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Devising of materials that afforded dual applicability in decontamination and pollutant detection were still a towering challenge owing to the increasing flux of discharge toxic contaminants over the years. Herein, the NiFe2O4 nanoparticles-loaded on cube-like SrTiO3 (NiFe2O4/SrTiO3) composite was fabricated by a two-step hydrothermal approach providing remarkable photocatalytic treatment and electrochemical sensing of noxious pollutants in wastewater. The material traits of the fabricated composite were scrutinized by myriad characterization approaches. The NiFe2O4/SrTiO3 hybrid material demonstrated high surface area of 19.81 m2/g, adequate band gap energy of 2.75 eV, and prominent photoluminescence characteristics. In the presence of visible light, the NiFe2O4/SrTiO3 exhibited profound photocatalysis capability to eliminate sewage effluent-bearing chlortetracycline hydrochloride (CTCH) with 88.6% COD removal in 120 min, outperforming other pure materials. Meanwhile, the toxicity examination of effluent, the possible degradation pathway of CTCH and the proposed photocatalysis mechanism were also divulged. More importantly, the glassy carbon electrode was modified with synergized NiFe2O4/SrTiO3 (NiFe2O4/SrTiO3-GCE) was adopted for the precise quantification of Hydrazine (Hz). The NiFe2O4/SrTiO3-GCE obeyed first-order response for the Hz detection within the range of 1-10 mM: cyclic voltametric: limit of detection (LOD) of 0.119 µM with sensitivity of 18.9 µA µM-1 cm-2, and linear sweep voltametric: LOD of 0.222 µM with a sensitivity of 12.05 µA µM-1 cm-2. The stability and interference of modified electrode were also inspected. This work furnished valuable insights to yield a composite with the prominent S-scheme heterojunction system for quenching of charge carrier recombination and consequently contributing to the future realization into the domains of environmental clean-up and toxic chemical detection.
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Ni-Ti intercalated bentonite catalysts (Ni-Ti-bentonite) and Ni-TiO2 supported bentonite catalysts (Ni-TiO2 /bentonite) were prepared, and the effects of Ni-Ti supported and intercalated bentonite on the selective hydrogenation of cinnamaldehyde were investigated. Ni-Ti intercalated bentonite enhanced the Brønsted acid sites strength, decreased the acid amount and Lewis's acid sites strength, which inhibited the activation of the C=O bond and contributed to selective hydrogenation of the C=C bond. When Ni-TiO2 was supported on bentonite, the acid amount and Lewis's acid strength of the catalyst increased, providing additional adsorption sites and increased the acetals byproducts. Due to the higher surface area, mesoporous volume, and suitable acidity, compared with Ni-TiO2 /bentonite in methanol solvent, 2â MPa, 120 °C for 1â h, Ni-Ti-bentonite exhibited a higher cinnamaldehyde (CAL) conversion of 98.8 %, as well as a higher hydrocinnamaldehyde (HCAL) selectivity of 95 %, and no acetals were found in the product.
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Two-dimensional (2D) photocatalysts have attracted considerable research interest in the past decades due to their unique optical, physical and chemical properties. Constructing 2D/2D heterojunctions with large interface area has been considered as an effective approach to enhance the transfer rate and the separation efficiency of the charge carriers, leading to dramatic increase in the photocatalytic performance of the photocatalysts. Here, the state-of-the-art progress on heterojunctions based on 2D materials is reviewed, including the photocatalysis principles using 2D heterojunctions, the categories of 2D heterojunctions and their application in different photocatalytic reactions, and the theoretical studies of the 2D heterojunctions. Moreover, the advantages and disadvantages of the 2D heterojunctions are also discussed. Finally, the ongoing challenges and opportunities for the future development of 2D photocatalysts with built-in heterojunctions are proposed.
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CO2 is activated in a plasma reactor followed by hydrogenation over a Cu-Fe-Ce/HZSM-5 catalyst, and the intrinsic kinetics of the plasma catalytic process are studied. Compared with CO2 hydrogenation using Cu-Fe-Ce/HZSM-5 alone, the CO2 conversion and the dimethyl ether selectivity for the plasma catalytic process are increased by 16.3 %, and 10.1 %, respectively, indicating that the CO2 was activated by the plasma to promote hydrogenation. A study of the intrinsic kinetics shows that the activation energies of methanol formation, the reverse water-gas shift reaction, and methanol dehydration to dimethyl ether are 149.34, 75.47, and 73.18â kJ mol-1 , respectively, which are lower than if Cu-Fe-Ce/HZSM-5 is used without plasma, indicating that the activation of CO2 in the plasma reduces the activation energy of the hydrogenation reaction and improves the yield of dimethyl ether.
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Two-component catalysts have garnered significant attention in the field of catalysis due to their ability to inhibit Ni sintering. In the present work, honeycomb-structured Al2O3-supported Ni and B were prepared to enhance coke tolerance during dry reforming of methane (DRM). Transmission electron microscopy (TEM) revealed that the average particle sizes on Ni/Al2O3 and Ni-0.16B/Al2O3 were 7.6 nm and 4.2 nm, respectively, indicating that B can effectively inhibit Ni sintering. After a 100-hour reaction, the conversion of CH4 and CO2 on Ni/Al2O3 decreased by approximately 5%, whereas on Ni-0.16B/Al2O3, there was no significant decrease in CH4 and CO2 conversion, with values of approximately 81.6% and 87.2%, respectively. In situ DRIFT spectra demonstrated that Ni-0.16B/Al2O3 enhanced the activation of CO2, thus improving the catalyst's stability. A Langmuir-Hinshelwood-Hougen-Watson (LHHW) model was developed for intrinsic kinetics, and the resulting kinetic expressions were well fit to the experimental data, with R2 values exceeding 0.9. The activation energies were also calculated. The outstanding stability of Ni-0.16B/Al2O3 can be attributed to its stable honeycomb structure and B's ability to significantly inhibit Ni sintering, reduce catalyst particle size, and enhance coke tolerance.
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The slow water-absorption speed of starch-based superabsorbent resin (St-SAP) limits its application. In this study, porous St-SAP (P-St-SAP) was prepared by inverse suspension polymerization and supercritical CO2 drying, the aim is to provide a preparation method of fast absorbent resin. The P-St-SAP at 33 % starch content had an interpenetrating porous structure with macropores, mesopores and micropores, and the surface area, pore volume and average pore diameter were 32.06 m2·g-1, 0.116 cm3·g-1 and 21.6 nm, respectively. The water-absorption process included rapid-section, medium-section and slow-section, according with internal diffusion, double-constant and quasi second-order kinetic models, respectively. In the initial 30 s, a water-absorption speed of 262.6 g·g-1·min-1 in distilled water was much higher than some previous research results, and the equilibrium absorption value of 517.9 g·g-1 in distilled water and 72.9 g·g-1 in 0.9 % saline was better than that of non-porous St-SAP at similar starch content. Moreover, at the same stage the percentage of saline absorption ratio to equilibrium absorption value was 1.0- 2.0 times higher than that of distilled water. These research results indicate that the P-St-SAP has fast water-absorption speed and good salt resistance, which will have greater application prospects in sanitary materials, building concrete pouring, and flood control blocking piping.
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Dióxido de Carbono , Água , Água/química , Amido/química , Porosidade , PolimerizaçãoRESUMO
The photocatalytic CO2 reduction strategy driven by visible light is a practical way to solve the energy crisis. However, limited by the fast recombination of photogenerated electrons and holes in photocatalysts, photocatalytic efficiency is still low. Herein, a WO3/BiOBr S-scheme heterojunction was formed by combining WO3 with BiOBr, which facilitated the transfer and separation of photoinduced electrons and holes and enhanced the photocatalytic CO2 reaction. The optimized WO3/BiOBr heterostructures exhibited best activity for photocatalytic CO2 reduction without any sacrificial reagents, and the CO yield reached 17.14 µmol g-1 after reaction for 4 h, which was 1.56 times greater than that of BiOBr. The photocatalytic stability of WO3/BiOBr was also improved.
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The recent development of nanotechnology has laid the foundation for the design and preparation of various nanostructured materials [...].
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The magnetic polymer microsphere is a promising adsorbent due to its high adsorption efficiency and good regeneration ability from wastewater. Cassava starch magnetic porous microspheres (AAM-MSMPMs) were synthesized by graft copolymerization in inverse emulsion. Mechanically activated cassava starch (MS) was used to graft skeletons, vinyl monomers [acrylic acid (AA) and acrylamide (AM)] as copolymerized unsaturated monomers, methyl methacrylate (MMA) as the dispersing agent, and polyethylene glycol/methanol (PEG2000/MeOH) as the porogen. It was found that the AAM-MSMPM adsorbent is superparamagnetic, the saturation magnetization is 14.9 emu·g-1, and it can be rapidly and directionally separated from Cd(II) ions in aqueous solution. The FTIR indicated that the carboxyl and hydroxyl groups were grafted into MS. The AAM-MSMPM had good speroidization and a uniform size. After the porogen was added, the particle size of the AAM-MSMPM decreased from 19.00 to 7.00 nm, and the specific surface area increased from 7.00 to 35.00 m2·g-1. The pore volume increased from 0.03 to 0.13 cm3·g-1. The AAM-MSMPM exhibited a large specific surface area and provided more adsorption active sites for Cd(II) ions. The maximum adsorption capacity of the AAM-MSMPM for Cd(II) ions was 210.68 mg·g-1, i.e., 81.02% higher than that without porogen. Additionally, the Cd(II) ion adsorption process on the AAM-MSMPM can be described by Langmuir isothermal and pseudo-second-order kinetic models. A chemical reaction dominated the Cd(II) ion adsorption process on the AAM-MSMPM, and chemisorption was the rate-controlling step during the Cd(II) ion adsorption process. The AAM-MSMPM still had excellent stability after five consecutive reuses.
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To improve the water absorbency and water-retention rate of superabsorbent materials, a porous calcium carbonate composite superabsorbent polymer (PCC/PAA) was prepared by copolymerization of acrylic acid and porous calcium carbonate prepared from ground calcium carbonate. The results showed that the binding energies of C-O and C=O in the O 1s profile of PCC/PAA had 0.2 eV and 0.1-0.7 eV redshifts, respectively, and the bonding of -COO- groups on the surface of the porous calcium carbonate led to an increase in the binding energy of O 1s. Furthermore, the porous calcium carbonate chelates with the -COO- group in acrylic acid through the surface Ca2+ site to form multidirectional crosslinking points, which would increase the flexibility of the crosslinking network and promote the formation of pores inside the PCC/PAA to improve the water storage space. The water absorbency of PCC/PAA with 2 wt% porous calcium carbonate in deionized water and 0.9 wt% NaCl water solution increased from 540 g/g and 60 g/g to 935 g/g and 80 g/g, respectively. In addition, since the chemical crosslinker N,N'-methylene bisacrylamide is used in the polymerization process of PCC/PAA, N,N'-methylene bisacrylamide and porous calcium carbonate enhance the stability of the PCC/PAA crosslinking network by double-crosslinking with a polyacrylic acid chain, resulting in the crosslinking network of PCC/PAA not being destroyed after water absorption saturation. Therefore, PCC/PAA with 2 wt% porous calcium carbonate improved the water-retention rate by 244% after 5 h at 60 °C, and the compressive strength was approximately five-times that of the superabsorbent without porous calcium carbonate.
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Photocatalytic CO2 reduction is a tactic for solving the environmental pollution caused by greenhouse gases. Herein, NH4H2PO4 was added as a phosphorus source in the process of the hydrothermal treatment of melamine for the first time, and phosphorus-doped hollow tubular g-C3N4 (x-P-HCN) was fabricated and used for photocatalytic CO2 reduction. Here, 1.0-P-HCN exhibited the largest CO production rate of 9.00 µmol·g-1·h-1, which was 10.22 times higher than that of bulk g-C3N4. After doping with phosphorus, the light absorption range, the CO2 adsorption capacity, and the specific surface area of the 1.0-P-HCN sample were greatly improved. In addition, the separation of photogenerated electron-hole pairs was enhanced. Furthermore, the phosphorus-doped g-C3N4 effectively activated the CO2 adsorbed on the surface of phosphorus-doped g-C3N4 photocatalysts, which greatly enhanced the CO production rate of photocatalytic CO2 reduction over that of g-C3N4.
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Temperature-sensitive carboxylated cellulose nanocrystals/N-isopropyl acrylamide aerogels (CCNC-NIPAMs) were developed as novel pesticide-controlled release formulas. Ammonium persulfate (APS) one-step oxidation was used to prepare bagasse-based CCNCs, and then the monomer N-isopropyl acrylamide (NIPAM) was successfully introduced and constructed into the temperature-sensitive CCNC-NIPAMs through polymerization. The results of the zeta potential measurement and Fourier infrared transform spectrum (FTIR) show that the average particle size of the CCNCs was 120.9 nm, the average surface potential of the CCNCs was -34.8 mV, and the crystallinity was 62.8%. The primary hydroxyl group on the surface of the CCNCs was replaced by the carboxyl group during oxidation. The morphology and structure of CCNC-NIPAMs were characterized via electron microscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), compression performance, porosity analysis, and thermogravimetric (TG) analysis. The results demonstrate that CCNC-NIPAM has a high porosity and low density, as well as good thermal stability, which is conducive to loading and releasing pesticides. In the swelling, drug loading, and controlled release process, the CCNC-NIPAM exhibited significant temperature sensitivity. Under the same NIPAM reaction amount, the equilibrium swelling rate of the CCNC-NIPAM first increased and then decreased with increasing temperature, and the cumulative drug release ratio of the CCNC-NIPAM at 39 °C was significantly higher than that at 25 °C. The loading efficiency of the CCNC-NIPAM on the model drug thiamethoxam (TXM) was up to 23 wt%, and the first-order model and Korsmyer-Peppas model could be well-fitted in the drug release curves. The study provides a new method for the effective utilization of biomass and pesticides.
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Constructing an efficient photoelectron transfer channel to promote the charge carrier separation is a great challenge for enhancing photocatalytic hydrogen evolution from water. In this work, an ultrathin 2D/2D Ti3 C2 Tx /ZnIn2 S4 heterostructure is rationally designed by coupling the ultrathin ZnIn2 S4 with few-layered Ti3 C2 Tx via the electrostatic self-assembly strategy. The 2D/2D Ti3 C2 Tx /ZnIn2 S4 heterostructure possesses larger contact area and strong electronic interaction to promote the charge carrier transfer at the interface, and the sulfur vacancy on the ZnIn2 S4 acting as the electron trap further enhances the separation of the photoinduced electrons and holes. As a consequence, the optimal 2D/2D Ti3 C2 Tx /ZnIn2 S4 composite exhibits a high photocatalytic hydrogen evolution rate of 148.4 µmol h-1 , which is 3.6 times and 9.2 times higher than that of ZnIn2 S4 nanosheet and flower-like ZnIn2 S4 , respectively. Moreover, the stability of the ZnIn2 S4 is significantly improved after coupling with the few-layered Ti3 C2 Tx . The characterizations and density functional theory calculation demonstrate that the synergistic effect of the sulfur vacancy and Ti3 C2 Tx cocatalyst can greatly promote the electrons transfer from ZnIn2 S4 to Ti3 C2 Tx and the separation of photogenerated charge carriers, thus enhancing the photocatalytic hydrogen evolution from water.
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Atomically dispersed Pt species supported on Fe2O3 (Pt1/Fe2O3) are successfully constructed by a simple ball milling process. In the selective hydrogenation of cinnamaldehyde (CAL), Pt1/Fe2O3 achieves an excellent cinnamyl alcohol (COL) selectivity of 81.7% at a CAL conversion of 91.2% in pure water medium due to the superior dissociation ability of H2 and preferential adsorption of CAL via CîO.
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In this work, 1-[(2â³-fluorophenyl)(methylimino)methyl]cyclopentan-1-ol (2-fluorodeschlorohydroxylimine) was identified as a suspected chemical precursor of 2-fluorodeschloroketamine (2-FDCK) using gas chromatography-mass spectrometry (GC-MS) and gas chromatography-quadrupole/time-of-flight mass spectrometry (GC-Q/TOF-MS) and comparing the data with those of ketamine and its chemical precursor, hydroxylimine. Furthermore, the entire fragmentation pathway of 2-fluorodeschlorohydroxylimine was theorized from the GC-MS spectrum recorded using an electron ionization (EI) source, and the mechanisms and decomposition pathways of 2-fluorodeschlorohydroxylimine were elucidated. In protic solvents, the nitrogen atom in the CâN group of 2-fluorodeschlorohydroxylimine underwent a protonation reaction. Thereafter, the traces of water present in protic solvents promoted the hydrolysis of the protonated imine, and a carbon cation was obtained following the loss of methylamine. The carbon cation could follow the classical decomposition mechanism of imines and yield an α-hydroxyl ketone, which was the major decomposition product, (2'-fluorophenyl)(1â³-hydroxycyclopentyl)methanone. The cation could also undergo a loop expansion rearrangement and yield another α-hydroxyl ketone, 2-(2'-fluorophenyl)-2-hydroxycyclohexan-1-one. The structures of the two aforementioned decomposition products were elucidated using several techniques including theoretical calculation, GC-MS, nuclear magnetic resonance (NMR), the prediction and assistance elucidation functions of ACDLabs-Structure Elucidator Suite, and the virtual separation technology of diffusion-ordered spectroscopy. The aforementioned study revealed important information about the chemical precursor of 2-FDCK and its decomposition. Furthermore, a set of methods for the qualitative analysis of 2-fluorodeschlorohydroxylimine were established, which facilitated accurate analysis of 2-fluorodeschlorohydroxylimine samples following decomposition or destruction.
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Carbono , Cetonas , Cromatografia Gasosa-Espectrometria de Massas/métodos , SolventesRESUMO
An InYO3 photocatalyst was prepared through a precipitation method and used for the degradation of molasses fermentation wastewater. The InYO3 photocatalyst characterized by X-ray diffraction (XRD), UV-Vis diffuse reflectance spectroscopy, surface area and porosimetry. Energy band structures and density of states were achieved using the Cambridge Serial Total Energy package (CASTEP). The results indicated that the photodegradation of molasses fermentation wastewater was significantly enhanced in the presence of InYO3 when compared with PbWO4. The calcination temperature was found to have a significant effect on the photocatalytic activity of InYO3. Specifically, InYO3 calcined at 700 degrees C had a considerably larger surface area and lower reflectance intensity and showed higher photocatalytic activity. The mathematical simulation results indicated that InYO3 is a direct band gap semiconductor, and its conduction band is composed of In 5p and Y 4d orbitals, whereas its valence band is composed of O 2p and In 5s orbitals.
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Fermentação , Melaço , Fotólise , Eliminação de Resíduos Líquidos/métodos , CatáliseRESUMO
Here, new and effective microsphere adsorbents were synthesized by NaOH activating slag based geopolymer (Na-SGS). These microsphere adsorbents upset the adsorption equilibrium with the maximum Ni2+ adsorption capacity of 414.38â¯mg/g which is much larger than that of other geopolymer materials. After Ni2+ adsorption from simulated nickel electroplating wastewater, more active positions for the adsorption Ni2+ ions on Na-SGS were provided as shifts from the average pore diameter of 22.00-7.44â¯nm, the pore volume of 0.06 to 0.25 cm3/g, the Brunauer-Emmett-Teller (BET) surface area of 10.46-125.35â¯m2/g and the apparent change of new morphology. Moreover, the adsorbed Ni2+ species were distributed uniformly on Na-SGS. Thermodynamic performance reflected an exothermic, spontaneous and molecular disorder adsorption process, which can be easily controlled by the pH, dosage, initial concentration, contact time and temperature. Through the controllable adsorption, Na-SGS after Ni2+ adsorption (Na-SGS-Ni) was recycled and then reduced to be directly supported nickel catalysts (red-Na-SGS-Ni), which showed superior catalytic activity for CO2 methanation. Although the highest percent of CO2 conversation (XCO2 =99.54%) and methane selectivity (SCH4 =99.5%) are both at 300⯰C, red-Na-SGS-Ni performed good XCO2 (99.48%) and SCH4 (98.2%) at low temperatures (100⯰C).
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In the presence of O(3), the oxidative decolorization reaction on molasses fermentation wastewater with SnO(2) as a catalyst was studied. The results showed that SnO(2) accelerated the ozone oxidation reaction and the oxidative decolorization of molasses fermentation wastewater was accelerated. Influences on SnO(2) catalytic ozonation activity by precipitants and the calcination temperature were studied by XRD, IR and TG-DSC. SnO(2) prepared by ammonia as the precipitant had higher catalytic activity and a stronger dehydroxylation. The IR spectra of adsorbed pyridine showed that there were Lewis acid sites on the surface of this SnO(2) catalyst. The main factors influencing molasses fermentation wastewater oxidative decolorization were the wastewater concentration, the O(3) concentration, the pH value and the catalyst dosage. The decolorization of wastewater was improved with the increase of the wastewater dilution ratio, the ozone concentration and the catalyst dosage. High activity *OH was found to be existing with less amount and low concentration in the process of SnO(2) catalyzed ozonation decolorization.
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Fermentação , Melaço , Ozônio/química , Compostos de Estanho/química , Poluentes da Água/química , Adsorção , Varredura Diferencial de Calorimetria , Catálise , Cor , Concentração de Íons de Hidrogênio , Difração de Raios XRESUMO
Photocatalytic hydrogen evolution from water has received enormous attention due to its ability to address a number of global environmental and energy-related issues. Here, we synthesize 2D/2D Ti3C2/g-C3N4 composites by electrostatic self-assembly technique and demonstrate their use as photocatalysts for hydrogen evolution under visible light irradiation. The optimized Ti3C2/g-C3N4 composite exhibited a 10 times higher photocatalytic hydrogen evolution performance (72.3 µmol h-1 gcat-1) than that of pristine g-C3N4 (7.1 µmol h-1 gcat-1). Such enhanced photocatalytic performance was due to the formation of 2D/2D heterojunctions in the Ti3C2/g-C3N4 composites. The intimate contact between the monolayer Ti3C2 and g-C3N4 nanosheets promotes the separation of photogenerated charge carriers at the Ti3C2/g-C3N4 interface. Furthermore, the ultrahigh conductivity of Ti3C2 and the Schottky junction formed between g-C3N4/MXene interfaces facilitate the photoinduced electron transfer and suppress the recombination with photogenerated holes. This work demonstrates that the 2D/2D Ti3C2/g-C3N4 composites are promising photocatalysts thanks to the ultrathin MXenes as efficient co-catalysts for photocatalytic hydrogen production.
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SnO2 was prepared by precipitation method and mental oxides modified SnO2 catalysts were prepared by coprecipitation method. High concentration molasses fermentation wastewater degradation by SnO2 catalyzed ozonation was used as a probe reaction and IR spectra were used to study the adsorption of O3 at SnO2 and different metal oxides modification SnO2 surface. The results showed, that in the infrared absorption spectra of adsorption of O3 prepared by pure O2 at SnO2 catalyst surface, two obvious bidentate absorption double peaks were found at 1 027 and 1 055 cm(-1), and 2 099 and 2 122 cm(-1), respectively. However, there was competitive adsorption between O3 prepared by air, and CO and CO2. Then the O3 adsorption decreased, leading to the decrease in the degradation of molasses fermentation wastewater by SnO2 catalytic ozonation, and after 60 min reaction, the degradation rate by pure oxygen as oxygen source was 79.2%. It was 33.1% more by air as oxygen source. Similar strength adsorption peaks in the infrared spectra were found at 2 236, 2213 cm(-1) and 1 628, 1 599 cm (-1) with Fe2O3, NiO, CuO, ZnO, MgO, SrO and BaO modified SnO2. But the adsorption of CO2 and CO was different on modifier-SnO2, There was a wide absorption peak at 1 580-1 070 cm(-1) in the infrared spectra of transition metal modified SnO2, and two new peaks at 1 298 and 1 274 cm(-1) were found between 1 580 and 1 070 cm(-1) in the infrared spectra of alkaline-earth metals modified SnO2 catalysts. These changes leaded to a different catalytic ozonation activity of modifier-SnO2, the results of molasses fermentation wastewater degradation by ozone combined with alkaline-earth metal modified SnO2 was obviously better than ozone combined with transition metal modified SnO2. And among them, the ozonation catalytic activity of BaO-SnO2 was the best.