In-situ-reduced synthesis of cyano group modified g-C3N4/CaCO3 composite with highly enhanced photocatalytic activity for nicotine elimination

Graphite carbon nitride has many excellent properties as a two-dimensional semiconductor material so that it has a wide application prospect in the field of photocatalysis. However, the traditional problems such as high recombination rate of photogenerated carriers limit its application. In this work, we introduce nitrogen deficiency into g-C₃N₄ to solve this problem a simple and safe in-situ reduction method. g-C₃N₄/CaCO₃ was obtained by a simple and safe one-step calcination method with industrial-grade micron particles CaCO₃. Cyano group modification was in-situ reduced during the thermal polymerization process, which would change the internal electronic structure of g-C₃N₄. The successful combination of g-C₃N₄ and CaCO₃ and the introduction of cyanide have been proved by Fourier transform infrared spectroscopy and X-ray photoelectron spectrometer. The formation of the cyano group, an electron-absorbing group, promotes the effective separation of photogenic electron hole pairs and inhibits the recombination of photogenic carriers. These advantages result in the generation of more •O₂⁻ and ¹O₂ in the catalytic system, which increases the photocatalytic efficiency of nicotine degradation by ten times. Furthermore, the degradation process of nicotine has been studied in this work to provide a basis for the degradation of nicotine organic pollutants in the air.     

Enhancement of solar-driven photocatalytic activity of oxygen vacancy-rich Bi/BiOBr/Sr2LaF7:Yb3+,Er3+ composites through synergetic strategy of upconversion function and plasmonic effect

For better use of solar energy,the development of efficient broadband photocatalyst has attracted extraordinary attention.In this study,a ternary composite consisting of Sr₂ LaF₇:Yb³⁺,Er³⁺ upconversion(UC) nanocrystals and Bi nanoparticles loaded BiOBr nanosheets with oxygen vacancies(OVs,SLFBB) was designed and synthesized by multistep solvent-thermal method.Mechanisms of in-situ formation of Bi nanoparticles and OVs in BiOBr/Sr₂ LaF_7<...     

Fe-N co-doped coral-like hollow carbon shell toward boosting peroxymonosulfate activation for efficient degradation of tetracycline: Singlet oxygen-dominated non-radical pathway

Fe-N co-doped coral-like hollow carbon shell (Fe-N-CS) was synthesized via a simply impregnation-pyrolysis method. The Fe-N-CS showed an excellent ability for activating peroxymonosulfate (PMS), which could degrade about 93.74% tetracycline (20 mg/L) in 12 min. The Fe-N-CS/PMS system exhibited a good anti-interference capacity of various pH, inorganic anions, HA and different water qualities. More importantly, the Fe nanoparticles were anchored uniformly in the carbon layer, effectively limiting the metal leaching. The quenching tests and electron spin resonance (ESR) manifested that non-radical singlet oxygen (¹O₂) was the main reactive oxygen species (ROS) for TC degradation. The mechanism study showed that Fe nanoparticles, defect and graphite N played a key role in activating PMS to produce ROS. Moreover, three probable degradation pathways were proposed by using LC-MS measurements. Generally, this work had a new insight for the synthesis of heterogeneous Fe-N-C catalysts in the advanced oxidation process based on PMS.     

Mitigating phytotoxicity of tetracycline by metal-free 8-hydroxyquinoline functionalized carbon nitride photocatalyst

Photooxidative removal of pharmaceuticals and organic dyes is an effective way to eliminate growing micropollutants. However, photooxidation often results in byproducts as secondary hazardous substances such as phytotoxins. Herein, we found that photooxidation of common antibiotic tetracycline hydrochloride (TCH) over a metal-free 8-hydroxyquinoline (8-HQ) functionalized carbon nitride (CN) photocatalyst significantly reduces the TCH phytotoxic effect. The phytotoxicity test of photocatalytic treated TCH-solution evaluated towards seed growth of Cicer arietinum plant model endowed natural root and shoot growth. This study highlights the conceptual insights in designing of metal-free photocatalyst for environmental remediation.     

In situ preparation of g-C3N4/polyaniline hybrid composites with enhanced visible-light photocatalytic performance

The graphic carbon nitride/polyaniline (g-C₃N₄/PANI) hybrid composites were successfully synthesized by a facile in situ polymerization process under ice water bath. The photocatalytic activities of the g-C₃N₄/PANI composites were evaluated by using oxytetracycline (OTC) as model pollutants. The optimal g-C₃N₄/PANI composite (5%PANI: the g-C₃N₄/PANI hybrid with 5 wt.% of PANI) showed an enhancement degradation rate of 5-fold compared to that of conventional g-C₃N₄ under simulated-sunlight irradiation. In addition, the 5%PANI demonstrate significantly photocatalytic evolution H₂ rate (163.2 μmol/(g?hr)) under the visible light irradiation. Furthermore, based on the results of optical performance and electrochemical testing, a possible mechanism was proposed, indicating that the incorporation of PANI into the traditional g-C₃N₄ can effectively tune the electronic structures, improve the photo-generated electrons-holes separation and enhance extensive absorption of visible light. Such a g-C₃N₄/PANI hybrid nanocomposites could be envisaged to possess great potentials in practical wastewater treatment and water splitting.     

Effect of different reduction methods on Pd/Al2O3 for o-xylene oxidation at low temperature

Pd/Al₂O₃ was pretreated by CO, H₂ and NaBH₄ reduction, respectively. The reduced catalysts were tested for o-xylene oxidation and characterized by power X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and temperature-programmed decomposition of palladium hydride (TPDH). The characterizations indicate the pretreatments lead to distinct Pd particle sizes and amount of surface activated oxygen species, which are responsible for the catalytic performance. Compared with H₂ and NaBH₄ reduction methods, CO reduction shows a strong interaction between Pd and Al₂O₃ with smaller Pd particle size and more surface activated oxygen. It exhibited excellent catalytic performance, complete oxidation of 50 ppmV o-xylene at 85°C with a WHSV of 60,000 mL/(g∙hr).     

Assembly of SPS/MgSi assisted by dopamine with excellent removal performance for ciprofloxacin

In this work, magnesium silicate-based sulfonated polystyrene sphere composites(SPS/Mg Si) were synthesized by one-step(SMD1) and two-step(SMD2) methods. For SMD1, Mg Si particles were densely assembled on the surface of SPS, assisted by complexation between Fe 3 + and hydroxyl phenol. For SMD2, SPS/Si O 2 was firstly obtained by the same method as SMD1, and then SPS/Si O 2 was transformed directly to SPS/Mg Si under hydrothermal conditions. Therefore, Mg Si obtained by the two-step method had a...     

Construction of dual Z-scheme Bi2WO6/g-C3N4/black phosphorus quantum dots composites for effective bisphenol A degradation

In this work, a novel dual Z-scheme Bi₂WO₆/g-C₃N₄/black phosphorus quantum dots (Bi₂WO₆/g-C₃N₄/BPQDs) composites were fabricated and utilized towards photocatalytic degradation of bisphenol A (BPA) under visible-light irradiation. Optimizing the content of g-C₃N₄ and BPQDs in Bi₂WO₆/g-C₃N₄/BPQDs composites to a suitable mass ratio can enhance the visible-light harvesting capacity and increase the charge separation efficiency and the transfer rate of excited-state electrons and holes, resulting in much higher photocatalytic activity for BPA degradation (95.6%, at 20 mg/L in 120 min) than that of Bi₂WO₆ (63.7%), g-C₃N₄ (25.0%), BPQDs (8.5%), and Bi₂WO₆/g-C₃N₄ (79.6%), respectively. Radical trapping experiments indicated that photogenerated holes (h⁺) and superoxide radicals (•O₂⁻) played crucial roles in photocatalytic BPA degradation. Further, the possible degradation pathway and photocatalytic mechanism was proposed by analyzing the BPA intermediates. This work also demonstrated that the Bi₂WO₆/g-C₃N₄/BPQDs as effective photocatalysts was stable and have promising potential to remove environmental contaminants from real water samples.     

Graphitic carbon nitride/biochar composite synthesized by a facile ball-milling method for the adsorption and photocatalytic degradation of enrofloxacin

In order to enhance the removal performance of graphitic carbon nitride (g-C₃N₄) on organic pollutant, a simultaneous process of adsorption and photocatalysis was achieved via the compounding of biochar and g-C₃N₄. In this study, g-C₃N₄ was obtained by a condensation reaction of melamine at 550°C. Then the g-C₃N₄/biochar composites were synthesized by ball milling biochar and g-C₃N₄ together, which was considered as a simple, economical, and green strategy. The characterization of resulting g-C₃N₄/biochar suggested that biochar and g-C₃N₄ achieved effective linkage. The adsorption and photocatalytic performance of the composites were evaluated with enrofloxacin (EFA) as a model pollutant. The result showed that all the g-C₃N₄/biochar composites displayed higher adsorption and photocatalytic performance to EFA than that of pure g-C₃N₄. The 50% g-C₃N₄/biochar performed best and removed 45.2% and 81.1% of EFA (10 mg/L) under darkness and light with a dosage of 1 mg/mL, while g-C₃N₄ were 19.0% and 27.3%, respectively. Besides, 50% g-C₃N₄/biochar showed the highest total organic carbon (TOC) removal efficiency (65.9%). Radical trapping experiments suggested that superoxide radical (?O₂^?) and hole (h⁺) were the main active species in the photocatalytic process. After 4 cycles, the composite still exhibited activity for catalytic removal of EFA.     

Initial carbon release characteristics, mechanisms and denitrification performance of a novel slow release carbon source

External carbon source addition is one of the effective methods for the treatment of wastewater with low carbon to nitrogen ratio (C/N). Compared with fast-release liquid carbon sources, slow-release solid carbon sources are more suitable for the denitrification process. A novel slow-release solid carbon source (corncob-polyvinyl alcohol sodium alginate- poly-caprolactone, i.e. CPSP) was prepared using corn cob (CC) and poly-caprolactone with polyvinyl alcohol sodium alginate as hybrid scaffold. The physical properties and carbon release characteristics of CPSP and three other carbon sources were compared. CPSP had stable framework and good carbon release performance, which followed the second order release equation. The formic acid, acetic acid, propionic acid and butyric acid released from CPSP accounted for 8.27% ± 1.66 %, 56.48% ± 3.71 %, 18.46% ± 2.69% and 16.79% ± 3.02% of the total released acids respectively. The start-up period of CPSP was shorter than that of the other carbon sources in denitrification experiment, and no COD pollution was observed in the start-up phase (25–72 h) and stable phase (73–240 hr). The composition and structure of the dissolved organic compounds released by CPSP and other carbon sources were analyzed by UV-Vis absorption spectroscopy and three-dimensional fluorescence spectroscopy, which indicated that CPSP was more suitable for denitrification than the other studied carbon sources.

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VxMn(4 − x)Mo3Ce3/Ti catalysts for selective catalytic reduction of NO by NH3

A series of vanadium based catalysts(VxMn(4-x)Mo3Ce3/Ti) with different vanadium(x wt.%) and manganese((4-x) wt.%) contents have been prepared by the wet impregnation method and investigated for selective catalytic reduction(SCR) of NO_x by NH_3 in the presence of 8 vol.% H_2O and 500 ppm V SO_2.The physicochemical characteristics of the catalysts were thoroughly characterized.The SCR of NO_x by NH_3(NH_3-SCR) activity, especially the low-temperature activity, significantly increased with increasing V_2O_5 content in the catalyst until the V_2O_5 content reached 1.5 wt.%, which corresponds well with the redox properties of the catalyst.All of the metal oxides were well dispersed and strongly interacted with each other on the catalyst surface.V mainly exists in the V~(5+)state in the catalysts.The strong synergistic effect between the vanadium and cerium species led to formation of more Ce~(3+)species, and that between the vanadium and manganese species contributed to formation of more manganese species with low valences.All of the catalysts exhibited strong acidity, while the redox properties determined the NH_3-SCR activity, especially the low-temperature activity.H_2O and SO_2 had severe inhibiting effects on the activity of V1.5Mn2.5Mo3Ce3/Ti.However, good H_2O and SO_2 resistance and high NO_x conversion by V1.5Mn2.5Mo3Ce3/Ti could be achieved in the presence of SO_2 and almost no decline was observed in a long-term test at 275℃ for 168 hr in the presence of SO_2 and H_2O, which can be attributed to the sulfate species formed on the catalyst surface.     

Enhanced activation of peroxydisulfate by strontium modified BiFeO3perovskite for ciprofloxacin degradation

A series of Sr-doped BiFeO₃ perovskites (Bi_1-xSr_xFeO₃, BSFO) fabricated via sol-gel method was applied as peroxydisulfate (PDS) activator for ciprofloxacin (CIP) degradation. Various technologies were used to characterize the morphology and physicochemical features of prepared BSFO samples and the results indicated that Sr was successfully inserted into the perovskites lattice. The catalytic performance of BiFeO₃ was significantly boosted by strontium doping. Specifically, Bi_0.9Sr_0.1FeO₃ (0.1BSFO) exhibited the highest catalytic performance for PDS activation to remove CIP, where 95% of CIP (10 mg/L) could be degraded with the addition of 1 g/L 0.1BSFO and 1 mmol/L PDS within 60 min. Moreover, 0.1BSFO displayed high reusability and stability with lower metal leaching. Weak acidic condition was preferred to neutral and alkaline conditions in 0.1BSFO/PDS system. The boosted catalytic performance can be interpreted as the lower oxidation state of Fe and the existence of affluent oxygen vacancies generated by Sr doping, that induced the formation of singlet oxygen (¹O₂) which was confirmed as the dominant reactive species by radical scavenging studies and electron spin resonance (ESR) tests. The catalytic oxidation mechanism related to major ¹O₂ and minor free radicals was proposed. Current study opens a new avenue to develop effective A-site modified perovskite and expands their application for PDS activation in wastewater remediation.     

A novel and stretchable carbon-nanotube/Ni@TiO2:W photocatalytic composite for the complete removal of diclofenac drug from the drinking water

We present the structural, morphological and photocatalytic properties of stretchable composites made with carbon nanotubes (CNTs), silicon rubber and Ni@TiO₂:W nanoparticles (TiWNi NPs) with average size of 37 ± 2 nm. Microscopy images showed that the TiWNi NPs decorated the surface of the CNT fibers, which are oriented in a preferential direction. TiWNi NPs presented a mixture of anatase/rutile phases with cubic structure. The performance of the TiWNi powders and stretchable composites was evaluated for the photocatalytic degradation of diclofenac (DCF) anti-inflammatory drug under ultraviolet-visible light. The results revealed that the maximum DCF degradation percentages were 34.6%, 91.9%, 97.1%, 98.5% and 100% for the CNT composite (stretched at 0%), TiWNi powders, CNT + TiWNi (stretched at 0%), CNT + TiWNi (stretched at 50%) and CNT + TiWNi (stretched at 100%), respectively. Thus, stretching the CNT + TiWNi composites was a good strategy to enhance the DCF degradation percentage from 97.1% to 100%, since stretching created additional defects (oxygen vacancies) that acted as electron sink, delaying the electron-hole recombination, and favors the DCF degradation. Raman/absorbance measurements confirmed the presence of such defects. Moreover, the reactive oxygen species (ROS) were determined by the scavenger's experiments and found that the main ROS were the ·OH and O₂⁻ radicals, which attacked the DCF molecules, causing their degradation. The results of this investigation confirmed that the stretchable CNT/TiWNi-based composites are a viable alternative to remove pharmaceutical contaminants from water and can be manually separated from the decontaminated water, which is unviable using photocatalytic powders.     

Innovatively employing magnetic CuO nanosheet to activate peroxymonosulfate for the treatment of high-salinity organic wastewater

Magnetic CuO nanosheet(Mag-CuO), as a cheap, stable, efficient and easily separated peroxymonosulfate(PMS) activator, was prepared by a simple one-step precipitation method for the removal of organic compounds from salt-containing wastewater.The experiments showed that the removal efficiencies of various organic pollutants including Acid Orange 7, Methylene Blue, Rhodamine B and atrazine in a high-salinity system(0.2 mol/L Na_2SO_4) with the Mag-CuO/PMS process were 95.81%, 74.57%, 100% and 100%,respectively.Meanwhile, Mag-CuO still maintained excellent catalytic activity in other salt systems including one or more salt components(NaCl, NaNO_3, Na_2HPO_4, NaHCO_3).A radical-quenching study and electron paramagnetic resonance analysis confirmed that singlet oxygen(~1O_2) was the dominant reactive oxygen species for the oxidation of organic pollutants in high-salinity systems, which is less susceptible to hindrance by background constituents in wastewater than radicals(~·OH or SO_4~(·-)).The surface hydroxylation of the catalyst and catalytic redox cycle including Cu and Fe are responsible for the generation of~1O_2.The developed Mag-CuO catalyst shows good application prospects for the removal of organic pollutants from saline wastewater.     

Surface characterization of metal oxides-supported activated carbon fiber catalysts for simultaneous catalytic hydrolysis of carbonyl sulfide and carbon disulfide

The sol–gel method was used to synthesize a series of metal oxides-supported activated carbon fiber (ACF) and the simultaneous catalytic hydrolysis activity of carbonyl sulfide (COS)and carbon disulfide (CS₂) at relatively low temperatures of 60°C was tested.The effects of preparation conditions on the catalyst properties were investigated,including the kinds and amount of metal oxides and calcination temperatures.The activity tests indicated that catalysts with 5 wt.%Ni after calcini...     

Ferroelectric polarization effect on the photocatalytic activity of Bi0.9Ca0.1FeO3/CdS S-scheme nanocomposites

BiFeO₃ (BFO), as a kind of narrow band-gap semiconductor material, has gradually emerged advantages in the application of photocatalysis. In this paper, Ca doped BFO nanoparticles Bi_0.9Ca_0.1FeO₃ (BCFO) were prepared by sol-gel method. And BCFO and CdS nanocomposites with two morphologies were obtained by controlling the time of loading CdS under a low temperature liquid phase process. It is found that the band gap becomes narrower after doping Ca into BFO, which is conducive to the absorption of visible light. Among all the samples, the composite of CdS nanowires and BCFO nanoparticles obtained by reaction time of 10 min has the best photocatalytic performance. The degradation rate of Methyl Orange solution was 94% after 90 min under visible light irradiation, which was much higher than that of pure BCFO and CdS. Furthermore, significant enhancement in the degradation rate (100% degradation in 60 min) can be achieved in poled samples after electric polarization process. The highest degradation rate is due to the promoted separation of photogenerated carriers induced by the internal polarization field and the formation of S-scheme heterostructure between BCFO and CdS. Such BCFO-CdS nanocomposites may bring new insights into designing highly efficient photocatalyst.     

One-step preparation of a novel graphitic biochar/Cu0/Fe3O4 composite using CO2-ambiance pyrolysis to activate peroxydisulfate for dye degradation

Herein,a one-step co-pyrolysis protocol was adopted for the first time to prepare a novel pyrogenic carbon-Cu⁰/Fe₃O₄ heteroatoms (FCBC) in CO₂ ambiance to discern the roles of each component in PDS activation.During co-pyrolysis,CO₂ catalyzed formation of reducing gases by biomass which facilitated reductive transformation of Fe³⁺ and Cu²⁺ to Cu⁰ and Fe₃O₄,respectively.According to the a...     

Preparation of MnO2 decorated Co3Fe1Ox powder/monolithic catalyst with improved catalytic activity for toluene oxidation

In this paper, KMnO₄ was used to pre-treat Co₃ Fe-layered double hydroxides(LDH) precursor to prepare MnO₂ decorated Co₃Fe₁O_x catalyst. The toluene oxidation performance of the catalyst was investigated systematically. The optimized 0.1 Mn CF-LDO catalyst exhibited the best catalytic performance, and the temperatures of 50% and 90% toluene conversion( T₅₀ and T₉₀) were 218 and 243 ℃, respectively. The apparen...     

Preparation and characterization of a novel blue-TiO2/PbO2-carbon nanotube electrode and its application for degradation of phenol

In this study, we fabricated a blue-TiO₂/PbO₂-carbon nanotube (CNT) electrode in which blue TiO₂ nanotube arrays (blue-TNA) served as the substrate for PbO₂-CNT eletrodeposition. Scanning electron microscope (SEM) showed compact surface structure of the electrode. The β-PbO₂ crystal structure was detected by X-ray diffraction (XRD). The distribution of Pb, O, C, and Na elements on the electrode surface have been confirmed by X-ray photoelectron spectroscopy (XPS). Blue-TiO₂/PbO₂-CNT electrode had higher response current (213.12 mA), larger active surface area and lower charge transfer resistance (2.22 Ω/cm²) than conventional TiO₂/PbO₂-CNT electrode. The influences of current density, initial phenol concentration, initial solution pH, and Na₂SO₄ concentration on the electrochemical oxidation of phenol have been analyzed. The results showed that the 100 mg/L phenol could be destroyed completely after 210 min, and chemical oxygen demand (COD) removal rate was 89.3% within 240 min. Additionally, the electrode showed long actual lifetime (5468.80 hr) and low energy consumption (0.08 kWh/gCOD). A phenol degradation mechanism was proposed by analyzing the intermediate products with high-performance liquid chromatography-mass spectrometry (HPLC-MS). Importantly, the blue-TiO₂/PbO₂-CNT electrode exhibited superior stability and high degradation efficiency after 15 times reuse, demonstrating its promising application potential on phenol-containing wastewater treatment.     

Strategies for improving the photocatalytic performance of metal-organic frameworks for CO2 reduction: A review

Photocatalytic CO₂ reduction is an appealing strategy for mitigating the environmental effects of greenhouse gases while simultaneously producing valuable carbon-neutral fuels. Numerous attempts have been made to produce effective and efficient photocatalysts for CO₂ reduction. In contrast, the selection of competitive catalysts continues to be a substantial hindrance and a considerable difficulty in the development of photocatalytic CO₂ reduction. It is vital to emphasize different techniques for building effective photocatalysts to improve CO₂ reduction performance in order to achieve a long-term sustainability. Metal-organic frameworks (MOFs) are recently emerging as a new type of photocatalysts for CO₂ reduction due to their excellent CO₂ adsorption capability and unique structural characteristics. This review examines the most recent breakthroughs in various techniques for modifying MOFs in order to improve their efficiency of photocatalytic CO₂ reduction. The advantages of MOFs using as photocatalysts are summarized, followed by different methods for enhancing their effectiveness for photocatalytic CO₂ reduction via partial ion exchange of metal clusters, design of bimetal clusters, the modification of organic linkers, and the embedding of metal complexes. For integrating MOFs with semiconductors, metallic nanoparticles (NPs), and other materials, a number of different approaches have been also reviewed. The final section of this review discusses the existing challenges and future prospects of MOFs as photocatalysts for CO₂ reduction. Hopefully, this review can stimulate intensive research on the rational design and development of more effective MOF-based photocatalysts for visible-light driven CO₂ conversion.