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1.
Cancer Med ; 12(16): 16687-16696, 2023 08.
Article in English | MEDLINE | ID: mdl-37602656

ABSTRACT

BACKGROUND: Circulating tumor DNA (ctDNA)-based minimal residual disease (MRD) detection, which can identify disease relapse ahead of radiological imaging, has shown promising performance. The objective of this study was to develop and validate OriMIRACLE S (Minimal Residual Circulating Nucleic Acid Longitudinal Detection in Solid Tumor), a highly sensitive and specific tumor-informed assay for MRD detection. METHODS: Tumor-specific somatic single nucleotide variants (SNVs) were identified via whole exome sequencing of tumor tissue and matched germline DNA. Clonal SNVs were selected using the OriSelector algorithm for patient-specific, multiplex PCR-based NGS assays in MRD detection. Plasma-free DNA from patients with gastrointestinal tumors prior to and following an operation, and during monitoring, were ultradeep sequenced. RESULTS: The detection of three positive sites was sufficient to achieve nearly 100% overall sample level sensitivity and specificity and was determined by calculating binomial probability based on customized panels containing 21 to 30 variants. A total of 127 patients with gastrointestinal tumors were enrolled in our study. Preoperatively, MRD was positive in 18 of 26 patients (69.23%). Following surgery, MRD was positive in 24 of 82 patients (29.27%). The positivity rate for MRD was 33.33% (n = 18) for gastric adenocarcinoma and 32.26% (n = 62) for colorectal cancer. Twenty (20) of 59 patients (34.48%) experienced a change in MRD status over the monitoring period. Patients 8 and 31 responded to 3 cycles of systemic therapy, after which levels for all ctDNA dropped below the detection limit. Patient 53 was an example of using MRD to predict tumor metastasis. Patient 55 showed a weak response to treatments first and respond to new systemic therapy after tumor progression. CONCLUSION: Our study identified a sensitive and specific clinical detection method for low frequency ctDNA, and explored the detection performance of this technology in gastrointestinal tumors.


Subject(s)
Carcinoma , Circulating Tumor DNA , Gastrointestinal Neoplasms , Humans , Circulating Tumor DNA/genetics , Neoplasm, Residual/genetics , Neoplasm Recurrence, Local , Gastrointestinal Neoplasms/diagnosis , Gastrointestinal Neoplasms/genetics
2.
Front Microbiol ; 13: 927889, 2022.
Article in English | MEDLINE | ID: mdl-35847091

ABSTRACT

Rhizosphere colonization is a pre-requisite for the favorable application of plant growth-promoting rhizobacteria (PGPR). Exchange and mutual recognition of signaling molecules occur frequently between plants and microbes. Here, the luciferase luxAB gene was electrotransformed into the phosphate-solubilizing strain Pseudomonas sp. WS32, a type of plant growth-promoting rhizobacterium with specific affinity for wheat. A labeled WS32 strain (WS32-L) was applied to determine the temporal and spatial traits of colonization within the wheat rhizosphere using rhizoboxes experimentation under natural condition. The effects of colonization on wheat root development and seedling growth were evaluated, and RNA sequencing (RNA-seq) was performed to explore the transcriptional changes that occur in wheat roots under WS32 colonization. The results showed that WS32-L could survive in the wheat rhizosphere for long periods and could expand into new zones following wheat root extension. Significant increases in seedling fresh and dry weight, root fresh and dry weight, root surface area, number of root tips, and phosphorus accumulation in the wheat leaves occurred in response to WS32 rhizosphere colonization. RNA-seq analysis showed that a total of 1485 genes in wheat roots were differentially expressed between the inoculated conditions and the uninoculated conditions. Most of the transcriptional changes occurred for genes annotated to the following functional categories: "phosphorus and other nutrient transport," "hormone metabolism and organic acid secretion," "flavonoid signal recognition," "membrane transport," and "transcription factor regulation." These results are therefore valuable to future studies focused on the molecular mechanisms underlying the growth-promoting activities of PGPR on their host plants.

3.
PLoS One ; 14(4): e0215339, 2019.
Article in English | MEDLINE | ID: mdl-30986222

ABSTRACT

Titanium dioxide nanoparticles co-modified with CuOx (0≤x≤2) and carbonaceous materials were prepared with a simple hydrolysis and photo-reduction method for photocatalytic hydrogen generation. SEM/TEM and XPS analysis indicated that the carbonaceous materials were mostly coated on the TiO2 surface and clearly revealed that the Cu species exhibited multivalence states, existing as CuOx (0≤x≤2). The optimal catalyst showed a 56-fold enhanced hydrogen evolution rate compared with that of the pure C/TiO2 catalyst. Further, an intensive multiple electron transfer effect originating from CuOx and the carbonaceous materials is proposed to be responsible for the elevated photoactivity. CuOx species serve as electron donors facilitating charge carrier transfer and proton reduction sites. The carbonaceous materials function as the "bridge" that transfers the electrons of TiO2 to the CuOx species, which provides a new route for electron transfer and reinforces the effect of CuOx as a co-catalyst. In this study, the CuOx and C co-modified TiO2 catalyst was prepared with multiple electron transport pathways and enhanced hydrogen production evolution, which provides a deep understanding for the design of co-catalyst-based photocatalysts.


Subject(s)
Copper/chemistry , Hydrogen/chemistry , Models, Chemical , Nanoparticles/chemistry , Photochemical Processes , Titanium/chemistry , Catalysis , Electron Transport
4.
Environ Sci Pollut Res Int ; 25(30): 30160-30169, 2018 Oct.
Article in English | MEDLINE | ID: mdl-30151788

ABSTRACT

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) are ubiquitous and highly toxic emerging endocrine disruptors found in surface and subsurface soils and clay deposits. Seriously, they could be easily transformed to the more toxic dioxins (PBDD/Fs) in photochemical processes and incineration, but the spontaneous formation of PBDD/Fs has rarely been reported. This study focused on the formation of 1,3,8-tribromodibenzo-p-dioxin (1,3,8-TrBDD) and 2,4,6,8-tetrabromodibenzofuran (2,4,6,8-TeBDF) from 2'-OH-BDE-68 and 2,2'-diOH-BB-80 under the oxidization of iron and manganese oxides (goethite and MnOx). Approximately 0.09 µmol/kg (2.33%) and 0.17 µmol/kg (4.15%) were transformed to 1,3,8-TrBDD and 2,4,6,8-TeBDF by goethite in 8 days and a higher conversion 0.15 µmol/kg (3.77%) and 0.23 µmol/kg (5.74%) were observed for MnOx in 4 days. However, the formation of PBDD/Fs, probably proceeding via Smiles rearrangements and bromine elimination processes, was greatly inhibited by the presence of water. Transformation of OH-PBDEs by goethite and MnOx was accompanied by release of Fe and Mn ions and the possible pathways for the formation of reaction products were proposed. In view of the ubiquity of OH-PBDEs and metal oxides in the environment, oxidation of OH-PBDEs mediated by goethite and MnOx is likely an abiotic route for the formation of PBDD/Fs.


Subject(s)
Benzofurans/chemistry , Dioxins/chemistry , Halogenated Diphenyl Ethers/chemical synthesis , Iron/chemistry , Manganese Compounds/chemistry , Oxides/chemistry , Bromine/chemistry , Halogenated Diphenyl Ethers/chemistry , Hydroxylation , Incineration , Oxidation-Reduction
5.
J Hazard Mater ; 355: 74-81, 2018 08 05.
Article in English | MEDLINE | ID: mdl-29775880

ABSTRACT

Polychlorinated dibenzo-p-dioxins (PCDDs), as a group of notorious anthropogenic environmental toxicants, are arguably ubiquitous in nature. In this study, we investigated the photocatalytic reductive dechlorination of 2-chlorodibenzo-p-dioxin (2-CDD) over Pd/g-C3N4 catalysts under UV-vis irradiation. The g-C3N4 and a series of Pd/g-C3N4 catalysts were prepared by thermal polymerization and mechanical mixing-illumination method and characterized by XRD, TEM, BET, SEM and UV-vis DRS analyses. Among all the samples, the Pd/g-C3N4 (5 wt%) yielded the optimal dechlorination activity with a total 2-CDD conversion of 54% within 4 h, and 76% of those converted 2-CDD were evolved to dibenzo-p-dioxin (DD). The kinetics of dechlorination could be described as pseudo-first-order decay model (R2 > 0.84). Corresponding rate constants (k) increased from 0.052 to 0.17 h-1 with Pd contents up to 5 wt% and decreased to 0.13 h-1 with a 10 wt% of Pd. The enhanced activities originated from the surface plasmonic resonance (SPR) effect of Pd nanoparticles and the formation of Schottky barrier between Pd and g-C3N4, which extend the spectrum responsive range and suppress the charge recombination of g-C3N4. This is the first report on the photocatalytic reductive removal of PCDDs and may provide a new approach for PCDDs pollution control.

6.
PLoS One ; 11(8): e0161397, 2016.
Article in English | MEDLINE | ID: mdl-27575246

ABSTRACT

Extensively spectral-responsive photocatalytic hydrogen production was achieved over g-C3N4 photo-sensitized by Au nanoparticles. The photo-sensitization, which was achieved by a facile photo-assisted reduction route, resulted in an extended spectral range of absorption from 460 to 640 nm. The photo-sensitized g-C3N4 (Au/g-C3N4) photocatalysts exhibit significantly enhanced photocatalytic hydrogen evolution with a TOF value of 223 µmol g-1 h-1, which is a 130-fold improvement over g-C3N4. The hydrogen production result confirms that Au nanoparticles are effective photo-sensitizers for the visible light-responsive substrate g-C3N4. UV-vis diffuse reflection spectra (DRS), photoluminescence spectra (PL), electron spin resonance (ESR), and electrochemical measurements were used to investigate the transfer process of photogenerated electrons. The optimal Au/g-C3N4 photocatalyst displays the lowest charge transfer resistance of 18.45 Ω cm-2 and a high electron transfer efficiency, as determined by electrochemical impedance spectroscopy (EIS). The photo-sensitized g-C3N4 shows a broad range of response to visible light (400-640 nm), with significantly high incident photon-to-current efficiency (IPCE) values of 14.52%, 2.9%, and 0.74% under monochromatic light irradiation of 400, 550, and 640 nm, respectively. ESR characterization suggests that Au nanoparticles are able to absorb visible light of wavelengths higher than 460 nm and to generate hot electrons due to the SPR effect.


Subject(s)
Gold/chemistry , Graphite/chemistry , Hydrogen/chemistry , Nitriles/chemistry , Catalysis , Dielectric Spectroscopy , Electron Spin Resonance Spectroscopy , Light , Nanocomposites/chemistry , Photochemical Processes
7.
Chem Commun (Camb) ; 51(23): 4785-8, 2015 Mar 21.
Article in English | MEDLINE | ID: mdl-25704549

ABSTRACT

NH3 is a potential hydrogen energy carrier. Here we use alcohols as hole scavengers to investigate the nitrogen photofixation mechanisms including direct and indirect electron transfer processes. The t-butanol system exhibited the highest quantum yield of 36.1%, ascribing to the in situ-formed indirect electronic transmitter ˙CO2(-).

8.
PLoS One ; 9(8): e103671, 2014.
Article in English | MEDLINE | ID: mdl-25090093

ABSTRACT

BACKGROUND PURPOSE: Photocatalytic water splitting for hydrogen evolution is a potential way to solve many energy and environmental issues. Developing visible-light-active photocatalysts to efficiently utilize sunlight and finding proper ways to improve photocatalytic activity for H2 evolution have always been hot topics for research. This study attempts to expand the use of sunlight and to enhance the photocatalytic activity of TiO2 by N doping and Au loading. METHODS: Au/N-doped TiO2 photocatalysts were synthesized and successfully used for photocatalytic water splitting for H2 evolution under irradiation of UV and UV-vis light, respectively. The samples were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy (DRS), photoluminescence spectroscopy (PL), and photoelectrochemical characterizations. RESULTS: DRS displayed an extension of light absorption into the visible region by doping of N and depositing with Au, respectively. PL analysis indicated electron-hole recombination due to N doping and an efficient inhibition of electron-hole recombination due to the loaded Au particles. Under the irradiation of UV light, the photocatalytic hydrogen production rate of the as-synthesized samples followed the order Au/TiO2 > Au/N-doped TiO2 > TiO2 > N-doped TiO2. While under irradiation of UV-vis light, the N-TiO2 and Au/N-TiO2 samples show higher H2 evolution than their corresponding nitrogen-free samples (TiO2 and Au/TiO2). This inconsistent result could be attributed to the doping of N and the surface plasmonic resonance (SPR) effect of Au particles extending the visible light absorption. The photoelectrochemical characterizations further indicated the enhancement of the visible light response of Au/N-doped TiO2. CONCLUSION: Comparative studies have shown that a combination of nitrogen doping and Au loading enhanced the visible light response of TiO2 and increased the utilization of solar energy, greatly boosting the photocatalytic activity for hydrogen production under UV-vis light.


Subject(s)
Gold/chemistry , Hydrogen/chemistry , Nitrogen/chemistry , Titanium/chemistry , Ultraviolet Rays , Catalysis/radiation effects , Dielectric Spectroscopy , Electricity , Electrochemical Techniques , Microscopy, Electron, Transmission , Optical Phenomena , Photoelectron Spectroscopy , Spectrometry, X-Ray Emission , Spectrophotometry, Ultraviolet , Surface Properties , Water/chemistry , X-Ray Diffraction
9.
Huan Jing Ke Xue ; 34(5): 1871-6, 2013 May.
Article in Chinese | MEDLINE | ID: mdl-23914541

ABSTRACT

Photocatalytic oxidation (PCO) of toluene and benzaldehyde in indoor air by N doped TiO2 (N-TiO2) was conducted under UV irradiation of 254 nm. The intermediates were identified and monitored on real-time by proton transfer reaction-mass spectrometry. The health risks of PCO of toluene and benzaldehyde were assessed based on health risk influence index (eta). Results indicated that both the conversion rate and mineralization rate of toluene and benzaldehyde were relatively high, however, the volatile aldehyde compounds (VAs), including acetaldehyde and formaldehyde generated from ring-opening, significantly influenced the health risks of PCO of toluene and benzaldehyde. Acetaldehyde played a crucial role on health risks, which was inclined to desorb from the surface of catalysts, accumulate in gas-phase, and increase the health risks of PCO of the aromatic compounds. The concentration of formaldehyde kept stable at a relatively low level, however its impact cannot be neglected. In the PCO process of toluene and benzaldehyde, eta reached the maximum values of 8 499.68 and 21.43, with the eta(VAs), contribution of VAs to the health risk influence index of outlet, reaching 99.3% and 98.3%, respectively. The average values of eta in the PCO process of 30 min were 932.86 and 8.52, and for which eta(VAs), reached 98.5% and 98.0%, respectively. When PCO of toluene and benzaldehyde reached steady state, eta were 236.09 and 2.30, and eta(VAs) reached 97.9% and 97.8%, respectively. Hence, eta(VAs), can be taken as a characteristic parameter in assessment of health risks of PCO of aromatic compounds.


Subject(s)
Air Pollution, Indoor/prevention & control , Benzaldehydes/chemistry , Hydrocarbons, Aromatic/chemistry , Photolysis , Volatile Organic Compounds/chemistry , Acetaldehyde/adverse effects , Acetaldehyde/analysis , Catalysis , Formaldehyde/adverse effects , Formaldehyde/analysis , Health Impact Assessment , Oxidation-Reduction , Titanium/chemistry , Toluene/chemistry , Ultraviolet Rays
10.
Chemosphere ; 91(7): 1002-8, 2013 May.
Article in English | MEDLINE | ID: mdl-23461839

ABSTRACT

To evaluate the health risk of vacuum ultraviolet (VUV) photolysis of naphthalene (NP) in indoor air, intermediates were detected by gas chromatograph-mass spectrometry and proton transfer reaction-mass spectrometry. Results showed that 13 volatile organic compounds (VOCs) in gas phase and five semi-volatile organic compounds (SVOCs) in oil phase were the main intermediates. VUV photolysis pathways of NP can be divided into five stages including functionalization, partition, condensation, fragmentation, and mineralization. Initially NP was converted into several SVOCs via functionalization by oxidative radicals. SVOCs with high boiling points and polarity groups would partition between aerosol and gas phase. Certain amount of SVOCs in aerosol phase were transformed to oily substances by condensation, which can be washed out by conventional gas washing technique like wet scrubber easily. A majority of SVOCs in gas phase were converted to VOCs by fragmentation, which can be further mineralized into CO2. The accumulation of VOCs, especially highly harmful aldehydes, resulted in an increase of health risk influence index (η) to 150 after VUV irradiation of 2.81min, while the mineralization of VOCs led to a sharp decline of η to 28 after VUV irradiation of 7.01min. It can be concluded that the mineralization of VOCs is a key factor to alleviate the health risk of photolysis. The results will guide a safe and economical application of VUV photolysis technology in indoor air purification.


Subject(s)
Air Pollutants/analysis , Air Pollution, Indoor/analysis , Naphthalenes/analysis , Photolysis , Volatile Organic Compounds/analysis , Air Pollutants/chemistry , Gas Chromatography-Mass Spectrometry , Humans , Mass Spectrometry , Naphthalenes/chemistry , Oxidation-Reduction , Vacuum , Volatile Organic Compounds/chemistry
11.
Sci Total Environ ; 438: 201-9, 2012 Nov 01.
Article in English | MEDLINE | ID: mdl-23000545

ABSTRACT

Concentrations of 13 gaseous intermediates in photocatalytic oxidation (PCO) of toluene in indoor air were determined in real-time by proton transfer reaction mass spectrometry and desorption intensities of 7 adsorbed intermediates on the surface of photocatalysts were detected by temperature-programmed desorption-mass spectrometry. Effects of relative humidity (RH), photocatalysts, and vacuum ultraviolet (VUV) irradiation on the distribution and category of the intermediates and health risk influence index (η) were investigated. RH enhances the formation rate of hydroxide radicals, leading to more intermediates with higher oxidation states in gas phase. N doping promotes the separation of photo-generated electrons and holes and enhances PCO activity accordingly. VUV irradiation results in higher mineralization rate and more intermediates with higher oxidation states and lower toxicity e.g. carboxylic acids. Health risk analysis indicates that higher RH, N doping of TiO(2), and VUV lead to "greener" intermediates and smaller η. Finally, a conceptual diagram was proposed to exhibit the scenario of η varied with extent of mineralization for various toxicities of inlet pollutants.


Subject(s)
Air Pollutants/chemistry , Air Pollution, Indoor/analysis , Air Pollution, Indoor/statistics & numerical data , Humidity , Photochemical Processes , Toluene/chemistry , Air Pollutants/toxicity , Catalysis , Electron Spin Resonance Spectroscopy , Mass Spectrometry , Molecular Structure , Oxidation-Reduction , Risk Assessment , Temperature , Toluene/toxicity , Ultraviolet Rays
12.
J Hazard Mater ; 192(3): 1548-54, 2011 Sep 15.
Article in English | MEDLINE | ID: mdl-21767910

ABSTRACT

Mesoporous wide bandgap semiconductors offer high photocatalytic oxidation and mineralization activities. In this study, mesoporous ß-Ga(2)O(3) diamond nanorods with 200-300 nm in diameter and 1.0-1.2 µm in length were synthesized via a urea-based hydrothermal method using polyethylene glycol (PEG) as template agent. The UV photocatalytic oxidation activity of ß-Ga(2)O(3) for gaseous toluene was evaluated, and 7 kinds of intermediates were monitored online by a proton transfer reaction mass spectrometry. Photoluminescence spectra manifested that the dosage and molecular weight of PEG are crucial for formation of vacancies and photocatalytic oxidation activities. A PEG-assisted hydrothermal formation mechanism of mesoporous ß-Ga(2)O(3) diamond nanorods was proposed. Based on the health risk influence index (η) of the intermediates, the calculated health risks revealed that the ß-Ga(2)O(3) nanorods with a η value of 9.6 are much safer than TiO(2) (η = 17.6).


Subject(s)
Gallium/chemistry , Nanotechnology/methods , Nanotubes/chemistry , Polyethylene Glycols/chemistry , Catalysis , Environment , Light , Mass Spectrometry/methods , Microscopy, Electron, Transmission/methods , Models, Statistical , Oxygen/chemistry , Photochemistry/methods , Protons , Risk , Toluene/chemistry , Urea/chemistry
13.
J Hazard Mater ; 187(1-3): 526-33, 2011 Mar 15.
Article in English | MEDLINE | ID: mdl-21315507

ABSTRACT

Ozonation of Cationic Red X-GRL was investigated in a semi-batch column reactor under various operating conditions such as gas flow rate Q(G), temperature T, initial concentration C(D,0), and pH. The relative contributions of ozone direct oxidation and OH-facilitated indirect oxidation of the dyestuff were quantified, and the overall rate constant k(T) and the kinetic regime of the reaction were determined by interpreting the experimental data with a newly derived kinetic model. The Hatta number of the reaction was found between 0.053 and 0.080, indicating that the reaction occurred in the liquid bulk, i.e. the slow kinetic regime. The ratio γ of indirect oxidation rate constant k(R) to k(T) decreased from 11.50% at pH 9.24 to 2.47% at pH 3.15. A mechanistically sounder model was derived to describe the reaction kinetics, which takes into account mechanisms of ozone decomposition and dyestuff degradation, and gas-liquid mass transfer. Good agreements were obtained between the experimental and calculated concentrations of Cationic Red X-GRL C(D), dissolved ozone C(A), ozone in off gas C(A,G), and nitrate. Furthermore, a model-based sensitivity analysis of C(D)/C(D,0), C(A), and C(A,G) was performed with respect to various model parameters.


Subject(s)
Coloring Agents/chemistry , Models, Chemical , Ozone/chemistry , Cations , Kinetics , Oxidation-Reduction , Solutions , Water
14.
Nanotechnology ; 20(23): 235701, 2009 Jun 10.
Article in English | MEDLINE | ID: mdl-19451679

ABSTRACT

Novel carbon doped TiO(2) nanotubes, nanowires and nanorods were fabricated by utilizing the nanoconfinement of hollow titanate nanotubes (TNTs). The fabrication process included adsorption of ethanol molecules in the inner space of TNTs and thermal treatment of the complex in inert N(2) atmosphere. The structural morphology of carbon doped TiO(2) nanostructures can be tuned using the calcination temperature. X-ray diffraction, Raman and Brunauer-Emmett-Teller studies proved that the doped carbon promoted the crystallization and phase transition by acting as nucleation seeds. X-ray photoelectron spectroscopy (XPS) showed that O-Ti-C and Ti-O-C bonds were formed in the nanostructures. Additional electronic states from the XPS valence band due to carbon doping were observed. This evidence indicated the electronic origin of the band gap narrowing and visible light absorption. The differences in chemical and electronic states between the surface and bulk of as-prepared samples confirmed that carbon was doped into the lattice of TiO(2) nanostructure through an inner doping process. The as-prepared catalysts exhibited enhanced photocatalytic activity for degradation of toluene in gas phase under both visible and simulated solar light irradiation compared with that of commercial Degussa P25. This novel fabrication approach can valuably contribute to designing nanostructured photocatalytic materials and modifying various nanotube materials.

15.
J Hazard Mater ; 162(2-3): 763-70, 2009 Mar 15.
Article in English | MEDLINE | ID: mdl-18586393

ABSTRACT

Multi-type nitrogen doped TiO(2) nanoparticles were prepared by thermal decomposition of the mixture of titanium hydroxide and urea at 400 degrees C for 2h. The as-prepared photocatalysts were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectra (UV-vis DRS), and photoluminescence (PL). The results showed that the as-prepared samples exhibited strong visible light absorption due to multi-type nitrogen doped in the form of substitutional (N-Ti-O and Ti-O-N) and interstitial (pi* character NO) states, which were 0.14 and 0.73 eV above the top of the valence band, respectively. A physical model of band structure was established to clarify the visible light photocatalytic process over the as-prepared samples. The photocatalytic activity was evaluated for the photodegradation of gaseous toluene under visible light irradiation. The activity of the sample prepared from wet titanium hydroxide and urea (TiO(2)-Nw, apparent reaction rate constant k = 0.045 min(-1)) was much higher than other samples including P25 (k = 0.0013 min(-1)). The high activity can be attributed to the results of the synergetic effects of strong visible light absorption, good crystallization, large surface hydroxyl groups, and enhanced separation of photoinduced carriers.


Subject(s)
Light , Metal Nanoparticles , Nitrogen/chemistry , Titanium/chemistry , Catalysis , Crystallography, X-Ray , Photochemistry , Spectrophotometry, Ultraviolet
16.
J Hazard Mater ; 157(1): 57-63, 2008 Aug 30.
Article in English | MEDLINE | ID: mdl-18249491

ABSTRACT

Nitrogen doped TiO(2) nanocrystals with anatase and rutile mixed phases were prepared by incomplete oxidation of titanium nitride at different temperatures. The as-prepared samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), core level X-ray photoelectron spectroscopy (CL XPS), valence band X-ray photoelectron spectroscopy (VB XPS), UV-vis diffuse reflectance spectra (UV-vis DRS), and visible light excited photoluminescence (PL). The photocatalytic activity was evaluated for photocatalytic degradation of toluene in gas phase under visible light irradiation. The visible light absorption and photoactivities of these nitrogen doped TiO(2) nanocrystals can be clearly attributed to the change of the additional electronic (N(-)) states above the valence band of TiO(2) modified by N dopant as revealed by the VB XPS and visible light induced PL. A band gap structure model was established to explain the electron transfer process over nitrogen doped TiO(2) nanocrystals under visible light irradiation, which was consistent with the previous theoretical and experimental results. This model can also be applied to understand visible light induced photocatalysis over other nonmetal doped TiO(2).


Subject(s)
Light , Nanoparticles/chemistry , Nitrogen/chemistry , Titanium/chemistry , Nanoparticles/radiation effects , Oxidation-Reduction , Titanium/radiation effects
17.
Nanotechnology ; 19(36): 365607, 2008 Sep 10.
Article in English | MEDLINE | ID: mdl-21828878

ABSTRACT

A novel method was developed for preparing high specific surface area (156.2 m(2) g(-1)) one-dimensional TiO(2) nanostructures co-doped with C, N and S by the nano-confinement effect. A nonmetal doping source (thiourea) was first intercalated into the inner space of H-titanate nanotubes prepared by the hydrothermal method, and then calcined at 450 °C for 2 h in air. The as-prepared C, N and S co-doped TiO(2) nanowires exhibited high visible light and enhanced UV-vis activities in photocatalytic degradation of toluene in the gas phase. The samples were characterized by x-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy, fast Fourier transform analysis, x-ray photoelectron spectroscopy, UV-vis diffuse reflectance spectra and photoluminescence. The results indicated that the anatase nanowires grew along the [101] direction. Doping TiO(2) nanowires with C, N and S could not only broaden the light adsorption spectra into the visible region (400-600 nm), but also inhibit the recombination of photo-induced carriers. A mechanism is proposed to elucidate the nano-confinement effect of H-titanate nanotubes in the formation of C, N and S co-doping. Based on this mechanism, the effect of C, N and S co-doping on the band structure of TiO(2) nanowires is also discussed.

18.
J Environ Sci (China) ; 19(2): 226-31, 2007.
Article in English | MEDLINE | ID: mdl-17915734

ABSTRACT

A laboratory-scale well-mixed thermostatic reactor with continuously blasting air was used to investigate the oxidation inhibition of sulfite in dual alkali flue gas desulfurization (FGD) system. The effects of operating parameters such as pH value and catalyst concentration on the oxidation were studied. Sodium thiosulfate was used in the system, and was found that it significantly inhabited the sulfite oxidation. In the absence of catalyst, sodium thiosulfate at 12.67 mmol/L had an inhibition efficiency of approximately 98%. While in the presence of catalyst, sodium thiosulfate at 26.72 mmol/L had an inhibition efficiency less than 85.0%. The oxidation reaction order of sulfite in the sodium thiosulfate was determined to be -1.90 and -0.55 in the absence and presence of the catalyst, respectively. Apparent activation energy of oxidation inhibition was calculated to be 53.9 kJ/mol. Pilot tests showed that the consumption rate of thiosulfate agreed well with the laboratory-scale experimental results.


Subject(s)
Air Pollutants/chemistry , Air Pollution/prevention & control , Sulfites/chemistry , Thiosulfates/chemistry , Alkalies , Catalysis , Hydrogen-Ion Concentration , Magnesium Sulfate/chemistry , Oxidation-Reduction , Sulfur , Waste Management/methods
19.
J Hazard Mater ; 145(3): 488-94, 2007 Jul 16.
Article in English | MEDLINE | ID: mdl-17188430

ABSTRACT

A catalyst based on MnO(x)/TiO(2) was prepared by sol-gel method for low-temperature selective catalytic reduction (SCR) of NO with NH(3). Focusing on the effects of the operating parameters, the SCR reaction was investigated at temperatures from 353 to 523K under steady and transient states. Under the optimal conditions, the efficiency of NO removal could exceed 90% at temperature of 423K. Furthermore, within the range investigated, the reaction order of NO, NH(3), O(2) was determined to be 1, 0, and 0.5, respectively. Apparent activation energy was also calculated to be 38kJ/mol, lower than that for most of the catalysts reported by previous investigations.


Subject(s)
Ammonia/chemistry , Magnesium Oxide/chemistry , Nitric Oxide/chemistry , Titanium/chemistry , Catalysis , Gels , Oxidation-Reduction , Solutions , Temperature
20.
Chemosphere ; 66(1): 185-90, 2007 Jan.
Article in English | MEDLINE | ID: mdl-16806397

ABSTRACT

TiO2 loading on woven glass fabric is applied to treat nitrogen oxides (NOx) by photocatalytic oxidation (PCO). In this paper, the PCO behavior of NO at high concentrations was studied by PCO of NOx at source levels (20-168 ppm). The PCO efficiency reached 27% in this experiment, while the inlet NOx concentration was 168 ppm (147 ppm NO). The dependency of the reaction rate on several key influencing factors (relative humidity, space time, inlet concentration, oxygen percentage) was also studied. The results illustrate that the resulting hydroxyl radical and active oxide play an important role in the oxidation of NOx. The reactions are limited by the thermodynamic equilibrium after ca. 15s space time. A possible explanation for the catalyst deactivation is the accumulation of nitric acid and nitrous acid on the TiO2 surface during the PCO of NOx. However, the photocatalytic activity can be recovered with a simple heat treatment. The results from the study of the effect of the inlet concentration were described with the Langmuir-Hinshelwood model.


Subject(s)
Glass/chemistry , Nitrogen Oxides/chemistry , Titanium/chemistry , Catalysis , Oxidation-Reduction/radiation effects , Photochemistry/methods
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