We developed a novel approach for the preparation of N-doped TiO2 photocatalysts by calcining ammonium titanium oxalate at different temperatures. The structures of N-TiO2 were characterized by powder X-ray diffractio...We developed a novel approach for the preparation of N-doped TiO2 photocatalysts by calcining ammonium titanium oxalate at different temperatures. The structures of N-TiO2 were characterized by powder X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy, diffuse reflectance UV-Vis spectroscopy, and scanning electron microscope. The N-doped TiO2 photocatalysts calcined below 700 ℃ are the pure anatase phase but that calcined at 700 ℃ is a mixture of anatase and rutile phases. The doped N locates at the interstitial site of TiO2 which leads to the narrowing of bad gap of pure anatase N-TiO2. Among all photocatalysts, N-TiO2 photocatalysts calcined at 600 and 400 ℃ exhibit the best performance in the photodegradation of methyl orange under the UV light and all-wavelength light illuminations, respectively; however, because of the perfect crystallinity and the existence of anatase-rutile phase junctions, N-TiO2 photocatalyst calcined at 700 ℃ exhibits the highest specific photodegradation rate, i.e., the highest quantum yield, under both the UV light and all-wavelength light illuminations.展开更多
A novel visible light-active photocatalyst formulation（NdT/OP） was obtained by supporting N-doped TiO2（NdT） particles on up-conversion luminescent organic phosphors（OP）. The photocatalytic activity of such catal...A novel visible light-active photocatalyst formulation（NdT/OP） was obtained by supporting N-doped TiO2（NdT） particles on up-conversion luminescent organic phosphors（OP）. The photocatalytic activity of such catalysts was evaluated for the mineralization process of spiramycin in aqueous solution. The effect of NdT loading in the range 15–60 wt.% on bulk and surface characteristics of NdT/OP catalysts was investigated by several chemicophysical characterization techniques. The photocatalytic performance of NdT/OP catalysts in the removal of spyramicin from aqueous solution was assessed through photocatalytic tests under visible light irradiation. Total organic carbon（TOC） of aqueous solution,and CO and CO2 gas concentrations evolved during the photodegradation were analyzed. A dramatic enhancement of photocatalytic activity of the photostructured visible active NdT/OP catalysts,compared to NdT catalyst,was observed. Only CO2 was detected in gas-phase during visible light irradiation,proving that the photocatalytic process is effective in the mineralization of spiramycin,reaching very high values of TOC removal. The photocatalyst NdT/OP at 30 wt.% of NdT loading showed the highest photocatalytic activity（58%of TOC removed after 180 min irradiation against only 31% removal after 300 min of irradiation of NdT）. We attribute this enhanced activity to the high effectiveness in the utilization of visible light through improved light harvesting and exploiting. OP particles act as ＂photoactive support＂,able to be excited by the external visible light irradiation,and reissue luminescence of wavelength suitable to promote NdT photomineralization activity.展开更多
N-doped TiO2 nanoparticle photocatalysts were prepared through a sol-gel procedure using NH4C1 as the nitrogen source and followed by calcination at certain temperature. Systematic studies for the preparation paramete...N-doped TiO2 nanoparticle photocatalysts were prepared through a sol-gel procedure using NH4C1 as the nitrogen source and followed by calcination at certain temperature. Systematic studies for the preparation parameters and their impact on the structure and photocatalytic activity under ultraviolet （UV） and visible light irra-diation were carried out. Multiple techniques （XRD, TEM, DRIF, DSC, and XPS） were commanded to characterize the crystal structures and chemical binding of N-doped TiO2. Its photocatalytic activity was examined by the deg- radation of organic compounds. The catalytic activity of the prepared N-doped TiO2 nanoparticles under visible light （λ〉400nm） irradiation is evidenced by the decomposition of 4-chlorophenol, showing that nitrogen atoms in the N-doped TiO2 nanoparticle catalyst are responsible for the visible light catalytic activity. The N-doped TiO2 nanoparticle catalyst prepared with this modified route exhibits higher catalytic activity under UV irradiation in contrast to TiO2 without N-doping. It is suggested that the doped nitrogen here is located at the interstitial site of TiO2 lattice.展开更多
The hierarchical nanostructured N-doped TiO2 immobilized activated carbon fiber(N-TiO2/ACF)porous composites are fabricated to removal dynamic toluene gas.The results show that nitrogen ions doping and ACF modificatio...The hierarchical nanostructured N-doped TiO2 immobilized activated carbon fiber(N-TiO2/ACF)porous composites are fabricated to removal dynamic toluene gas.The results show that nitrogen ions doping and ACF modification can decrease the band gap of TiO2,leading to red shift toward visible light region.Interestingly,N-TiO2/ACF exhibits strongly synergistic effect owing to high surface area,good crystallinity,enhanced bandgap structure and light harvesting.The toluene removal rate of N-TiO2/ACF composites is 2.29 times higher than that of TiO2.The N-TiO2/ACF for toluene degradation followed the Langmuir-Hinshelwood kinetic model,and the rate constant is enhanced 8 times compared with TiO2.The possible photodegradation pathway and mechanisms are proposed.展开更多
Photocatalytic reduction of CO2 into various types of fuels has attracted great interest,and serves as a potential solution to addressing current global warming and energy challenges.In this work,Ag-Cu nanoparticles a...Photocatalytic reduction of CO2 into various types of fuels has attracted great interest,and serves as a potential solution to addressing current global warming and energy challenges.In this work,Ag-Cu nanoparticles are densely supported on N-doped TiO2 nanowire through a straightforward nanofabrication approach.The range of light absorption by N-doped TiO2 can be tuned to match the plasmonic band of Ag nanoparticles,which allows synergizing a resonant energy transfer process with the Schottky junction.Meanwhile,Cu nanoparticles can provide active sites for the reduction of CO2 molecules.Remarkably,the performance of photocatalytic CO2 reduction is improved to produce CH4 at a rate of 720μmol·g-1·h-1 under full-spectrum irradiation.展开更多
CO_(2) conversion to CO via the reverse water-gas shift(RWGS)reaction is limited by a low CO_(2) conversion rate and CO selectivity.Herein,an efficient RWGS catalyst is constructed through Enteromorpha prolifera–deri...CO_(2) conversion to CO via the reverse water-gas shift(RWGS)reaction is limited by a low CO_(2) conversion rate and CO selectivity.Herein,an efficient RWGS catalyst is constructed through Enteromorpha prolifera–derived N-rich mesoporous biochar(EPBC)supported atomic-level Cu-Mo_(2)C clusters(Cu-Mo_(2)C/EPBC).Unlike traditional acti-vated carbon(AC)supported Cu-Mo_(2)C particles(Cu-Mo_(2)C/AC),the Cu-Mo_(2)C/EPBC not only presents the better graphitization degree and larger specific surface area,but also uniformly andfirmly anchors atomic-level Cu-Mo_(2)C clusters due to the existence of pyridine nitrogen.Furthermore,the pyridine N of Cu-Mo_(2)C/EPBC strengthens an unblocked electron transfer between Mo_(2)C and Cu clusters,as verified by X-ray absorption spectroscopy.As a result,the synergistic effect between pyridinic N anchoring and the clusters interaction in Cu-Mo_(2)C/EPBC facilitates an improved CO selectivity of 99.95%at 500℃ compared with traditional Cu-Mo_(2)C/AC(99.60%),as well as about 3-fold CO_(2) conversion rate.Density functional theory calculations confirm that pyr-idine N-modified carbon activates the local electronic redistribution at Cu-Mo_(2)C clusters,which contributes to the decreased energy barrier of the transition state of CO^(*)+O^(*)+2H^(*),thereby triggering the transformation of rate-limited step during the redox pathway.This biomass-derived strategy opens perspective on producing sustain-able fuels and building blocks through the RWGS reaction.展开更多
The electrochemical reduction of carbon dioxide(CO_(2)RR)is a promising strategy for achieving carbon neutralization.The Ni-N_(4) site is well known as the active site in metal single atoms on N-doped carbon catalysts...The electrochemical reduction of carbon dioxide(CO_(2)RR)is a promising strategy for achieving carbon neutralization.The Ni-N_(4) site is well known as the active site in metal single atoms on N-doped carbon catalysts,while its symmetric charge distribution nature is not favorable for electron transfer and then hindering the efficient CO_(2)RR.Herein,we constructed a Ni SA/CNs single-atom catalyst.Notably,it features unique Ni-N_(4)-O active sites,featuring one axial O atom and four planar N atoms,constituting a broken symmetrical electronic structure of Ni-N_(4) sites.Furthermore,hierarchical pore structures were obtained with the assistance of NaNO_(3) pore-forming agent during thermal treatment process,which promote electronic and mass transfer.And the resulting high specific surface area can host more Ni-N_(4)-O active sites.These specialized active sites promote the key intermediate(∗CO)adsorption/desorption and suppresses hydrogen evolution.Consequently,the Ni SA/CNs catalyst exhibits a high turnover frequency(TOF)value,reaching 34,081 h^(-1) at-0.98 V vs.RHE.Additionally,it achieves an excellent CO Faradaic efficiency,exceeding 90%,over a wide potential range from-0.4 V to-1.0 V vs.RHE.This work not only offers a new method for the rational synthesize single-atom catalysts with unique Ni-N_(4)-O active sites,but also provides in-depth insight into the origin of catalytic activity of porous carbon-base catalysts.展开更多
The paper reports the fabrication of Zn-doped TiO_2 nanotubes(Zn-TONT)/ZnO nanoflakes heterostructure for the first time,which shows improved performance as a photoanode in dye-sensitized solar cell(DSSC).The layered ...The paper reports the fabrication of Zn-doped TiO_2 nanotubes(Zn-TONT)/ZnO nanoflakes heterostructure for the first time,which shows improved performance as a photoanode in dye-sensitized solar cell(DSSC).The layered structure of this novel nanoporous structure has been analyzed unambiguously by Rutherford backscattering spectroscopy,scanning electron microscopy,and X-ray diffractometer.The cell using the heterostructure as photoanode manifests an enhancement of about an order in the magnitude of the short circuit current and a seven-fold increase in efficiency,over pure TiO_2 photoanodes.Characterizations further reveal that the Zn-TONT is preferentially oriented in [001] direction and there is a Ti metal-depleted interface layer which leads to better band alignment in DSSC.展开更多
The N-doped TiO2 polycrystalline powder was synthesized through calcining the hydrolysis prodact of tetra-butyl titanate with ammonia. The photocatalytic activity of N-doped TiO2 powder with anatase phone calcined at ...The N-doped TiO2 polycrystalline powder was synthesized through calcining the hydrolysis prodact of tetra-butyl titanate with ammonia. The photocatalytic activity of N-doped TiO2 powder with anatase phone calcined at 400℃ was 2.7 times higher than that of Degussa P25 for phenol decomposition under visible light. All samples had mesoporoas structures. X- ray photoelectron spectroscopy confirmed that a trace amount of N atoms remained in the anatase polycrystaUine TiO2 powder when calcined at 400 ℃ as substitutional atoms at the oxygen sites. UV-Vis and EPR analyses indicated that oxygen vacancy states were created during the course of N-doped TiO2 powder formation. It is considered that substitutional N atoms, oxygen vacancy, states, large BET surface areas and mesoporoas structure are important facwrs for the N-doped photocatalyst to present a high vis-activity.展开更多
A systematic study on geometry, electronic structure and vibrational properties of N-doped TiO2 anatase cluster, within the framework of the density functional theory, has been performed in this work. The calculations...A systematic study on geometry, electronic structure and vibrational properties of N-doped TiO2 anatase cluster, within the framework of the density functional theory, has been performed in this work. The calculations confirmed that the most structures in substitutional model consist of a two-coordinate bridge structure and a three-coordinate hollow structure. The calculated results can well explain the red shift in N-doped TiO2 observed in experiments. The study provides an illustration for the N-doped anatase from the viewpoint of chemical bonding theory.展开更多
In this paper, ultrafine nitrogen-doped TiO2 photocatalyst with enhanced photocatalytic water-splitting properties was successfully fabricated via a solvothermal method. Herein, polyvinylpyrrolidone（PVP） was used as...In this paper, ultrafine nitrogen-doped TiO2 photocatalyst with enhanced photocatalytic water-splitting properties was successfully fabricated via a solvothermal method. Herein, polyvinylpyrrolidone（PVP） was used as both nitrogen source and stabilizer. The enhancement in water-splitting process can be attributed to the doping of element nitrogen, which could supply an intermediate energy level and promote the separation of photo-excited holes and electrons. Moreover, this paper provides a new application of high-molecular polymer to synthesize solar-driven water-splitting photocatalysts.展开更多
TiO2 nano powders with Mn concentration of 0 at%-12 at% were synthesized by the sol-gel process, and were annealed at 500 ℃ and 800 ℃ in air for 2 hrs. X-ray diffraction （XRD） measurements indicate that the Mn-TiO...TiO2 nano powders with Mn concentration of 0 at%-12 at% were synthesized by the sol-gel process, and were annealed at 500 ℃ and 800 ℃ in air for 2 hrs. X-ray diffraction （XRD） measurements indicate that the Mn-TiO2 nano powders with Mn concentration of 1 at% and 2 at% annealed at 500 and 800 ℃ are of pure anatase and rutile, respectively. The scanning electron microscope （SEM） observations reveal that the crystal grain size increases with the annealing temperature, and the high resolution transmission electron microscopy （HRTEM） investigations further indicate that the samples are well crystallized, confirming that Mn has doped into the TiO2 crystal lattice effectively. The room temperature ferromagnetism, which could be explained within the scope of the bound magnetic polaron （BMP） theory, is detected in the Mn-TiO2 samples with Mn concentration of 2 at%, and the magnetization of the powders annealed at 500 ℃ is stronger than that of the sample treated at 800 ℃. The UV-VIS diffuse reflectance spectra results demonstrate that the absorption of the TiO2 powders could be enlarged by the enhanced trapped electron absorption caused by Mn doping.展开更多
The catalysts of iron-doped Mn-Ce/TiO2 （Fe-Mn-Ce/TiO2） prepared by sol-gel method were investigated for low temperature selective catalytic reduction （SCR） of NO with NH3. It was found that the NO conversion over ...The catalysts of iron-doped Mn-Ce/TiO2 （Fe-Mn-Ce/TiO2） prepared by sol-gel method were investigated for low temperature selective catalytic reduction （SCR） of NO with NH3. It was found that the NO conversion over Fe-Mn-Ce/TiO2 was obviously improved after iron doping compared with that over Mn-Ce/TiO2. Fe-Mn-Ce/TiO2 with the molar ratio of Fe/Ti = 0.1 exhibited the highest activity. The results showed that 96.8% NO conversion was obtained over Fe（0.1）-Mn-Ce/TiO2 at 180~C at a space velocity of 50,000 hr-1. Fe-Mn-Ce/TiO2 exhibited much higher resistance to H2O and SO2 than that of Mn-Ce/TiO2. The properties of the catalysts were characterized using X-ray diffraction （XRD）, N2 adsorption, temperature programmed desorption （NH3-TPD and NOx-TPD）, and X- ray photoelectron spectroscopy （XPS） techniques. BET, NH3-TPD and NOx-TPD results showed that the specific surface area and NH3 and NOx adsorption capacity of the catalysts increased with iron doping. It was known from XPS analysis that iron valence state on the surface of the catalysts were in Fe^3＋ state. The doping of iron enhanced the dispersion and oxidation state of Mn and Ce on the surface of the catalysts. The oxygen concentrations on the surface of the catalysts were found to increase after iron doping. Fe-Mn-Ce/TiO2 represented a promising catalyst for low temperature SCR of NO with NH3 in the presence of H20 and SO2.展开更多
A visible-light photocatalyst was prepared by calcination of the hydrolysis product of Ti(SO_4)_2 with ammonia as precipitator. The color of this photocatalyst was vivid yellow. It could absorb light under 550 nm wave...A visible-light photocatalyst was prepared by calcination of the hydrolysis product of Ti(SO_4)_2 with ammonia as precipitator. The color of this photocatalyst was vivid yellow. It could absorb light under 550 nm wavelength. The crystal structure of anatase was characterized by XRD. The structure analysis result of X-ray fluorescence(XRF) shows that doped-nitrogen was presented in the sample. The photocatalytic activities were evaluated using methyl orange and phenol as model pollutants. The photocatalytic activities of samples were increasing gradually with calcination temperature from 400℃ to 700℃ under UV irradiation. It can be seen that the degradation of methyl orange follows zero-order kinetics. However, the calcination temperatures have no significant influence on the degradation of phenol under sunlight. The N-doped catalyst shows higher activity than the bare one under solar irradiation.展开更多
Photocatalysis based on semiconductors has recently been receiving considerable research interest because of its extensive applications in environmental remediation and renewable energy generation.Various semiconducto...Photocatalysis based on semiconductors has recently been receiving considerable research interest because of its extensive applications in environmental remediation and renewable energy generation.Various semiconductor-based materials that are vital to solar energy utilization have been extensively investigated,among which titanium oxide(TiO_(2))has attracted considerable attention because of its exceptional physicochemical characteristics.However,the sluggish responsiveness to visible light in the solar spectrum and the inefficient separation of photoinduced electron-hole pairs hamper the practical application of TiO_(2) materials.To overcome the aforementioned serious drawbacks of TiO_(2),numerous strategies,such as doping with foreign atoms,particularly nitrogen(N),have been improved in the past few decades.This review aims to provide a comprehensive update and description of the recent developments of N-doped TiO_(2) materials for visible lightresponsive photocatalysis,such as(1)the preparation of N-doped/co-doped TiO_(2) photocatalysts and(2)mechanistic studies on the reasons for visible light response.Furthermore,the most recent and significant advances in the field of solar energy applications of modified N-doped TiO_(2) are summarized.The analysis indicated the critical need for further development of these types of materials for the solar-to-energy conversion,particularly for water splitting purposes.展开更多
A carbon‐doped TiO2/fly ash support(C‐TiO2/FAS)composite photocatalyst was successfully synthesized through sol impregnation and subsequent carbonization.The carbon dopants were derived from the organic species gene...A carbon‐doped TiO2/fly ash support(C‐TiO2/FAS)composite photocatalyst was successfully synthesized through sol impregnation and subsequent carbonization.The carbon dopants were derived from the organic species generated during the synthesis of the C‐TiO2/FAS composite.A series of analytical techniques,such as scanning electron microscopy(SEM),attenuated total reflection‐Fourier transform infrared(ATR‐FTIR)spectroscopy,X‐ray photoelectron spectroscopy(XPS),and ultraviolet‐visible diffuse reflectance spectroscopy(UV‐Vis DRS),were used to characterize the properties of the prepared samples.The results indicated that C‐TiO2 was successfully coated on the FAS surface.Coupling between C‐TiO2 and FAS resulted in the formation of Si–O–C and Al–O–Ti bonds at their interface.The formation of Si–O–C and Al–O–Ti bonds gave rise to a positive shift of the valence band edge of C‐TiO2 and enhanced its oxidation capability of photogenerated holes as well as photodegradation efficiency of methyl orange.Moreover,the C‐TiO2/FAS photocatalyst exhibited favorable reusability and separability.This work may provide a new route for tuning the electronic band structure of TiO2.展开更多
Zn-doped TiO2 (Zn?TiO2) thin films were prepared by the sol?gel method on titanium substrates with heat treatment at different temperatures. The effects of heat treatment temperatures and Zn doping on the structure, p...Zn-doped TiO2 (Zn?TiO2) thin films were prepared by the sol?gel method on titanium substrates with heat treatment at different temperatures. The effects of heat treatment temperatures and Zn doping on the structure, photocathodic protection and photoelectrochemical properties of TiO2 thin films were investigated. It is indicated that the photoelectrical performance of the Zn?TiO2 films is enhanced with the addition of Zn element compared with the pure-TiO2 film and the largest decline by 897 mV in the electrode potential is achieved under 300 °C heat treatment. SEM?EDS analyses show that Zn element is unevenly distributed in Zn?TiO2 films; XRD patterns reveal that the grain size of Zn?TiO2 is smaller than that of pure-TiO2; FTIR results indicate that Zn - O bond forms on Zn?TiO2 surface. Ultraviolet visible absorption spectra prove that Zn?TiO2 shifts to visible light region.Mott?Shottky curves show that the flat-band potential of Zn?TiO2 is more negative and charge carrier density is bigger than that ofpure-TiO2, implying that under the synergy of the width of the space-charge layer, carrier density and flat-band potential, Zn?TiO2 with 300 °C heat treatment displays the best photocathodic protection performance.展开更多
With great superiorities in energy density,rate capability and structural stability,Na_(3)V_(2)(PO_(4))_(2) F_(3)(NVPF)has attracted much attentions as cathode of sodium ion battery(SIB),but it also faces challenges o...With great superiorities in energy density,rate capability and structural stability,Na_(3)V_(2)(PO_(4))_(2) F_(3)(NVPF)has attracted much attentions as cathode of sodium ion battery(SIB),but it also faces challenges on its poor intrinsic electronic conductivity and the controversial de/sodiation mechanism.Herein,a series of Zr-doped NVPF coated by N-doped carbon layer(~5 nm in thickness,homogenously)materials are fabricated by a sol-gel method,and the optimized heteroatom-doping amounts of Zr and N doping improve intrinsic properties on enlarging lattice distance and enhancing electronic conductivity,respectively.Specifically,among all samples of Na_(3) V_(2-x)Zr_(x)(PO_(4))_(2) F_(3)/NC(NVPF-Zr-x/NC,x=0,0.01,0.02,0.05,and 0.1),the optimized electrode of NVPF-Zr-0.02/NC delivers high reversible capacities(119.2 mAh g^(-1) at0.5 C),superior rate capability(98.1 mA h g^(-1) at 20 C)and excellent cycling performance.The structural evolution of NVPF-Zr-0.02/NC electrode,in-situ monitored by X-ray diffractometer,follows a step-wise Na-extraction/intercalation mechanism with reversible multi-phase changes,not just a solid-solutionreaction one.Full cells of NVPF-Zr-0.02/NC//hard carbon demonstrate high capacity(99.8 mA h g^(-1) at 0.5 C),high out-put voltage(3.5 V)and good cycling stability.This work is favorable to accelerate the development of high-performance cathode materials and explore possible redox reaction mechanisms of SIBs.展开更多
The conversion of carbon dioxide into valuable organic compounds is a highly promising approach to address the energy issues and environmental problems(e.g., global warming). Herein, we presents a facile and efficient...The conversion of carbon dioxide into valuable organic compounds is a highly promising approach to address the energy issues and environmental problems(e.g., global warming). Herein, we presents a facile and efficient method to prepare highly dense and well-dispersed SnO2 nanocrystals on 1 D N-doped carbon nanowires as advanced catalysts for the efficient electroreduction of CO2 to formate. The ultrasmall SnO2 coated on the N-doped carbon nanowires(SnO2@N-CNW) has been synthesized via the simple hydrothermal treatment coupled with a pyrolysis process. The unique structure enables to expose the active tin oxide and also provides the facile pathways for rapid transfer of electron and electrolyte along with the highly porous carbon foam composed with interconnected carbon nanowires. Therefore, SnO2@NCNW electrocatalyst exhibits good durability and high selectivity for formate formation with a Faradaic efficiency of ca. 90%. This work demonstrates a simple method to rationally design high-dense tin oxide nanocrystals on the conductive carbon support as advanced catalysts for CO2 electroreduction.展开更多
Low cost,highly selective and efficient electrocatalysts for CO_(2)reduction reaction(CO_(2)RR)is crucial for lowering the global carbon footprint and mitigating energy shortages.Here,we first report a highly selectiv...Low cost,highly selective and efficient electrocatalysts for CO_(2)reduction reaction(CO_(2)RR)is crucial for lowering the global carbon footprint and mitigating energy shortages.Here,we first report a highly selective and efficient electrocatalyst for CO_(2)RR to CO using a surface-regulated Ni nanoparticles supported on N-doped CMK-3(N,O-Ni/CMK3).Compared with most Ni metal catalysts previously reported with severe competitive hydrogen evolution during the CO_(2)RR,the N,O-Ni/CMK3 catalyst presents a superior CO faradaic efficiency of about 97%,a high CO partial current density(13.01 mA cm^(-1))and turnover frequency(4.25 s^(–1)).The comprehensive characterization provides evidence that the N,O co-regulated Ni acts as the active center.Taking advantage of the N,O co-regulated chemical environment,N,O-Ni/CMK3 also displays a decent stability at negative potentials.Our work paves a novel approach for developing transition metal catalysts for CO_(2)RR with enhanced activity and selectivity via regulating surface chemical environment.展开更多
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China （No.20773113）, the Solar Energy Project of Chinese Academy of Sciences, the Ministry of Education program for PCSIRT （No.IRT0756）, and the Max Planck Gesellschaft of Chinese Academy of Sciences partner group.
文摘We developed a novel approach for the preparation of N-doped TiO2 photocatalysts by calcining ammonium titanium oxalate at different temperatures. The structures of N-TiO2 were characterized by powder X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy, diffuse reflectance UV-Vis spectroscopy, and scanning electron microscope. The N-doped TiO2 photocatalysts calcined below 700 ℃ are the pure anatase phase but that calcined at 700 ℃ is a mixture of anatase and rutile phases. The doped N locates at the interstitial site of TiO2 which leads to the narrowing of bad gap of pure anatase N-TiO2. Among all photocatalysts, N-TiO2 photocatalysts calcined at 600 and 400 ℃ exhibit the best performance in the photodegradation of methyl orange under the UV light and all-wavelength light illuminations, respectively; however, because of the perfect crystallinity and the existence of anatase-rutile phase junctions, N-TiO2 photocatalyst calcined at 700 ℃ exhibits the highest specific photodegradation rate, i.e., the highest quantum yield, under both the UV light and all-wavelength light illuminations.
文摘A novel visible light-active photocatalyst formulation（NdT/OP） was obtained by supporting N-doped TiO2（NdT） particles on up-conversion luminescent organic phosphors（OP）. The photocatalytic activity of such catalysts was evaluated for the mineralization process of spiramycin in aqueous solution. The effect of NdT loading in the range 15–60 wt.% on bulk and surface characteristics of NdT/OP catalysts was investigated by several chemicophysical characterization techniques. The photocatalytic performance of NdT/OP catalysts in the removal of spyramicin from aqueous solution was assessed through photocatalytic tests under visible light irradiation. Total organic carbon（TOC） of aqueous solution,and CO and CO2 gas concentrations evolved during the photodegradation were analyzed. A dramatic enhancement of photocatalytic activity of the photostructured visible active NdT/OP catalysts,compared to NdT catalyst,was observed. Only CO2 was detected in gas-phase during visible light irradiation,proving that the photocatalytic process is effective in the mineralization of spiramycin,reaching very high values of TOC removal. The photocatalyst NdT/OP at 30 wt.% of NdT loading showed the highest photocatalytic activity（58%of TOC removed after 180 min irradiation against only 31% removal after 300 min of irradiation of NdT）. We attribute this enhanced activity to the high effectiveness in the utilization of visible light through improved light harvesting and exploiting. OP particles act as ＂photoactive support＂,able to be excited by the external visible light irradiation,and reissue luminescence of wavelength suitable to promote NdT photomineralization activity.
基金Supported by the Science and Technology Research Program of Chongqing Education Commission （KJ050702）, and the Natural Science Foundation Project of Chongqing Science and Technology（Commission （No.2007BB7208）.
文摘N-doped TiO2 nanoparticle photocatalysts were prepared through a sol-gel procedure using NH4C1 as the nitrogen source and followed by calcination at certain temperature. Systematic studies for the preparation parameters and their impact on the structure and photocatalytic activity under ultraviolet （UV） and visible light irra-diation were carried out. Multiple techniques （XRD, TEM, DRIF, DSC, and XPS） were commanded to characterize the crystal structures and chemical binding of N-doped TiO2. Its photocatalytic activity was examined by the deg- radation of organic compounds. The catalytic activity of the prepared N-doped TiO2 nanoparticles under visible light （λ〉400nm） irradiation is evidenced by the decomposition of 4-chlorophenol, showing that nitrogen atoms in the N-doped TiO2 nanoparticle catalyst are responsible for the visible light catalytic activity. The N-doped TiO2 nanoparticle catalyst prepared with this modified route exhibits higher catalytic activity under UV irradiation in contrast to TiO2 without N-doping. It is suggested that the doped nitrogen here is located at the interstitial site of TiO2 lattice.
基金This study was supported by the CNPC Research Institute of Safety and Environmental Protection Technology(No.PPCIP2017005).
文摘The hierarchical nanostructured N-doped TiO2 immobilized activated carbon fiber(N-TiO2/ACF)porous composites are fabricated to removal dynamic toluene gas.The results show that nitrogen ions doping and ACF modification can decrease the band gap of TiO2,leading to red shift toward visible light region.Interestingly,N-TiO2/ACF exhibits strongly synergistic effect owing to high surface area,good crystallinity,enhanced bandgap structure and light harvesting.The toluene removal rate of N-TiO2/ACF composites is 2.29 times higher than that of TiO2.The N-TiO2/ACF for toluene degradation followed the Langmuir-Hinshelwood kinetic model,and the rate constant is enhanced 8 times compared with TiO2.The possible photodegradation pathway and mechanisms are proposed.
基金supported by the National Key R&D Program of China (2017YFA0207301)National Natural Science Foundation of China (No.21725102, No.21471141,No.21601173)+3 种基金CAS Key Research Program of Frontier Sciences(QYZDB-SSWSLH018)CAS Interdisciplinary Innovation Team,Innovative Program of Development Foundation of Hefei Center for Physical Science and Technology (No.2016FXCX003)Anhui Provincial Natural Science Foundation (No.1608085QB24)Chinese Universities Scientific Fund (WK2310000067)
文摘Photocatalytic reduction of CO2 into various types of fuels has attracted great interest,and serves as a potential solution to addressing current global warming and energy challenges.In this work,Ag-Cu nanoparticles are densely supported on N-doped TiO2 nanowire through a straightforward nanofabrication approach.The range of light absorption by N-doped TiO2 can be tuned to match the plasmonic band of Ag nanoparticles,which allows synergizing a resonant energy transfer process with the Schottky junction.Meanwhile,Cu nanoparticles can provide active sites for the reduction of CO2 molecules.Remarkably,the performance of photocatalytic CO2 reduction is improved to produce CH4 at a rate of 720μmol·g-1·h-1 under full-spectrum irradiation.
基金support from National Natural Science Foundation of China(32101474 and 42377249)National Key Research and Development Program of China(2023YFD2201605).
文摘CO_(2) conversion to CO via the reverse water-gas shift(RWGS)reaction is limited by a low CO_(2) conversion rate and CO selectivity.Herein,an efficient RWGS catalyst is constructed through Enteromorpha prolifera–derived N-rich mesoporous biochar(EPBC)supported atomic-level Cu-Mo_(2)C clusters(Cu-Mo_(2)C/EPBC).Unlike traditional acti-vated carbon(AC)supported Cu-Mo_(2)C particles(Cu-Mo_(2)C/AC),the Cu-Mo_(2)C/EPBC not only presents the better graphitization degree and larger specific surface area,but also uniformly andfirmly anchors atomic-level Cu-Mo_(2)C clusters due to the existence of pyridine nitrogen.Furthermore,the pyridine N of Cu-Mo_(2)C/EPBC strengthens an unblocked electron transfer between Mo_(2)C and Cu clusters,as verified by X-ray absorption spectroscopy.As a result,the synergistic effect between pyridinic N anchoring and the clusters interaction in Cu-Mo_(2)C/EPBC facilitates an improved CO selectivity of 99.95%at 500℃ compared with traditional Cu-Mo_(2)C/AC(99.60%),as well as about 3-fold CO_(2) conversion rate.Density functional theory calculations confirm that pyr-idine N-modified carbon activates the local electronic redistribution at Cu-Mo_(2)C clusters,which contributes to the decreased energy barrier of the transition state of CO^(*)+O^(*)+2H^(*),thereby triggering the transformation of rate-limited step during the redox pathway.This biomass-derived strategy opens perspective on producing sustain-able fuels and building blocks through the RWGS reaction.
基金financially supported by National High-Level Talent FundNational Natural Science Foundation of China (Nos. 22372138,22461160253,22121001,and 22072118)+3 种基金thank financial support from State Key Laboratory of Physical Chemistry of Solid Surfaces of Xiamen UniversityShenzhen Science and Technology Program (No. JCYJ20220530143401002)supported by Science and Technology Projects of Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM) (No. HRTP-[2022]-3)the Fundamental Research Funds for the Central Universities (No. 20720220008)
文摘The electrochemical reduction of carbon dioxide(CO_(2)RR)is a promising strategy for achieving carbon neutralization.The Ni-N_(4) site is well known as the active site in metal single atoms on N-doped carbon catalysts,while its symmetric charge distribution nature is not favorable for electron transfer and then hindering the efficient CO_(2)RR.Herein,we constructed a Ni SA/CNs single-atom catalyst.Notably,it features unique Ni-N_(4)-O active sites,featuring one axial O atom and four planar N atoms,constituting a broken symmetrical electronic structure of Ni-N_(4) sites.Furthermore,hierarchical pore structures were obtained with the assistance of NaNO_(3) pore-forming agent during thermal treatment process,which promote electronic and mass transfer.And the resulting high specific surface area can host more Ni-N_(4)-O active sites.These specialized active sites promote the key intermediate(∗CO)adsorption/desorption and suppresses hydrogen evolution.Consequently,the Ni SA/CNs catalyst exhibits a high turnover frequency(TOF)value,reaching 34,081 h^(-1) at-0.98 V vs.RHE.Additionally,it achieves an excellent CO Faradaic efficiency,exceeding 90%,over a wide potential range from-0.4 V to-1.0 V vs.RHE.This work not only offers a new method for the rational synthesize single-atom catalysts with unique Ni-N_(4)-O active sites,but also provides in-depth insight into the origin of catalytic activity of porous carbon-base catalysts.
基金UGC-DAE CSR,Indore,for funding through a collaborative project and SAIF IIT Bombay for the help with SEMsupported by the Michigan Space Grant Consortium+1 种基金by Hope CollegeDAE-BRNS for funding the preliminary works
文摘The paper reports the fabrication of Zn-doped TiO_2 nanotubes(Zn-TONT)/ZnO nanoflakes heterostructure for the first time,which shows improved performance as a photoanode in dye-sensitized solar cell(DSSC).The layered structure of this novel nanoporous structure has been analyzed unambiguously by Rutherford backscattering spectroscopy,scanning electron microscopy,and X-ray diffractometer.The cell using the heterostructure as photoanode manifests an enhancement of about an order in the magnitude of the short circuit current and a seven-fold increase in efficiency,over pure TiO_2 photoanodes.Characterizations further reveal that the Zn-TONT is preferentially oriented in [001] direction and there is a Ti metal-depleted interface layer which leads to better band alignment in DSSC.
基金Funded by National "973"Plan Research Project ( No.2004CB619204)and Educational Ministry Scientific and Technologi-cal Research Key Project(No.02052)
文摘The N-doped TiO2 polycrystalline powder was synthesized through calcining the hydrolysis prodact of tetra-butyl titanate with ammonia. The photocatalytic activity of N-doped TiO2 powder with anatase phone calcined at 400℃ was 2.7 times higher than that of Degussa P25 for phenol decomposition under visible light. All samples had mesoporoas structures. X- ray photoelectron spectroscopy confirmed that a trace amount of N atoms remained in the anatase polycrystaUine TiO2 powder when calcined at 400 ℃ as substitutional atoms at the oxygen sites. UV-Vis and EPR analyses indicated that oxygen vacancy states were created during the course of N-doped TiO2 powder formation. It is considered that substitutional N atoms, oxygen vacancy, states, large BET surface areas and mesoporoas structure are important facwrs for the N-doped photocatalyst to present a high vis-activity.
基金Supported by the National Natural Science Foundation of China (No. 20503021)National Basic Research Program of China (2007CB815301)
文摘A systematic study on geometry, electronic structure and vibrational properties of N-doped TiO2 anatase cluster, within the framework of the density functional theory, has been performed in this work. The calculations confirmed that the most structures in substitutional model consist of a two-coordinate bridge structure and a three-coordinate hollow structure. The calculated results can well explain the red shift in N-doped TiO2 observed in experiments. The study provides an illustration for the N-doped anatase from the viewpoint of chemical bonding theory.
基金supported financially by the National Natural Science Foundation of China(Grant No.51272107 and Grant No.51572126)the Department of Education of Jiangsu Province(KYLX_0352)Fundamental Research Funds for the Central Universities(No.30920140132038)
文摘In this paper, ultrafine nitrogen-doped TiO2 photocatalyst with enhanced photocatalytic water-splitting properties was successfully fabricated via a solvothermal method. Herein, polyvinylpyrrolidone（PVP） was used as both nitrogen source and stabilizer. The enhancement in water-splitting process can be attributed to the doping of element nitrogen, which could supply an intermediate energy level and promote the separation of photo-excited holes and electrons. Moreover, this paper provides a new application of high-molecular polymer to synthesize solar-driven water-splitting photocatalysts.
基金Project supported by the Innovation Foundation of BUAA for PhD Graduates (Grant No. 292122)Equipment Research Foundation of China
文摘TiO2 nano powders with Mn concentration of 0 at%-12 at% were synthesized by the sol-gel process, and were annealed at 500 ℃ and 800 ℃ in air for 2 hrs. X-ray diffraction （XRD） measurements indicate that the Mn-TiO2 nano powders with Mn concentration of 1 at% and 2 at% annealed at 500 and 800 ℃ are of pure anatase and rutile, respectively. The scanning electron microscope （SEM） observations reveal that the crystal grain size increases with the annealing temperature, and the high resolution transmission electron microscopy （HRTEM） investigations further indicate that the samples are well crystallized, confirming that Mn has doped into the TiO2 crystal lattice effectively. The room temperature ferromagnetism, which could be explained within the scope of the bound magnetic polaron （BMP） theory, is detected in the Mn-TiO2 samples with Mn concentration of 2 at%, and the magnetization of the powders annealed at 500 ℃ is stronger than that of the sample treated at 800 ℃. The UV-VIS diffuse reflectance spectra results demonstrate that the absorption of the TiO2 powders could be enlarged by the enhanced trapped electron absorption caused by Mn doping.
基金supported by the National Natural Science Foundation of China (No. 90610018,50976050)the New Century Excellent Talents in University (No. NCET-07-0457)the National Key Technologies R&D Program of Tianjin (No. 09ZCKFSH01900)
文摘The catalysts of iron-doped Mn-Ce/TiO2 （Fe-Mn-Ce/TiO2） prepared by sol-gel method were investigated for low temperature selective catalytic reduction （SCR） of NO with NH3. It was found that the NO conversion over Fe-Mn-Ce/TiO2 was obviously improved after iron doping compared with that over Mn-Ce/TiO2. Fe-Mn-Ce/TiO2 with the molar ratio of Fe/Ti = 0.1 exhibited the highest activity. The results showed that 96.8% NO conversion was obtained over Fe（0.1）-Mn-Ce/TiO2 at 180~C at a space velocity of 50,000 hr-1. Fe-Mn-Ce/TiO2 exhibited much higher resistance to H2O and SO2 than that of Mn-Ce/TiO2. The properties of the catalysts were characterized using X-ray diffraction （XRD）, N2 adsorption, temperature programmed desorption （NH3-TPD and NOx-TPD）, and X- ray photoelectron spectroscopy （XPS） techniques. BET, NH3-TPD and NOx-TPD results showed that the specific surface area and NH3 and NOx adsorption capacity of the catalysts increased with iron doping. It was known from XPS analysis that iron valence state on the surface of the catalysts were in Fe^3＋ state. The doping of iron enhanced the dispersion and oxidation state of Mn and Ce on the surface of the catalysts. The oxygen concentrations on the surface of the catalysts were found to increase after iron doping. Fe-Mn-Ce/TiO2 represented a promising catalyst for low temperature SCR of NO with NH3 in the presence of H20 and SO2.
文摘A visible-light photocatalyst was prepared by calcination of the hydrolysis product of Ti(SO_4)_2 with ammonia as precipitator. The color of this photocatalyst was vivid yellow. It could absorb light under 550 nm wavelength. The crystal structure of anatase was characterized by XRD. The structure analysis result of X-ray fluorescence(XRF) shows that doped-nitrogen was presented in the sample. The photocatalytic activities were evaluated using methyl orange and phenol as model pollutants. The photocatalytic activities of samples were increasing gradually with calcination temperature from 400℃ to 700℃ under UV irradiation. It can be seen that the degradation of methyl orange follows zero-order kinetics. However, the calcination temperatures have no significant influence on the degradation of phenol under sunlight. The N-doped catalyst shows higher activity than the bare one under solar irradiation.
基金supported by the National Natural Science Foundation of China(Nos.21633009,21925206,21901240)the National Key Research and Development Program of China(No.2020YFA0406102)。
文摘Photocatalysis based on semiconductors has recently been receiving considerable research interest because of its extensive applications in environmental remediation and renewable energy generation.Various semiconductor-based materials that are vital to solar energy utilization have been extensively investigated,among which titanium oxide(TiO_(2))has attracted considerable attention because of its exceptional physicochemical characteristics.However,the sluggish responsiveness to visible light in the solar spectrum and the inefficient separation of photoinduced electron-hole pairs hamper the practical application of TiO_(2) materials.To overcome the aforementioned serious drawbacks of TiO_(2),numerous strategies,such as doping with foreign atoms,particularly nitrogen(N),have been improved in the past few decades.This review aims to provide a comprehensive update and description of the recent developments of N-doped TiO_(2) materials for visible lightresponsive photocatalysis,such as(1)the preparation of N-doped/co-doped TiO_(2) photocatalysts and(2)mechanistic studies on the reasons for visible light response.Furthermore,the most recent and significant advances in the field of solar energy applications of modified N-doped TiO_(2) are summarized.The analysis indicated the critical need for further development of these types of materials for the solar-to-energy conversion,particularly for water splitting purposes.
文摘A carbon‐doped TiO2/fly ash support(C‐TiO2/FAS)composite photocatalyst was successfully synthesized through sol impregnation and subsequent carbonization.The carbon dopants were derived from the organic species generated during the synthesis of the C‐TiO2/FAS composite.A series of analytical techniques,such as scanning electron microscopy(SEM),attenuated total reflection‐Fourier transform infrared(ATR‐FTIR)spectroscopy,X‐ray photoelectron spectroscopy(XPS),and ultraviolet‐visible diffuse reflectance spectroscopy(UV‐Vis DRS),were used to characterize the properties of the prepared samples.The results indicated that C‐TiO2 was successfully coated on the FAS surface.Coupling between C‐TiO2 and FAS resulted in the formation of Si–O–C and Al–O–Ti bonds at their interface.The formation of Si–O–C and Al–O–Ti bonds gave rise to a positive shift of the valence band edge of C‐TiO2 and enhanced its oxidation capability of photogenerated holes as well as photodegradation efficiency of methyl orange.Moreover,the C‐TiO2/FAS photocatalyst exhibited favorable reusability and separability.This work may provide a new route for tuning the electronic band structure of TiO2.
基金Project(cstc2011jj A50008)supported by the Natural Science Foundation of Chongqing,ChinaProject(14ZB0025)supported by Education Department of Sichuan Province,China
文摘Zn-doped TiO2 (Zn?TiO2) thin films were prepared by the sol?gel method on titanium substrates with heat treatment at different temperatures. The effects of heat treatment temperatures and Zn doping on the structure, photocathodic protection and photoelectrochemical properties of TiO2 thin films were investigated. It is indicated that the photoelectrical performance of the Zn?TiO2 films is enhanced with the addition of Zn element compared with the pure-TiO2 film and the largest decline by 897 mV in the electrode potential is achieved under 300 °C heat treatment. SEM?EDS analyses show that Zn element is unevenly distributed in Zn?TiO2 films; XRD patterns reveal that the grain size of Zn?TiO2 is smaller than that of pure-TiO2; FTIR results indicate that Zn - O bond forms on Zn?TiO2 surface. Ultraviolet visible absorption spectra prove that Zn?TiO2 shifts to visible light region.Mott?Shottky curves show that the flat-band potential of Zn?TiO2 is more negative and charge carrier density is bigger than that ofpure-TiO2, implying that under the synergy of the width of the space-charge layer, carrier density and flat-band potential, Zn?TiO2 with 300 °C heat treatment displays the best photocathodic protection performance.
基金the National Natural Science Foundation of China(21975154)the Shanghai Municipal Education Commission(Innovation Program(2019-01-07-00-09E00021)+2 种基金Innovative Research Team of High-level Local Universities in Shanghaisupported by The Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher LearningShanghai Key Laboratory of Materials Protection and Advanced Materials in Electric Power。
文摘With great superiorities in energy density,rate capability and structural stability,Na_(3)V_(2)(PO_(4))_(2) F_(3)(NVPF)has attracted much attentions as cathode of sodium ion battery(SIB),but it also faces challenges on its poor intrinsic electronic conductivity and the controversial de/sodiation mechanism.Herein,a series of Zr-doped NVPF coated by N-doped carbon layer(~5 nm in thickness,homogenously)materials are fabricated by a sol-gel method,and the optimized heteroatom-doping amounts of Zr and N doping improve intrinsic properties on enlarging lattice distance and enhancing electronic conductivity,respectively.Specifically,among all samples of Na_(3) V_(2-x)Zr_(x)(PO_(4))_(2) F_(3)/NC(NVPF-Zr-x/NC,x=0,0.01,0.02,0.05,and 0.1),the optimized electrode of NVPF-Zr-0.02/NC delivers high reversible capacities(119.2 mAh g^(-1) at0.5 C),superior rate capability(98.1 mA h g^(-1) at 20 C)and excellent cycling performance.The structural evolution of NVPF-Zr-0.02/NC electrode,in-situ monitored by X-ray diffractometer,follows a step-wise Na-extraction/intercalation mechanism with reversible multi-phase changes,not just a solid-solutionreaction one.Full cells of NVPF-Zr-0.02/NC//hard carbon demonstrate high capacity(99.8 mA h g^(-1) at 0.5 C),high out-put voltage(3.5 V)and good cycling stability.This work is favorable to accelerate the development of high-performance cathode materials and explore possible redox reaction mechanisms of SIBs.
基金financially supported by Guangdong Province Science and Technology Plan Project for Public Welfare Fund and Ability Construction Project(JCYJ20180301171324915)the National Natural Science Foundation of China(No.21503116)+1 种基金Taishan Scholars Program of Shandong Province(No.tsqn20161004)the Youth 1000 Talent Program of China。
文摘The conversion of carbon dioxide into valuable organic compounds is a highly promising approach to address the energy issues and environmental problems(e.g., global warming). Herein, we presents a facile and efficient method to prepare highly dense and well-dispersed SnO2 nanocrystals on 1 D N-doped carbon nanowires as advanced catalysts for the efficient electroreduction of CO2 to formate. The ultrasmall SnO2 coated on the N-doped carbon nanowires(SnO2@N-CNW) has been synthesized via the simple hydrothermal treatment coupled with a pyrolysis process. The unique structure enables to expose the active tin oxide and also provides the facile pathways for rapid transfer of electron and electrolyte along with the highly porous carbon foam composed with interconnected carbon nanowires. Therefore, SnO2@NCNW electrocatalyst exhibits good durability and high selectivity for formate formation with a Faradaic efficiency of ca. 90%. This work demonstrates a simple method to rationally design high-dense tin oxide nanocrystals on the conductive carbon support as advanced catalysts for CO2 electroreduction.
文摘Low cost,highly selective and efficient electrocatalysts for CO_(2)reduction reaction(CO_(2)RR)is crucial for lowering the global carbon footprint and mitigating energy shortages.Here,we first report a highly selective and efficient electrocatalyst for CO_(2)RR to CO using a surface-regulated Ni nanoparticles supported on N-doped CMK-3(N,O-Ni/CMK3).Compared with most Ni metal catalysts previously reported with severe competitive hydrogen evolution during the CO_(2)RR,the N,O-Ni/CMK3 catalyst presents a superior CO faradaic efficiency of about 97%,a high CO partial current density(13.01 mA cm^(-1))and turnover frequency(4.25 s^(–1)).The comprehensive characterization provides evidence that the N,O co-regulated Ni acts as the active center.Taking advantage of the N,O co-regulated chemical environment,N,O-Ni/CMK3 also displays a decent stability at negative potentials.Our work paves a novel approach for developing transition metal catalysts for CO_(2)RR with enhanced activity and selectivity via regulating surface chemical environment.
