The selective cleavage of C-O and C-C is facing a challenge in the field of catalysis.In the present work,we studied the influence of doped Ni on the structure and electronic properties,as well as the selective C-O/C-...The selective cleavage of C-O and C-C is facing a challenge in the field of catalysis.In the present work,we studied the influence of doped Ni on the structure and electronic properties,as well as the selective C-O/C-C bond cleavages in the hydrodeoxygenation of palmitic acid over Ni-Mo_(2)C catalyst.The catalytic activity on Ni doped Mo_(2)C with TOF of 6.9×10^(3)h^(-1)is much superior to intrinsic Mo_(2)C catalyst,which is also higher than most noble metal catalysts.Structurally,the doped Ni raises the active particle dispersion and the coordination numbers of Mo species(Mo-C and Mo-O),improves the graphitization degree to promote the electron transfer,and increases the amount of Lewis and Br?nsted acid,which are responsible for the excellent hydrodeoxygenation performance.The Ni promotes simultaneously C-O and C-C bonds cleavage to produce pentadecane and hexadecane owing to the increase of electron-rich Mo sites after Ni doping.These findings contribute to the understanding of the nature of Ni-doped Mo_(2)C on the roles as catalytic active sites for C-O and C-C bonds cleavage.展开更多
Over the last two decades,extensive study has been done on two-dimensional Molybdenum Sulphide(MoS_(2))due to its outstanding features in energy storage applications.Although MoS_(2)has a lot of active sulphur edges,t...Over the last two decades,extensive study has been done on two-dimensional Molybdenum Sulphide(MoS_(2))due to its outstanding features in energy storage applications.Although MoS_(2)has a lot of active sulphur edges,the presence of inactive surfaces leads to limit conductivity and efficiency.Hence,in this article,we aimed to promote the additional active sites by doping various weight percentages(2%,4%,6%,8%and 10%)of Nickel(Ni)into the MoS_(2)matrix by simple hydrothermal technique,and their doping effects were investigated with the help of Physio-chemical analyses.X-ray diffraction(XRD)pattern,Raman,and chemical composition(XPS)analyses were used to confirm the Ni incorporation in MoS_(2)nanosheets.Microscopic investigations demonstrated that Ni-doped MoS_(2)nanosheets were vertically aligned with enhanced interlayer spacing.Cyclic voltammetry,Galvanostatic charge-discharge,and electrochemical impedance spectroscopy investigations were used to characterize the electrochemical characteristics.The 6%Ni-doped MoS_(2)electrode material showed better CSPof 528.7 F/g@1 A/g and excellent electrochemical stability(85%of capacitance retention after 10,000 cycles at 5 A/g)compared to other electrode materials.Furthermore,the solid-state asymmetric supercapacitor was assembled using Nidoped MoS_(2)and graphite as anode and cathode materials and analysed the electrochemical properties in the two-electrode system.To determine the impact of the Ni-atom on the MoS_(2)surface,firstprinciples computations were performed.Further,it was examined for electronic band structure,the projected density of states(PDOS)and Bader charge transfer analyses.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
The transition metal ion doped TiO 2 nanoparticles were prepared with hydrothermal method, and the effects of doping different metal ions on the ability of TiO 2 in photocatalyzing degradation of rhodamine B(RB) were ...The transition metal ion doped TiO 2 nanoparticles were prepared with hydrothermal method, and the effects of doping different metal ions on the ability of TiO 2 in photocatalyzing degradation of rhodamine B(RB) were studied. The results showed that the doping of Fe 3+ , Co 2+ , Ni 2+ and Cr 3+ in TiO 2 nanoparticles made the photocatalytic efficiency of the TiO 2 particles reduce and the higher the initial content of Fe 3+ , the lower the ability of TiO 2 in photocatalyzing the degradation of RB. But the doping of Zn 2+ and Cd 2+ , especially Zn 2+ , made the photocatalytic efficiency of the TiO 2 particles enhance, showing a great increase of the rate constant( k ) and the initial reaction rate( r ini ).展开更多
Nanocrystalline TiO 2 has been studied extensively in recent years as photocatalysts to deal with environmental pollutions, such as water purification, wastewater treatment and air purification. Here a novel sonochemi...Nanocrystalline TiO 2 has been studied extensively in recent years as photocatalysts to deal with environmental pollutions, such as water purification, wastewater treatment and air purification. Here a novel sonochemical method for directly preparing anatase nanocrystalline TiO 2 has been established. Nanocrystalline TiO 2 were synthesized by the hydrolysis of titanium tetrabutyl in the presence of water and ethanol under a high intensity ultrasonic irradiation(20 kHz, 100 W/cm 2) at 363 K for 3 h. The structure and particle sizes of the product were dependent upon the reaction temperature, the acidity of the medium and the reaction time. Characterization was accomplished by using various different techniques, such as powder X ray diffraction(XRD), transmission electron microscopy(TEM), thermogravimetry differential thermal analysis(TG DTA) and Fourier transform infrared(FTIR) spectroscopy. The TEM images showed that the particles of TiO 2 were columnar in shape and the average sizes were ca. 3 nm×7 nm . The formation mechanism of nanocrystalline TiO 2 under a high intensity ultrasonic irradiation was also investigated. The hydrolytic species of titanium tetrabutyl in water condensed to form a large number of tiny gel nuclei which aggregated to form larger clusters. Ultrasound irradiation generated a lot of local hot spots within the gel and the crystal structural unit was formed near the hot spots with the decrease of the gel nuclei, which lead to form nanocrystal particles.展开更多
基金financially supported by the National Natural Science Foundation of China(21972099)the Application Foundation Program of Sichuan Province(2021YJ0305)+1 种基金the 111 project(B17030).Shanghai Synchrotron Radiation Facility(SSRF)for XAS experiments and the support by the project from NPL of CAEP(2019BB08)。
文摘The selective cleavage of C-O and C-C is facing a challenge in the field of catalysis.In the present work,we studied the influence of doped Ni on the structure and electronic properties,as well as the selective C-O/C-C bond cleavages in the hydrodeoxygenation of palmitic acid over Ni-Mo_(2)C catalyst.The catalytic activity on Ni doped Mo_(2)C with TOF of 6.9×10^(3)h^(-1)is much superior to intrinsic Mo_(2)C catalyst,which is also higher than most noble metal catalysts.Structurally,the doped Ni raises the active particle dispersion and the coordination numbers of Mo species(Mo-C and Mo-O),improves the graphitization degree to promote the electron transfer,and increases the amount of Lewis and Br?nsted acid,which are responsible for the excellent hydrodeoxygenation performance.The Ni promotes simultaneously C-O and C-C bonds cleavage to produce pentadecane and hexadecane owing to the increase of electron-rich Mo sites after Ni doping.These findings contribute to the understanding of the nature of Ni-doped Mo_(2)C on the roles as catalytic active sites for C-O and C-C bonds cleavage.
文摘Over the last two decades,extensive study has been done on two-dimensional Molybdenum Sulphide(MoS_(2))due to its outstanding features in energy storage applications.Although MoS_(2)has a lot of active sulphur edges,the presence of inactive surfaces leads to limit conductivity and efficiency.Hence,in this article,we aimed to promote the additional active sites by doping various weight percentages(2%,4%,6%,8%and 10%)of Nickel(Ni)into the MoS_(2)matrix by simple hydrothermal technique,and their doping effects were investigated with the help of Physio-chemical analyses.X-ray diffraction(XRD)pattern,Raman,and chemical composition(XPS)analyses were used to confirm the Ni incorporation in MoS_(2)nanosheets.Microscopic investigations demonstrated that Ni-doped MoS_(2)nanosheets were vertically aligned with enhanced interlayer spacing.Cyclic voltammetry,Galvanostatic charge-discharge,and electrochemical impedance spectroscopy investigations were used to characterize the electrochemical characteristics.The 6%Ni-doped MoS_(2)electrode material showed better CSPof 528.7 F/g@1 A/g and excellent electrochemical stability(85%of capacitance retention after 10,000 cycles at 5 A/g)compared to other electrode materials.Furthermore,the solid-state asymmetric supercapacitor was assembled using Nidoped MoS_(2)and graphite as anode and cathode materials and analysed the electrochemical properties in the two-electrode system.To determine the impact of the Ni-atom on the MoS_(2)surface,firstprinciples computations were performed.Further,it was examined for electronic band structure,the projected density of states(PDOS)and Bader charge transfer analyses.
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.
文摘The transition metal ion doped TiO 2 nanoparticles were prepared with hydrothermal method, and the effects of doping different metal ions on the ability of TiO 2 in photocatalyzing degradation of rhodamine B(RB) were studied. The results showed that the doping of Fe 3+ , Co 2+ , Ni 2+ and Cr 3+ in TiO 2 nanoparticles made the photocatalytic efficiency of the TiO 2 particles reduce and the higher the initial content of Fe 3+ , the lower the ability of TiO 2 in photocatalyzing the degradation of RB. But the doping of Zn 2+ and Cd 2+ , especially Zn 2+ , made the photocatalytic efficiency of the TiO 2 particles enhance, showing a great increase of the rate constant( k ) and the initial reaction rate( r ini ).
文摘Nanocrystalline TiO 2 has been studied extensively in recent years as photocatalysts to deal with environmental pollutions, such as water purification, wastewater treatment and air purification. Here a novel sonochemical method for directly preparing anatase nanocrystalline TiO 2 has been established. Nanocrystalline TiO 2 were synthesized by the hydrolysis of titanium tetrabutyl in the presence of water and ethanol under a high intensity ultrasonic irradiation(20 kHz, 100 W/cm 2) at 363 K for 3 h. The structure and particle sizes of the product were dependent upon the reaction temperature, the acidity of the medium and the reaction time. Characterization was accomplished by using various different techniques, such as powder X ray diffraction(XRD), transmission electron microscopy(TEM), thermogravimetry differential thermal analysis(TG DTA) and Fourier transform infrared(FTIR) spectroscopy. The TEM images showed that the particles of TiO 2 were columnar in shape and the average sizes were ca. 3 nm×7 nm . The formation mechanism of nanocrystalline TiO 2 under a high intensity ultrasonic irradiation was also investigated. The hydrolytic species of titanium tetrabutyl in water condensed to form a large number of tiny gel nuclei which aggregated to form larger clusters. Ultrasound irradiation generated a lot of local hot spots within the gel and the crystal structural unit was formed near the hot spots with the decrease of the gel nuclei, which lead to form nanocrystal particles.
