalysts for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)at high current density under industrial temperatures is crucial for large-scale industrial hydrog...The development of bifunctional electrocatalysts for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)at high current density under industrial temperatures is crucial for large-scale industrial hydrogen production from water splitting.In this work,M-MnO_(2)@TNTA composite electrodes were prepared by depositing various metal ion-doped manganese oxide nanoparticles on the titania nanotube array(TNTA)by successive ionic layer adsorption reaction(SILAR)method,and their HER and OER electrocatalytic performances were investigated in 1 M KOH.Results show that the CoFe-MnO_(2)@TNTA composite electrode prepared by simultaneous doping of Co^(3+)and Fe^(3+)in MnO_(2) exhibits optimal catalytic performance.Compared with MnO_(2)@TNTA without ion doping,the overpotentials of CoFe-MnO_(2)@TNTA at 10 mA cm^(-2)(η_(10))for HER and OER are reduced by 571 and 665 mV.In addition,the electrode perfor-mance can be significantly enhanced by increasing the test temperature,and the porous array structure enables CoFe-MnO_(2)@TNTA to exhibit better performance at high current densities.At 50℃,which is the common industrial electrolytic water temperature,the η_(10) of CoFe-MnO_(2)@TNTA for HER is almost equal to that of the Pt/C electrode.The η_(100) of CoFe-MnO_(2)@TNTA for HER is reduced by 35 mV compared with the Pt/C electrode.Moreover,η_(200) of CoFe-MnO_(2)@TNTA for OER is significantly lowered by 111 and 184 mV compared with IrO_(2) and RuO_(2) electrodes.Utilizing CoFe-MnO_(2)@TNTA as both the cathode and anode for overall water splitting,the electrolysis voltage is merely 2.33 V under the current density of 200 mA cm^(-2),much lower than that of IrO_(2)(+)||Pt/C(-)(2.68 V).The present work may provide a valuable reference for the development of self-supporting bifunctional electrodes suitable for high-current-density water splitting at industrial temperatures.展开更多
The effects of additive agents and growth behavior of perovskite phase as well as temperature change of slag at semi industry scale test were studied. The results show that the increase of steel slag does good to tita...The effects of additive agents and growth behavior of perovskite phase as well as temperature change of slag at semi industry scale test were studied. The results show that the increase of steel slag does good to titania enrichment, however, it isn’t useful for the growth and coarsening of the perovskite phase. The additive Si-Fe powder can promote titania enrichment and make perovskite phase grow up easily. While air is blown into the molten slag, the reduced components in slag are oxidized and the released heat raises the temperature of slag.展开更多
The catalytic hydrogenation of p-nitrophenol to p-aminophenol was investigated over Ni/TiO2 catalysts prepared by a liquid-phase chemical reduction method. The catalysts were characterized by inductively coupled plasm...The catalytic hydrogenation of p-nitrophenol to p-aminophenol was investigated over Ni/TiO2 catalysts prepared by a liquid-phase chemical reduction method. The catalysts were characterized by inductively coupled plasma (ICP), X-ray powder diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS) and temperature-programmed reduction (TPR). Results show that the titania structure has favorable influence on physio-chemical and catalytic properties of Ni/TiO2 catalysts. Compared to commercial Raney nickel, the catalytic activity of Ni/TiO2 catalyst is much superior, irrespective of the titania structure. The catalytic activity of anatase titania supported nickel catalyst Ni/TiO2(A) is higher than that of rutile titania supported nickel catalyst Ni/TiO2(R), possibly because the reduction of nickel oxide to metallic nickel for Ni/TiO2(A) is easier than that for Ni/TiO2(R) at similar reaction conditions.展开更多
Solar-powered carbon dioxide （CO_2）-to-fuel conversion presents itself as an ideal solution for both CO_2 mit- igation and the rapidly growing world energy demand. In this work, the heating effect of light irradiati...Solar-powered carbon dioxide （CO_2）-to-fuel conversion presents itself as an ideal solution for both CO_2 mit- igation and the rapidly growing world energy demand. In this work, the heating effect of light irradiation onto a bed of supported nickel （Ni） catalyst was utilized to facilitate CO_2 conversion. Ceria （CeO_2）-titania （TiO_2） oxide supports of different compositions were employed and their effects on photothermal CO_2 conver- sion examined, Two factors are shown to be crucial for instigating photothermal CO_2 methanation activity： ① Fine nickel deposits are required for both higher active catalyst area and greater light absorption capacity for the initial heating of the catalyst bed; and ② the presence of defect sites on the support are necessary to promote adsorption of C02 for its subsequent activation, Titania inclusion within the support plays a crucial role in maintaining the oxygen vacancy defect sites on the （titanium-doped） cerium oxide. The combination of elevated light absorption and stabilized reduced states for CO_2 adsorption subsequently invokes effective Dhotothermal CO_2 methanation when the ceria and titania are blended in the ideal ratio（s）.展开更多
The expandable graphite(EG)modified TiO_(2) nanocomposites were prepared by the high shearmethod using the TiO_(2) nanoparticles(NPs)and EG as precursors,in which the amount of EG doped in TiO_(2) was 10 wt.%.Followed...The expandable graphite(EG)modified TiO_(2) nanocomposites were prepared by the high shearmethod using the TiO_(2) nanoparticles(NPs)and EG as precursors,in which the amount of EG doped in TiO_(2) was 10 wt.%.Followed by the impregnation method,adjusting the pH of the solution to 10,and using the electrostatic adsorption to achieve spatial confinement,the Pt elementswere mainly distributed on the exposed TiO_(2),thus generating the Pt/10EG-TiO_(2)-10 catalyst.The best CO oxidation activity with the excellent resistance to H_(2)O and SO_(2) was obtained over the Pt/10EG-TiO_(2)-10 catalyst:CO conversion after 36 hr of the reaction was ca.85%under the harsh condition of 10 vol.%H_(2)O and 100 ppm SO_(2) at a high gaseous hourly space velocity(GHSV)of 400,000 hr−1.Physicochemical properties of the catalystswere characterized by various techniques.The results showed that the electrostatic adsorption,which riveted the Pt elements mainly on the exposed TiO_(2) of the support surface,reduced the dispersion of Pt NPs on EG and achieved the effective dispersion of Pt NPs,hence significantly improving CO oxidation activity over the Pt/10EG-TiO_(2)-10 catalyst.The 10 wt.%EG doped in TiO_(2) caused the TiO_(2) support to form a more hydrophobic surface,which reduced the adsorption of H_(2)O and SO_(2) on the catalyst,greatly inhibited deposition of the TiOSO_(4) and formation of the PtSO4 species as well as suppressed the oxidation of SO_(2),thus resulting in an improvement in the resistance to H_(2)O and SO_(2) of the Pt/10EG-TiO_(2)-10 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 Ti^(3+)states and the coexistence of Ru SAs and NPs.With insights from literature,the role of Ti^(3+),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
We prepared TiO 2(anatase) and Sn doped TiO 2 nanoparticlate film by Plasma enhanced Chemical Vapor Deposition(PECVD) method. XRD and XPS experiments showed that Sn was doped into the lattice of TiO 2 with a ratio of ...We prepared TiO 2(anatase) and Sn doped TiO 2 nanoparticlate film by Plasma enhanced Chemical Vapor Deposition(PECVD) method. XRD and XPS experiments showed that Sn was doped into the lattice of TiO 2 with a ratio of n (Sn)∶ n (Ti)=1∶10 . Sn doping largely enhanced the photocatalytic activity of TiO 2 film for phenol degradation. The enhancement in photoactivity by doping was discussed, based on the characterization with AFM, FTIR and EFISPS. Sn doping produced localized level of Sn 4+ in the band gap of TiO 2, about 0.4 eV below the conduction band, which could capture photogenerated electrons and reduce O 2 adsorbed on the surface of TiO 2 film, thus accelerated the photocatalytic reaction.展开更多
基金financially supported by the National Natural Science Foundation of China(No.51972095).
文摘The development of bifunctional electrocatalysts for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)at high current density under industrial temperatures is crucial for large-scale industrial hydrogen production from water splitting.In this work,M-MnO_(2)@TNTA composite electrodes were prepared by depositing various metal ion-doped manganese oxide nanoparticles on the titania nanotube array(TNTA)by successive ionic layer adsorption reaction(SILAR)method,and their HER and OER electrocatalytic performances were investigated in 1 M KOH.Results show that the CoFe-MnO_(2)@TNTA composite electrode prepared by simultaneous doping of Co^(3+)and Fe^(3+)in MnO_(2) exhibits optimal catalytic performance.Compared with MnO_(2)@TNTA without ion doping,the overpotentials of CoFe-MnO_(2)@TNTA at 10 mA cm^(-2)(η_(10))for HER and OER are reduced by 571 and 665 mV.In addition,the electrode perfor-mance can be significantly enhanced by increasing the test temperature,and the porous array structure enables CoFe-MnO_(2)@TNTA to exhibit better performance at high current densities.At 50℃,which is the common industrial electrolytic water temperature,the η_(10) of CoFe-MnO_(2)@TNTA for HER is almost equal to that of the Pt/C electrode.The η_(100) of CoFe-MnO_(2)@TNTA for HER is reduced by 35 mV compared with the Pt/C electrode.Moreover,η_(200) of CoFe-MnO_(2)@TNTA for OER is significantly lowered by 111 and 184 mV compared with IrO_(2) and RuO_(2) electrodes.Utilizing CoFe-MnO_(2)@TNTA as both the cathode and anode for overall water splitting,the electrolysis voltage is merely 2.33 V under the current density of 200 mA cm^(-2),much lower than that of IrO_(2)(+)||Pt/C(-)(2.68 V).The present work may provide a valuable reference for the development of self-supporting bifunctional electrodes suitable for high-current-density water splitting at industrial temperatures.
基金Project(50234040) supported by the National Natural Science Foundation of China
文摘The effects of additive agents and growth behavior of perovskite phase as well as temperature change of slag at semi industry scale test were studied. The results show that the increase of steel slag does good to titania enrichment, however, it isn’t useful for the growth and coarsening of the perovskite phase. The additive Si-Fe powder can promote titania enrichment and make perovskite phase grow up easily. While air is blown into the molten slag, the reduced components in slag are oxidized and the released heat raises the temperature of slag.
基金Supported by the National Basic Research Program (No.2003CB615702) and the National Natural Science Foundation of Chin(No.20436030).
文摘The catalytic hydrogenation of p-nitrophenol to p-aminophenol was investigated over Ni/TiO2 catalysts prepared by a liquid-phase chemical reduction method. The catalysts were characterized by inductively coupled plasma (ICP), X-ray powder diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS) and temperature-programmed reduction (TPR). Results show that the titania structure has favorable influence on physio-chemical and catalytic properties of Ni/TiO2 catalysts. Compared to commercial Raney nickel, the catalytic activity of Ni/TiO2 catalyst is much superior, irrespective of the titania structure. The catalytic activity of anatase titania supported nickel catalyst Ni/TiO2(A) is higher than that of rutile titania supported nickel catalyst Ni/TiO2(R), possibly because the reduction of nickel oxide to metallic nickel for Ni/TiO2(A) is easier than that for Ni/TiO2(R) at similar reaction conditions.
基金financially supported by the Australian Research Council under the Laureate Fellowship Scheme (FL140100081)
文摘Solar-powered carbon dioxide （CO_2）-to-fuel conversion presents itself as an ideal solution for both CO_2 mit- igation and the rapidly growing world energy demand. In this work, the heating effect of light irradiation onto a bed of supported nickel （Ni） catalyst was utilized to facilitate CO_2 conversion. Ceria （CeO_2）-titania （TiO_2） oxide supports of different compositions were employed and their effects on photothermal CO_2 conver- sion examined, Two factors are shown to be crucial for instigating photothermal CO_2 methanation activity： ① Fine nickel deposits are required for both higher active catalyst area and greater light absorption capacity for the initial heating of the catalyst bed; and ② the presence of defect sites on the support are necessary to promote adsorption of C02 for its subsequent activation, Titania inclusion within the support plays a crucial role in maintaining the oxygen vacancy defect sites on the （titanium-doped） cerium oxide. The combination of elevated light absorption and stabilized reduced states for CO_2 adsorption subsequently invokes effective Dhotothermal CO_2 methanation when the ceria and titania are blended in the ideal ratio（s）.
基金supported by the National Key R&D Program of China (No.2017YFC0210303).
文摘The expandable graphite(EG)modified TiO_(2) nanocomposites were prepared by the high shearmethod using the TiO_(2) nanoparticles(NPs)and EG as precursors,in which the amount of EG doped in TiO_(2) was 10 wt.%.Followed by the impregnation method,adjusting the pH of the solution to 10,and using the electrostatic adsorption to achieve spatial confinement,the Pt elementswere mainly distributed on the exposed TiO_(2),thus generating the Pt/10EG-TiO_(2)-10 catalyst.The best CO oxidation activity with the excellent resistance to H_(2)O and SO_(2) was obtained over the Pt/10EG-TiO_(2)-10 catalyst:CO conversion after 36 hr of the reaction was ca.85%under the harsh condition of 10 vol.%H_(2)O and 100 ppm SO_(2) at a high gaseous hourly space velocity(GHSV)of 400,000 hr−1.Physicochemical properties of the catalystswere characterized by various techniques.The results showed that the electrostatic adsorption,which riveted the Pt elements mainly on the exposed TiO_(2) of the support surface,reduced the dispersion of Pt NPs on EG and achieved the effective dispersion of Pt NPs,hence significantly improving CO oxidation activity over the Pt/10EG-TiO_(2)-10 catalyst.The 10 wt.%EG doped in TiO_(2) caused the TiO_(2) support to form a more hydrophobic surface,which reduced the adsorption of H_(2)O and SO_(2) on the catalyst,greatly inhibited deposition of the TiOSO_(4) and formation of the PtSO4 species as well as suppressed the oxidation of SO_(2),thus resulting in an improvement in the resistance to H_(2)O and SO_(2) of the Pt/10EG-TiO_(2)-10 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).
文摘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 Ti^(3+)states and the coexistence of Ru SAs and NPs.With insights from literature,the role of Ti^(3+),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.
文摘We prepared TiO 2(anatase) and Sn doped TiO 2 nanoparticlate film by Plasma enhanced Chemical Vapor Deposition(PECVD) method. XRD and XPS experiments showed that Sn was doped into the lattice of TiO 2 with a ratio of n (Sn)∶ n (Ti)=1∶10 . Sn doping largely enhanced the photocatalytic activity of TiO 2 film for phenol degradation. The enhancement in photoactivity by doping was discussed, based on the characterization with AFM, FTIR and EFISPS. Sn doping produced localized level of Sn 4+ in the band gap of TiO 2, about 0.4 eV below the conduction band, which could capture photogenerated electrons and reduce O 2 adsorbed on the surface of TiO 2 film, thus accelerated the photocatalytic reaction.
