Doping engineering is an effective strategy for graphitic carbon nitride(g-C_(3)N_(4))to improve its photocat-alytic hydrogen evolution reaction(HER)performance.In this work,a novel nitrogen and sulfur co-doped g-C_(3...Doping engineering is an effective strategy for graphitic carbon nitride(g-C_(3)N_(4))to improve its photocat-alytic hydrogen evolution reaction(HER)performance.In this work,a novel nitrogen and sulfur co-doped g-C_(3)N_(4)(N,S-g-C_(3)N_(4))is elaborately designed on the basis of theoretical predictions of first-principle density functional theory(DFT).The calculated Gibbs free energy of adsorbed hydrogen(ΔGH∗)for N,S-g-C_(3)N_(4) at the N-doping active sites is extremely close to zero(0.01 eV).Inspired by the theoretical predictions,the N,S-g-C_(3)N_(4) is successfully fabricated through ammonia-rich pyrolysis synthesis strategy,in which ammonia is in-situ obtained by pyrolyzing melamine.Subsequent characterizations indicate that the N,S-g-C_(3)N_(4) possesses high specific surface area,outstanding light utilization,good hydrophilicity,and efficient carrier transfer efficiency.Consequently,the N,S-g-C_(3)N_(4) displays an extremely high H2 evolution rate of 8269.9μmol g−1 h−1,achieves an apparent quantum efficiency(AQE)of 3.24%,and also possesses outsatnding durability.Theoretical calculations further demonstrate that N and S dopants can not only introduce doping energy level to reduce the band gap,but also induce charge redistribution to facilitate hydrogen adsorption,thus promoting the photocatalytic HER process.Moreover,femtosecond transient absorption(fs-TA)spectroscopy further corroborates the efficient photogenerated carrier transport of N,S-g-C_(3)N_(4).This research highlights a promising and reliable strategy to achieve superior photocatalytic activity,and exhibits significant guidance for precise designing high-efficiency photocatalysts.展开更多
Modulating the electronic structure of a photocatalyst and constructing spatially separated redox sites are key strategies for achieving the photocatalytic dual-channel generation of H_(2)O_(2).In this study,a graphen...Modulating the electronic structure of a photocatalyst and constructing spatially separated redox sites are key strategies for achieving the photocatalytic dual-channel generation of H_(2)O_(2).In this study,a graphene-modified non-compensated Cu/N-co-doped titanium dioxide(Cu-N-TiO_(2)/rGO)photocatalyst was designed for the efficient synthesis of H_(2)O_(2) via a dual-channel pathway.Precise modulation of the TiO_(2) conduction band position was achieved through the synergistic coupling of Cu 3d orbitals hybridized with Ti 3d orbitals and hybridization of N 2p orbitals with O 2p orbitals.This approach significantly improved the utilization of sunlight while satisfying the redox potential requirements.Cu doping not only promoted the formation of oxygen vacancies but also reduced the formation of Ti^(3+)ions,the photogenerated charge recombination centers.The non-compensated doping of N effectively increased the solubility of Cu^(2+)ions in the titanium dioxide lattice,enhanced the adsorption of hydroxyl radical intermediates,and created conditions for the subsequent hydroxyl radical combinations promoting the generation of H_(2)O_(2).In addition,the introduction of highly conductive graphene improved the interfacial carrier separation efficiency while realizing the spatial separation of redox sites,creating conditions for dual-channel reactions.The experimental results showed that the H_(2)O_(2) yield of Cu-N-TiO_(2)/rGO under simulated sunlight reached 1266.7μmol/L,which was 25.2 times higher than that of pristine TiO_(2).This study elucidated the synergistic mechanism of the energy band structure modulation and interfacial optimization,which provided a new idea for the design of dual-channel H_(2)O_(2) production photocatalysts.展开更多
Y and Eu co-doped nano-TiO2 photocatalysts were successfully prepared via a sol-gel method and characterized by X-ray diffraction（XRD）, transmission electron microscopy（TEM）, ultraviolet-visible spectrophotometry...Y and Eu co-doped nano-TiO2 photocatalysts were successfully prepared via a sol-gel method and characterized by X-ray diffraction（XRD）, transmission electron microscopy（TEM）, ultraviolet-visible spectrophotometry（UV-vis）, photoluminescence（PL） and Fourier transform infrared（FT-IR） spectra. Experimental results indicated that Y and Eu doping inhibited the growth of crystalline size and the transformation from anatase to rutile phase and had the function of reducing particle reunion. At the same time, co-doping could also enhance the absorption in visible region and then narrowed the band gap. The photocatalytic activities of the samples were evaluated by the degradation of methylene blue（MB） under ultraviolet（UV） light irradiation, which showed much enhanced photocatalytic activities over un-doped TiO2. The degradation rate of 1.5% Y/Eu-TiO2 of methylene blue was 86%, which was about 5 times of that of un-doped TiO2, and the possible reasons for the improvement of photocatalytic activities were analyzed. In this experiment, the dopant amount of rare earth was 1.5% and the ratio of Y：Eu was 2：3 for the maximum photocatalytic degradation, and the sample calcined at 500℃ showed the best reactivity. For the best samples above, the removal rate of phenol under visble light was 53% whthin 2 h.展开更多
In this paper,a visible light-responsive Sn^(2+)and N co-doped TiO_(2)photocatalyst was prepared by facile one-pot hydrothermal method.All as-prepared samples were characterized in detail by a series of characterizati...In this paper,a visible light-responsive Sn^(2+)and N co-doped TiO_(2)photocatalyst was prepared by facile one-pot hydrothermal method.All as-prepared samples were characterized in detail by a series of characterization approaches.The results showed that the Sn^(2+)and N elements were co-doped into TiO_(2),while the catalyst still maintains anatase crystal structure and gets irregular little nanocluster in diameter of 9–10 nm with higher specific surface area.The absorption edge of Sn^(2+)and N co-doped TiO_(2)extends to the visible light region.Compared with Sn^(2+)-doped TiO_(2)and N-TiO_(2),the absorption edges have obvious red-shift of about 50 and 70 nm,respectively.The synergistic effect of O 2p-N 2p and O 2p-Sn 5s hybridization to form impurity levels is the main reason for the red-shift.The hydrogen production performance of the Sn^(2+)and N co-doping TiO_(2)(n(N)/n(Ti)=1)catalyst reached the maximum value of 0.37 mmol·h^(-1)·g^(-1)under visible light,which is higher than that of N-doped TiO_(2)and SnTiO_(2)-doped TiO_(2)singly.This result is due to the wider visible light region-responsive ability of Sn^(2+)and N codoped into TiO_(2).Furthermore,mild hydrothermal methods will not make the Sn^(2+)oxidized to Sn^(4+),which make the catalysts still maintain high photocatalytic performance.This work provides a simple and mild method for the preparation of dual-element co-doped TiO_(2)with high crystallinity,excellent performance and broad application prospects.展开更多
Undoped and Ni–S co-doped mesoporous TiO2 nano materials were synthesized by using sol–gel method.The characteristic features of as prepared catalyst samples were investigated using various advanced spectroscopic an...Undoped and Ni–S co-doped mesoporous TiO2 nano materials were synthesized by using sol–gel method.The characteristic features of as prepared catalyst samples were investigated using various advanced spectroscopic and analytical techniques.The characterization results of the samples revealed that all the samples exhibited anatase phase(XRD),decreasing band gap(2.68 eV)(UV–Vis-DRS),small particle size(9.2 nm)(TEM),high surface area(142.156 m^2·g^-1)(BET),particles with spherical shape and smooth morphology(SEM);there is a frequency shift observed for co-doped sample(FT-IR)and the elemental composition electronic states and position of the doped elements(Ni and S)in the TiO2 lattice analyzed by XPS and EDX.These results supported the photocatalytic degradation of Bismarck Brown Red(BBR)achieved with in 110 min and also exhibited the antibacterial activity on Staphylococcus aureus(MTCC-3160),Pseudomonas fluorescence(MTCC-1688)under visible light irradiation.展开更多
The existence form and effect of La on the phase composition,morphology,recombination of photocarriers,and optical absorptivity of La-F codoped TiO2 were investigated.Experimental results indicate that all the phase c...The existence form and effect of La on the phase composition,morphology,recombination of photocarriers,and optical absorptivity of La-F codoped TiO2 were investigated.Experimental results indicate that all the phase composition of samples is anatase TiO2,the grain sizes decrease with the increasing of La content The catalysts have a well-defined spherical structure with an average size of 12-14 nm,and the doping elements are uniformly dispersed.Compared with pure TiO2,the absorption edge of La1.5F5-TiO2 red shifts from 388 to 437 nm,accordingly the energy gap(Eg) reduces from 32 to 2.84 eV,Besides,the recombination rate of electron-holes in La1.5F5-TiO2 is the weakest among the prepared samples,and the specific surface area of La1.5F5-TiO2 reaches 105.27 m2/g.The apparent reaction rate constant k of La1.5F5-TiO2 for methylene blue(MB) degradation under visible light obtained from the apparent first-order model achieves 0.0166±0.52 min-1,which is greater than 0.0033±0.09 min 1 of TiO2.Moreover,high-resolution transmission electron microscopy(HRTEM) observation reveals that there coexist La2O3 particles in the co-doped TiO2.展开更多
Micro-porous TiO2 coatings co-doped with Zn^2＋ and Ag nanoparticles were fabricated on Ti by microarc oxidation （MAO） for 0.5, 1.5, 2 and 4 min, respectively. The evolutions of morphology and phase component of the...Micro-porous TiO2 coatings co-doped with Zn^2＋ and Ag nanoparticles were fabricated on Ti by microarc oxidation （MAO） for 0.5, 1.5, 2 and 4 min, respectively. The evolutions of morphology and phase component of the coating as a function of processing time were investigated. The microstructure of the 2 min treated coating was further observed by transmission electron microscopy to explore the coating formation mechanism. The amounts of Ag and Zn released from the 2 min treated coating were measured and the antibacterial properties of the coatings against Staphylococcus aureus （S. aureus） were also investigated. The obtained results showed that with prolonged MAO time, the contents of Ag and Zn on the coating surfaces increased. All the coatings were micro-porous with pore diameters of 1 -4μm; however, some pores were blocked by deposits on the 4 min treated coating. The 2 rain treated coating was composed of amorphous TiO2, anatase, futile, ZnO, Zn2TiO4 and homogenously distributed Ag nanoparticles. After immersion, Zn^2＋, Ag^＋, Ti^2＋ and Ca^2＋ were released from the coating and with the immersion time prolonged, the accumulated concentrations of these ions increased. After immersion for 36 weeks, the accumulated Zn2. and Ag^＋ concentrations were 6.88 and 0.684 ppm, respectively, which are higher than the minimal inhibitory concentration but much lower than the cytotoxic concentration. Compared with polished Ti control, the coatings co-doped with Zn^2＋ and Ag nanoparticles significantly inhibited the ad- hesions of S. uureus and reduced the amounts of planktonic bacteria in culture medium, indicating that the Zn and Ag co-doped TiO2 could be a bio-adaptable coating for long-lasting anti-microbial performance.展开更多
A series of Ce, H3PW12O40 co-doped TiO2 hollow fibers photocatalysts have been prepared by sol-gel method using ammonium ceric nitrate, H3PW12O40 and tetrabutyltitanate as precursors and cotton fibers as template, fol...A series of Ce, H3PW12O40 co-doped TiO2 hollow fibers photocatalysts have been prepared by sol-gel method using ammonium ceric nitrate, H3PW12O40 and tetrabutyltitanate as precursors and cotton fibers as template, followed by calcination at 500 ℃ in N2 atmosphere for 2 h. Scanning electron microscopy, X-ray diffraction, nitrogen adsorption-desorption mea- surements, and UV-Vis spectroscopy are employed to characterize the morphology, crystal structure, surface structure, and optical absorption properties of the samples. The photo- catalytic performance of the samples has been studied by photodegradation phenol in water under UV and visible light irradiation. The results show that the TiO2 fiber materials have hollow structures, and the co-doped TiO2 hollow fibers exhibit higher photocatalytic activities for the degradation of phenol than un-doped, single-doped TiO2 hollow fibers under UV and visible light. In addition, the recyclability of co-doped TiO2 fibers is also confirmed that the TiO2 fiber retains ca. 90% of its activity after being used four times. It is shown that the co-doped TiO2 fibers can be activated by visible light and may be potentially applied to the treatment of water contaminated by organic pollutants. The synergistic effect of Ce and H3PW12O40 co-doping plays an important role in improving the photocatalytic activity.展开更多
The N and C doping effects on the crystal structures, electronic and optical properties of fluorite structure CeO2 have been investigated using the first-principles calculation. Co-doping these two elements results in...The N and C doping effects on the crystal structures, electronic and optical properties of fluorite structure CeO2 have been investigated using the first-principles calculation. Co-doping these two elements results in the local lattice distortion and volume expansion of CeO2. Compared with the energy hand structure of pure CeO2, some local energy levels appear in the forbidden band, which may facilitate the light absorption. Moreover, the enhanced photo-catalytic properties of CeO2 were explained through the absorption spectra and the selection rule of the band-to-band transitions.展开更多
The cubic S/N co-doped TiO_(2)(TNSx,x is the calcination temperature)photocatalysts with rich oxygen vacancies were obtained by high temperature calcination of sulfur powder and titanium-based MOFs NH_(2)-MIL-125 for ...The cubic S/N co-doped TiO_(2)(TNSx,x is the calcination temperature)photocatalysts with rich oxygen vacancies were obtained by high temperature calcination of sulfur powder and titanium-based MOFs NH_(2)-MIL-125 for the photocatalytic removal of gaseous formaldehyde(a volatile organic compound).Among the obtained catalysts,the presence of oxygen vacancies restricted photogenerated electron and holes recombination.98.00%removal of gaseous formaldehyde in 150 min could be achieved over TNS600 by xenon lamp.The removal efficiency for formaldehyde was well retained for five cycle experiment.The results from PL,TRPL and EIS revealed that TNS600 had the best separation efficiency of photogenerated electrons and holes,and the enhanced charge separation led to a significant increase in photocatalytic activity.The photocatalytic oxidation mechanism indicated that the ^(•)OH and ^(•)O_(2)−radicals were mainly involved in the efficient elimination of gaseous formaldehyde and were able to mineralize formaldehyde to H_(2)O and CO_(2).展开更多
Nb and F co-doped anatase TiO2 layers were deposited by low pressure chemical vapor deposition (LPCVD) at pressure of 3 mtorr using titanium-tetra-iso-propoxide (TTIP), O2 and NbF5 as precursor, oxidant and dopant res...Nb and F co-doped anatase TiO2 layers were deposited by low pressure chemical vapor deposition (LPCVD) at pressure of 3 mtorr using titanium-tetra-iso-propoxide (TTIP), O2 and NbF5 as precursor, oxidant and dopant respectively. Resistivity beyond 100 Ωcm for undoped layer was decreased with increasing supply of the dopant and dependent on the supply ratio of O2 to TTIP and decreased to 0.2 Ωcm by the optimization. X-ray fluorescent spectroscopy showed Nb-content in the layer was decreased with the O2-supply ratio. X-ray photo-spectroscopy indicated that F substituted O-site in TiO2 by O2-supply but carbon-contamination and F missing substitution in the O-site were significantly increased by excess O2-supply. Further, it was suggested that the substituted F played an important role to reduce resistivity without significant contribution of O-vacancies. XRD spectra showed F missing substitution in the O-site degraded the crystallinity.展开更多
Hydrodeoxygenation of furfural(FF)into 2-methylfuran(MF)is a significant biomass utilization route.However,designing efficient and stable non-noble metal catalyst is still a huge challenge.Herein,we reported the N,O c...Hydrodeoxygenation of furfural(FF)into 2-methylfuran(MF)is a significant biomass utilization route.However,designing efficient and stable non-noble metal catalyst is still a huge challenge.Herein,we reported the N,O co-doped carbon anchored with Co nanoparticles(Co-SFB)synthesized by employing the organic ligands with the target heteroatoms.Raman,electron paramagnetic resonance(EPR),electrochemical impedance spectroscopy(EIS),and X-ray photoelectron spectroscopy(XPS)characterizations showed that the co-doping of N and O heteroatoms in the carbon support endows Co-SFB with enriched lone pair electrons,fast electron transfer ability,and strong metal-support interaction.These electronic properties resulted in strong FF adsorption as well as lower apparent reaction activation energy.At last,the obtained N,O co-doped Co/C catalyst showed excellent catalytic activity(nearly 100 mol%FF conversion and 94.6 mol%MF yield)and stability for in-situ dehydrogenation of FF into MF.This N,O co-doping strategy for the synthesis of highly efficient catalytic materials with controllable electronic state will provide an excellent opportunity to better understand the structure-function relationship.展开更多
Metal-free heteroatom doped nanocarbons are promising alternatives to the metal-based materials in catalytic ozonation for destruction of aqueous organic contaminants. In this study, N, S co-doped hollow carbon micros...Metal-free heteroatom doped nanocarbons are promising alternatives to the metal-based materials in catalytic ozonation for destruction of aqueous organic contaminants. In this study, N, S co-doped hollow carbon microspheres (NSCs) were synthesized from the polymerization products during persulfate wet air oxidation of benzothiazole. The contents of doped N and S as well as the structural stability were maneuvered by adjusting the subsequent N_(2)-annealing temperature. Compared with the prevailing single-walled carbon nanotubes, the N_(2)-annealed NSCs demonstrated a higher catalytic ozonation activity for benzimidazole degradation. According to the quantitative structure-activity relationship (QSAR) analysis, the synergistic effect between the graphitic N and the thiophene-S which redistributed the charge distribution of the carbon basal plane contributed to the activity enhancement of the N_(2)-annealed NSCs. Additionally, the hollow structure within the microspheres served as the microreactor to boost the mass transfer and reaction kinetics via the nanoconfinement effects. Quenching and electron paramagnetic resonance (EPR) tests revealed that benzimidazole degradation was dominated by the produced singlet oxygen (^(1)O_(2)) species, while hydroxyl radicals (^(·)OH) were also generated and participated. This study puts forward a novel strategy for synthesis of heteroatom-doped nanocarbons and sheds a light on the relationship between the active sites on the doped nanocarbons and the catalytic performance.展开更多
Designing a carbon material with a unique composition and surface functional groups for offering high specific capacity in a wide voltage window is of great significance to improve the energy density for the supercapa...Designing a carbon material with a unique composition and surface functional groups for offering high specific capacity in a wide voltage window is of great significance to improve the energy density for the supercapacitor in a cheap and eco-friendly aqueous electrolyte.Herein,we develop an efficient strategy to synthesize a N,O co-doped hierarchically porous carbon(NODPC-1.0)with moderate specific surface area and pore volume as well as rich heteroatoms using a deep eutectic solvent(DES)as an activator.It is found that NODPC-1.0 with a large proportion of pseudocapacitive functional groups(pyrrole-N,pyridineN and carbonyl-quinone)can work stable in an acidic 2 mol/L Li_(2)SO_(4)(pH 2.5)electrolyte,exhibiting specific capacities of 375 and 186 F/g at the current densities of 1.0 and 100 A/g,respectively.Also,the assembled symmetric capacitor using the NODPC-1.0 as the active material and 2 mol/L acidic Li_(2)SO_(4)(pH 2.5)as the electrolyte shows an outstanding energy density of 74.4 Wh/kg at a high power density of 1.44 k W/kg under a broad voltage window(2.4 V).Relevant comparative experiments indicate that H+of the acidic aqueous electrolyte plays a crucial part in enhancement the specific capacity,and the abundant pseudocapacitive functional groups on the surface of the NODPC-1.0 sample play the key role in the improvement of electrochemical cycle stability under a broad voltage window.展开更多
The N,S co-doped porous carbon nanofibers were fabricated by the carbonization of[Zn_(2)(tdc)_(2)(MA)]n MOFs/polyacrylonitrile nanofibers composite,which was produced by the electrospinning technology.The electrochemi...The N,S co-doped porous carbon nanofibers were fabricated by the carbonization of[Zn_(2)(tdc)_(2)(MA)]n MOFs/polyacrylonitrile nanofibers composite,which was produced by the electrospinning technology.The electrochemical results show that the N,S co-doped porous carbon nanofibers can achieve capacity of 201.2 mAh·g^(-1)at the current density of 0.05 A·g^(-1).Furthermore,the reversible capacity still has 161.3 mAh·g^(-1)even at a high current density of 1 A·g^(-1)after 600 cycles.The superior electrochemical performance shows that the N,S co-doped porous carbon nanofibers electrode material can be used as an ideal anode material for sodium-ion batteries.展开更多
A visible-light-active photocatalyst was prepared by calcination of the hydrolysis product of tetrabutyl titanate with ammonia as precipitant. The photocatalyst was characterized by X-ray diffraction (XRD), UV-Vis dif...A visible-light-active photocatalyst was prepared by calcination of the hydrolysis product of tetrabutyl titanate with ammonia as precipitant. The photocatalyst was characterized by X-ray diffraction (XRD), UV-Vis diffuse reflection spectra (DRS), thermal gravimetric-differential thermal analysis (TG-DTA), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM). The color of the photocatalyst was yellow and could absorb light wavelength under 550 nm as measured by DRS. The catalyst calcined at higher temperature will give lower absorbance for visible light. Structures of the sample were characterized mainly to be anatase by XRD except for the sample calcined at 700 ℃ which gave mixtures of anatase and rutile. TG-DTA results showed that temperature for anatase formation was 415 ℃. XPS results showed that doped-nitrogen was presented in the sample, they are important to show visible-light absorbency. The photocatalytic activities were evaluated using methyl orange and phenol as model pollutants, the results showed that over 90% of phenol could be degraded under visible light using N/TiO2 as the catalyst after 4 hours reaction. Almost the same activity was found for the TiO2 photocatalyst calcined at different temperature under sunlight but activities were different when the treatment was under UV light.展开更多
基金supported by the National Natural Science Foun-dation of China(No.62004143)the Key R&D Program of Hubei Province(No.2022BAA084)the Natural Science Foundation of Hubei Province(No.2021CFB133).
文摘Doping engineering is an effective strategy for graphitic carbon nitride(g-C_(3)N_(4))to improve its photocat-alytic hydrogen evolution reaction(HER)performance.In this work,a novel nitrogen and sulfur co-doped g-C_(3)N_(4)(N,S-g-C_(3)N_(4))is elaborately designed on the basis of theoretical predictions of first-principle density functional theory(DFT).The calculated Gibbs free energy of adsorbed hydrogen(ΔGH∗)for N,S-g-C_(3)N_(4) at the N-doping active sites is extremely close to zero(0.01 eV).Inspired by the theoretical predictions,the N,S-g-C_(3)N_(4) is successfully fabricated through ammonia-rich pyrolysis synthesis strategy,in which ammonia is in-situ obtained by pyrolyzing melamine.Subsequent characterizations indicate that the N,S-g-C_(3)N_(4) possesses high specific surface area,outstanding light utilization,good hydrophilicity,and efficient carrier transfer efficiency.Consequently,the N,S-g-C_(3)N_(4) displays an extremely high H2 evolution rate of 8269.9μmol g−1 h−1,achieves an apparent quantum efficiency(AQE)of 3.24%,and also possesses outsatnding durability.Theoretical calculations further demonstrate that N and S dopants can not only introduce doping energy level to reduce the band gap,but also induce charge redistribution to facilitate hydrogen adsorption,thus promoting the photocatalytic HER process.Moreover,femtosecond transient absorption(fs-TA)spectroscopy further corroborates the efficient photogenerated carrier transport of N,S-g-C_(3)N_(4).This research highlights a promising and reliable strategy to achieve superior photocatalytic activity,and exhibits significant guidance for precise designing high-efficiency photocatalysts.
文摘Modulating the electronic structure of a photocatalyst and constructing spatially separated redox sites are key strategies for achieving the photocatalytic dual-channel generation of H_(2)O_(2).In this study,a graphene-modified non-compensated Cu/N-co-doped titanium dioxide(Cu-N-TiO_(2)/rGO)photocatalyst was designed for the efficient synthesis of H_(2)O_(2) via a dual-channel pathway.Precise modulation of the TiO_(2) conduction band position was achieved through the synergistic coupling of Cu 3d orbitals hybridized with Ti 3d orbitals and hybridization of N 2p orbitals with O 2p orbitals.This approach significantly improved the utilization of sunlight while satisfying the redox potential requirements.Cu doping not only promoted the formation of oxygen vacancies but also reduced the formation of Ti^(3+)ions,the photogenerated charge recombination centers.The non-compensated doping of N effectively increased the solubility of Cu^(2+)ions in the titanium dioxide lattice,enhanced the adsorption of hydroxyl radical intermediates,and created conditions for the subsequent hydroxyl radical combinations promoting the generation of H_(2)O_(2).In addition,the introduction of highly conductive graphene improved the interfacial carrier separation efficiency while realizing the spatial separation of redox sites,creating conditions for dual-channel reactions.The experimental results showed that the H_(2)O_(2) yield of Cu-N-TiO_(2)/rGO under simulated sunlight reached 1266.7μmol/L,which was 25.2 times higher than that of pristine TiO_(2).This study elucidated the synergistic mechanism of the energy band structure modulation and interfacial optimization,which provided a new idea for the design of dual-channel H_(2)O_(2) production photocatalysts.
基金Project supported by National Natural Science Foundation of China(51174020)
文摘Y and Eu co-doped nano-TiO2 photocatalysts were successfully prepared via a sol-gel method and characterized by X-ray diffraction（XRD）, transmission electron microscopy（TEM）, ultraviolet-visible spectrophotometry（UV-vis）, photoluminescence（PL） and Fourier transform infrared（FT-IR） spectra. Experimental results indicated that Y and Eu doping inhibited the growth of crystalline size and the transformation from anatase to rutile phase and had the function of reducing particle reunion. At the same time, co-doping could also enhance the absorption in visible region and then narrowed the band gap. The photocatalytic activities of the samples were evaluated by the degradation of methylene blue（MB） under ultraviolet（UV） light irradiation, which showed much enhanced photocatalytic activities over un-doped TiO2. The degradation rate of 1.5% Y/Eu-TiO2 of methylene blue was 86%, which was about 5 times of that of un-doped TiO2, and the possible reasons for the improvement of photocatalytic activities were analyzed. In this experiment, the dopant amount of rare earth was 1.5% and the ratio of Y：Eu was 2：3 for the maximum photocatalytic degradation, and the sample calcined at 500℃ showed the best reactivity. For the best samples above, the removal rate of phenol under visble light was 53% whthin 2 h.
基金This study was financially supported by the Natural Science Foundation of China(No.21663009)the National Key R&D Projects of China(No.2018YFC1801706-01)the Science and Technology Supporting Project of Guizhou Province(Nos.[2019]2835 and[2021]480).
文摘In this paper,a visible light-responsive Sn^(2+)and N co-doped TiO_(2)photocatalyst was prepared by facile one-pot hydrothermal method.All as-prepared samples were characterized in detail by a series of characterization approaches.The results showed that the Sn^(2+)and N elements were co-doped into TiO_(2),while the catalyst still maintains anatase crystal structure and gets irregular little nanocluster in diameter of 9–10 nm with higher specific surface area.The absorption edge of Sn^(2+)and N co-doped TiO_(2)extends to the visible light region.Compared with Sn^(2+)-doped TiO_(2)and N-TiO_(2),the absorption edges have obvious red-shift of about 50 and 70 nm,respectively.The synergistic effect of O 2p-N 2p and O 2p-Sn 5s hybridization to form impurity levels is the main reason for the red-shift.The hydrogen production performance of the Sn^(2+)and N co-doping TiO_(2)(n(N)/n(Ti)=1)catalyst reached the maximum value of 0.37 mmol·h^(-1)·g^(-1)under visible light,which is higher than that of N-doped TiO_(2)and SnTiO_(2)-doped TiO_(2)singly.This result is due to the wider visible light region-responsive ability of Sn^(2+)and N codoped into TiO_(2).Furthermore,mild hydrothermal methods will not make the Sn^(2+)oxidized to Sn^(4+),which make the catalysts still maintain high photocatalytic performance.This work provides a simple and mild method for the preparation of dual-element co-doped TiO_(2)with high crystallinity,excellent performance and broad application prospects.
基金the University Grants Commission (UGC) for providing BSR fellowship
文摘Undoped and Ni–S co-doped mesoporous TiO2 nano materials were synthesized by using sol–gel method.The characteristic features of as prepared catalyst samples were investigated using various advanced spectroscopic and analytical techniques.The characterization results of the samples revealed that all the samples exhibited anatase phase(XRD),decreasing band gap(2.68 eV)(UV–Vis-DRS),small particle size(9.2 nm)(TEM),high surface area(142.156 m^2·g^-1)(BET),particles with spherical shape and smooth morphology(SEM);there is a frequency shift observed for co-doped sample(FT-IR)and the elemental composition electronic states and position of the doped elements(Ni and S)in the TiO2 lattice analyzed by XPS and EDX.These results supported the photocatalytic degradation of Bismarck Brown Red(BBR)achieved with in 110 min and also exhibited the antibacterial activity on Staphylococcus aureus(MTCC-3160),Pseudomonas fluorescence(MTCC-1688)under visible light irradiation.
基金Project supported by the Natural Science Foundation of China(21407084,51474133)
文摘The existence form and effect of La on the phase composition,morphology,recombination of photocarriers,and optical absorptivity of La-F codoped TiO2 were investigated.Experimental results indicate that all the phase composition of samples is anatase TiO2,the grain sizes decrease with the increasing of La content The catalysts have a well-defined spherical structure with an average size of 12-14 nm,and the doping elements are uniformly dispersed.Compared with pure TiO2,the absorption edge of La1.5F5-TiO2 red shifts from 388 to 437 nm,accordingly the energy gap(Eg) reduces from 32 to 2.84 eV,Besides,the recombination rate of electron-holes in La1.5F5-TiO2 is the weakest among the prepared samples,and the specific surface area of La1.5F5-TiO2 reaches 105.27 m2/g.The apparent reaction rate constant k of La1.5F5-TiO2 for methylene blue(MB) degradation under visible light obtained from the apparent first-order model achieves 0.0166±0.52 min-1,which is greater than 0.0033±0.09 min 1 of TiO2.Moreover,high-resolution transmission electron microscopy(HRTEM) observation reveals that there coexist La2O3 particles in the co-doped TiO2.
基金the financial support of the National Program on Key Basic Research Project of China ("973 Program", Grant No. 2012CB619103)the National Natural Science Foundation of China (Grant Nos. 51201129, 51371137, 51571158)+2 种基金the Natural Science Foundation of Shanxi Province (Grant No. 2015JQ5130)the Open Research Fund of State Key Laboratory of BioelectronicsSoutheast University and the Fundamental Research Funds for the Central Universities
文摘Micro-porous TiO2 coatings co-doped with Zn^2＋ and Ag nanoparticles were fabricated on Ti by microarc oxidation （MAO） for 0.5, 1.5, 2 and 4 min, respectively. The evolutions of morphology and phase component of the coating as a function of processing time were investigated. The microstructure of the 2 min treated coating was further observed by transmission electron microscopy to explore the coating formation mechanism. The amounts of Ag and Zn released from the 2 min treated coating were measured and the antibacterial properties of the coatings against Staphylococcus aureus （S. aureus） were also investigated. The obtained results showed that with prolonged MAO time, the contents of Ag and Zn on the coating surfaces increased. All the coatings were micro-porous with pore diameters of 1 -4μm; however, some pores were blocked by deposits on the 4 min treated coating. The 2 rain treated coating was composed of amorphous TiO2, anatase, futile, ZnO, Zn2TiO4 and homogenously distributed Ag nanoparticles. After immersion, Zn^2＋, Ag^＋, Ti^2＋ and Ca^2＋ were released from the coating and with the immersion time prolonged, the accumulated concentrations of these ions increased. After immersion for 36 weeks, the accumulated Zn2. and Ag^＋ concentrations were 6.88 and 0.684 ppm, respectively, which are higher than the minimal inhibitory concentration but much lower than the cytotoxic concentration. Compared with polished Ti control, the coatings co-doped with Zn^2＋ and Ag nanoparticles significantly inhibited the ad- hesions of S. uureus and reduced the amounts of planktonic bacteria in culture medium, indicating that the Zn and Ag co-doped TiO2 could be a bio-adaptable coating for long-lasting anti-microbial performance.
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China （No.41373127） and Liaon- ing Provincial Natural Science Foundation of China （No.2013020121）.
文摘A series of Ce, H3PW12O40 co-doped TiO2 hollow fibers photocatalysts have been prepared by sol-gel method using ammonium ceric nitrate, H3PW12O40 and tetrabutyltitanate as precursors and cotton fibers as template, followed by calcination at 500 ℃ in N2 atmosphere for 2 h. Scanning electron microscopy, X-ray diffraction, nitrogen adsorption-desorption mea- surements, and UV-Vis spectroscopy are employed to characterize the morphology, crystal structure, surface structure, and optical absorption properties of the samples. The photo- catalytic performance of the samples has been studied by photodegradation phenol in water under UV and visible light irradiation. The results show that the TiO2 fiber materials have hollow structures, and the co-doped TiO2 hollow fibers exhibit higher photocatalytic activities for the degradation of phenol than un-doped, single-doped TiO2 hollow fibers under UV and visible light. In addition, the recyclability of co-doped TiO2 fibers is also confirmed that the TiO2 fiber retains ca. 90% of its activity after being used four times. It is shown that the co-doped TiO2 fibers can be activated by visible light and may be potentially applied to the treatment of water contaminated by organic pollutants. The synergistic effect of Ce and H3PW12O40 co-doping plays an important role in improving the photocatalytic activity.
基金Project supported by the National Natural Science Foundation of China(Grant No.61306098)
文摘The N and C doping effects on the crystal structures, electronic and optical properties of fluorite structure CeO2 have been investigated using the first-principles calculation. Co-doping these two elements results in the local lattice distortion and volume expansion of CeO2. Compared with the energy hand structure of pure CeO2, some local energy levels appear in the forbidden band, which may facilitate the light absorption. Moreover, the enhanced photo-catalytic properties of CeO2 were explained through the absorption spectra and the selection rule of the band-to-band transitions.
基金supported by the National Natural Science Foundation of China(Nos.21876008 and 22276009).
文摘The cubic S/N co-doped TiO_(2)(TNSx,x is the calcination temperature)photocatalysts with rich oxygen vacancies were obtained by high temperature calcination of sulfur powder and titanium-based MOFs NH_(2)-MIL-125 for the photocatalytic removal of gaseous formaldehyde(a volatile organic compound).Among the obtained catalysts,the presence of oxygen vacancies restricted photogenerated electron and holes recombination.98.00%removal of gaseous formaldehyde in 150 min could be achieved over TNS600 by xenon lamp.The removal efficiency for formaldehyde was well retained for five cycle experiment.The results from PL,TRPL and EIS revealed that TNS600 had the best separation efficiency of photogenerated electrons and holes,and the enhanced charge separation led to a significant increase in photocatalytic activity.The photocatalytic oxidation mechanism indicated that the ^(•)OH and ^(•)O_(2)−radicals were mainly involved in the efficient elimination of gaseous formaldehyde and were able to mineralize formaldehyde to H_(2)O and CO_(2).
文摘Nb and F co-doped anatase TiO2 layers were deposited by low pressure chemical vapor deposition (LPCVD) at pressure of 3 mtorr using titanium-tetra-iso-propoxide (TTIP), O2 and NbF5 as precursor, oxidant and dopant respectively. Resistivity beyond 100 Ωcm for undoped layer was decreased with increasing supply of the dopant and dependent on the supply ratio of O2 to TTIP and decreased to 0.2 Ωcm by the optimization. X-ray fluorescent spectroscopy showed Nb-content in the layer was decreased with the O2-supply ratio. X-ray photo-spectroscopy indicated that F substituted O-site in TiO2 by O2-supply but carbon-contamination and F missing substitution in the O-site were significantly increased by excess O2-supply. Further, it was suggested that the substituted F played an important role to reduce resistivity without significant contribution of O-vacancies. XRD spectra showed F missing substitution in the O-site degraded the crystallinity.
基金supported by the National Key R&D Program of China(2021YFC2103704)the National Natural Science Foundation of China(22022812,21978259)+1 种基金Key R&D Program of Zhejiang(2022C01208)Institute of Zhejiang University-Quzhou S&T Planed Projects(IZQ2021KJ1001)。
文摘Hydrodeoxygenation of furfural(FF)into 2-methylfuran(MF)is a significant biomass utilization route.However,designing efficient and stable non-noble metal catalyst is still a huge challenge.Herein,we reported the N,O co-doped carbon anchored with Co nanoparticles(Co-SFB)synthesized by employing the organic ligands with the target heteroatoms.Raman,electron paramagnetic resonance(EPR),electrochemical impedance spectroscopy(EIS),and X-ray photoelectron spectroscopy(XPS)characterizations showed that the co-doping of N and O heteroatoms in the carbon support endows Co-SFB with enriched lone pair electrons,fast electron transfer ability,and strong metal-support interaction.These electronic properties resulted in strong FF adsorption as well as lower apparent reaction activation energy.At last,the obtained N,O co-doped Co/C catalyst showed excellent catalytic activity(nearly 100 mol%FF conversion and 94.6 mol%MF yield)and stability for in-situ dehydrogenation of FF into MF.This N,O co-doping strategy for the synthesis of highly efficient catalytic materials with controllable electronic state will provide an excellent opportunity to better understand the structure-function relationship.
基金financial supports from the National Natural Science Foundation of China (No21978324)Tianjin Municipal Science and Technology Bureau (No.18YFYSZ00170)+1 种基金Beijing Natural Science Foundation (No. 8192039)Science Foundation of China University of Petroleum,Beijing(No. 2462020YXZZ034)。
文摘Metal-free heteroatom doped nanocarbons are promising alternatives to the metal-based materials in catalytic ozonation for destruction of aqueous organic contaminants. In this study, N, S co-doped hollow carbon microspheres (NSCs) were synthesized from the polymerization products during persulfate wet air oxidation of benzothiazole. The contents of doped N and S as well as the structural stability were maneuvered by adjusting the subsequent N_(2)-annealing temperature. Compared with the prevailing single-walled carbon nanotubes, the N_(2)-annealed NSCs demonstrated a higher catalytic ozonation activity for benzimidazole degradation. According to the quantitative structure-activity relationship (QSAR) analysis, the synergistic effect between the graphitic N and the thiophene-S which redistributed the charge distribution of the carbon basal plane contributed to the activity enhancement of the N_(2)-annealed NSCs. Additionally, the hollow structure within the microspheres served as the microreactor to boost the mass transfer and reaction kinetics via the nanoconfinement effects. Quenching and electron paramagnetic resonance (EPR) tests revealed that benzimidazole degradation was dominated by the produced singlet oxygen (^(1)O_(2)) species, while hydroxyl radicals (^(·)OH) were also generated and participated. This study puts forward a novel strategy for synthesis of heteroatom-doped nanocarbons and sheds a light on the relationship between the active sites on the doped nanocarbons and the catalytic performance.
基金supported by the National Natural Science Foundation of China(Nos.21875071 and 22178125)the Guangdong key R&D Program of China(No.2019B090908001)。
文摘Designing a carbon material with a unique composition and surface functional groups for offering high specific capacity in a wide voltage window is of great significance to improve the energy density for the supercapacitor in a cheap and eco-friendly aqueous electrolyte.Herein,we develop an efficient strategy to synthesize a N,O co-doped hierarchically porous carbon(NODPC-1.0)with moderate specific surface area and pore volume as well as rich heteroatoms using a deep eutectic solvent(DES)as an activator.It is found that NODPC-1.0 with a large proportion of pseudocapacitive functional groups(pyrrole-N,pyridineN and carbonyl-quinone)can work stable in an acidic 2 mol/L Li_(2)SO_(4)(pH 2.5)electrolyte,exhibiting specific capacities of 375 and 186 F/g at the current densities of 1.0 and 100 A/g,respectively.Also,the assembled symmetric capacitor using the NODPC-1.0 as the active material and 2 mol/L acidic Li_(2)SO_(4)(pH 2.5)as the electrolyte shows an outstanding energy density of 74.4 Wh/kg at a high power density of 1.44 k W/kg under a broad voltage window(2.4 V).Relevant comparative experiments indicate that H+of the acidic aqueous electrolyte plays a crucial part in enhancement the specific capacity,and the abundant pseudocapacitive functional groups on the surface of the NODPC-1.0 sample play the key role in the improvement of electrochemical cycle stability under a broad voltage window.
文摘The N,S co-doped porous carbon nanofibers were fabricated by the carbonization of[Zn_(2)(tdc)_(2)(MA)]n MOFs/polyacrylonitrile nanofibers composite,which was produced by the electrospinning technology.The electrochemical results show that the N,S co-doped porous carbon nanofibers can achieve capacity of 201.2 mAh·g^(-1)at the current density of 0.05 A·g^(-1).Furthermore,the reversible capacity still has 161.3 mAh·g^(-1)even at a high current density of 1 A·g^(-1)after 600 cycles.The superior electrochemical performance shows that the N,S co-doped porous carbon nanofibers electrode material can be used as an ideal anode material for sodium-ion batteries.
文摘A visible-light-active photocatalyst was prepared by calcination of the hydrolysis product of tetrabutyl titanate with ammonia as precipitant. The photocatalyst was characterized by X-ray diffraction (XRD), UV-Vis diffuse reflection spectra (DRS), thermal gravimetric-differential thermal analysis (TG-DTA), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM). The color of the photocatalyst was yellow and could absorb light wavelength under 550 nm as measured by DRS. The catalyst calcined at higher temperature will give lower absorbance for visible light. Structures of the sample were characterized mainly to be anatase by XRD except for the sample calcined at 700 ℃ which gave mixtures of anatase and rutile. TG-DTA results showed that temperature for anatase formation was 415 ℃. XPS results showed that doped-nitrogen was presented in the sample, they are important to show visible-light absorbency. The photocatalytic activities were evaluated using methyl orange and phenol as model pollutants, the results showed that over 90% of phenol could be degraded under visible light using N/TiO2 as the catalyst after 4 hours reaction. Almost the same activity was found for the TiO2 photocatalyst calcined at different temperature under sunlight but activities were different when the treatment was under UV light.
