One-step ball milling-prepared nano Fe2O3 and nitrogen-doped graphene with high oxygen reduction activity and its application in microbial fuel cells

• Nano Fe₂O₃ and N-doped graphene was prepared via a one-step ball milling method. • The maximum power density of Fe-N-G in MFC was 390% of that of pristine graphite. • Active sites like nano Fe₂O₃, pyridinic N and Fe-N groups were formed in Fe-N-G. • The improvement of Fe-N-G was due to full exposure of active sites on graphene. Developing high activity, low-cost and long durability catalysts for oxygen reduction reaction is of great significance for the practical application of microbial fuel cells. The full exposure of active sites in catalysts can enhance catalytic activity dramatically. Here, novel Fe-N-doped graphene is successfully synthesized via a one-step in situ ball milling method. Pristine graphite, ball milling graphene, N-doped graphene and Fe-N-doped graphene are applied in air cathodes, and enhanced performance is observed in microbial fuel cells with graphene-based catalysts. Particularly, Fe-N-doped graphene achieves the highest oxygen reduction reaction activity, with a maximum power density of 1380±20 mW/m² in microbial fuel cells and a current density of 23.8 A/m² at –0.16 V in electrochemical tests, which are comparable to commercial Pt and 390% and 640% of those of pristine graphite. An investigation of the material characteristics reveals that the superior performance of Fe-N-doped graphene results from the full exposure of Fe₂O₃ nanoparticles, pyrrolic N, pyridinic N and excellent Fe-N-G active sites on the graphene matrix. This work not only suggests the strategy of maximally exposing active sites to optimize the potential of catalysts but also provides promising catalysts for the use of microbial fuel cells in sustainable energy generation.     

Catalytic oxidation of CO over Pt/Fe3O4 catalysts: Tuning O2 activation and CO adsorption

• Strong metal-support interaction exists on Pt/Fe₃O₄ catalysts. • Pt metal particles facilitate the formation of oxygen vacancies on Fe₃O₄. • Fe₃O₄ supports enhance the strength of CO adsorption on Pt metal particles. The self-inhibition behavior due to CO poisoning on Pt metal particles strongly impairs the performance of CO oxidation. It is an effective method to use reducible metal oxides for supporting Pt metal particles to avoid self-inhibition and to improve catalytic performance. In this work, we used in situ reductions of chloroplatinic acid on commercial Fe₃O₄ powder to prepare heterogeneous-structured Pt/Fe₃O₄ catalysts in the solution of ethylene glycol. The heterogeneous Pt/Fe₃O₄ catalysts achieved a better catalytic performance of CO oxidation compared with the Fe₃O₄ powder. The temperatures of 50% and 90% CO conversion were achieved above 260°C and 290°C at Pt/Fe₃O₄, respectively. However, they are accomplished on Fe₃O₄ at temperatures higher than 310°C. XRD, XPS, and H₂-TPR results confirmed that the metallic Pt atoms have a strong synergistic interaction with the Fe₃O₄ supports. TGA results and transient DRIFTS results proved that the Pt metal particles facilitate the release of lattice oxygen and the formation of oxygen vacancies on Fe₃O₄. The combined results of O₂-TPD and DRIFTS indicated that the activation step of oxygen molecules at surface oxygen vacancies could potentially be the rate-determining step of the catalytic CO oxidation at Pt/Fe₃O₄ catalysts. The reaction pathway involves a Pt-assisted Mars-van Krevelen (MvK) mechanism.     

PM-support interfacial effect and oxygen mobility in Pt,Pd or Rh-loaded (Ce,Zr,La)O2 catalysts

• Pt/CZL exhibits the optimum catalytic performance for HC and NO_x elimination. • The strong PM-Ce interaction favors the oxygen mobility and DOSC. • Pd/CZL shows higher catalytic activity for CO conversion due to more O_latt species. • Great oxygen mobility at high temperature broadens the dynamic operation window. • The relationship between DOSC and catalytic performance is revealed. The physicochemical properties of Pt-, Pd- and Rh- loaded (Ce,Zr,La)O₂ (shorted for CZL) catalysts before/after aging treatment were systematically characterized by various techniques to illustrate the relationship of the dynamic oxygen storage/release capacity and redox ability with their catalytic performances for HC, NO_x and CO conversions. Pt/CZL catalyst exhibits the optimum catalytic performance for HC and NO_x elimination, which mainly contribute to its excellent redox ability and dynamic oxygen storage/release capacity (DOSC) at lower temperature due to the stronger PM (precious metals)-support interaction. However, the worse stability of Pt-O-Ce species and volatile Pt oxides easily result in the dramatical decline in catalytic activity after aging. Pd/CZL shows higher catalytic activity for CO conversion by reason of more O_latt species as the active oxygen for CO oxidation reaction. Rh/CZL catalyst displays the widest dynamic operation window for NO_x elimination as a result of greater oxygen mobility at high temperature, and the ability to retain more Rh-O-Ce species after calcined at 1100°C effectively restrains sintering of active RhO_x species, improving the thermal stability of Rh/CZL catalyst.     

Low-temperature CO oxidation over Au-doped 13X-type zeolite catalysts: preparation and catalytic activity

Au-supported 13X-type zeolite (Au/13X) was synthesized using a common deposition–precipitation (DP) method with a solution of sodium carbonate as a precipitate agent. Further testing was conducted to test for catalytic oxidation of CO. A study was conducted on the effects of different preparation conditions (i.e., chloroauric acid concentration, solution temperature, pH of solution, and calcinations temperature) on Au/13X for CO oxidation. In respect to the catalytic activity, the relationship between different the preparation conditions and gold particles in 13X zeolite was analyzed using X-ray diffraction, TEM and XPS. The activity of Au/13X catalysts in CO oxidation was dependent on the chloroauric acid concentration. From XRD results, a higher chloroauric acid concentration induced larger gold nanoparticles, which resulted in lower catalytic activity. Results revealed that higher temperatures induced higher Au loading, homogeneous deposit, and smaller gold clusters on the support of 13X, resulting in higher CO activity. Furthermore, a pH of 5 or 6 generated greater amounts of Au loading and smaller Au particles on 13X than at a pH of 8 or 9. This may be a result of an effective exchange between Au(OH)2Cl2- and Au(OH)₃Cl^- on specific surface sites of zeolite under the pH’s 5 and 6. The sample calcined at 300°C showed the highest activity, which may be due to the sample’s calcined at 200°C inability to decompose completely to metallic gold while the sample calcined at 400°C had larger particles of gold deposited on the support. It can be concluded from this study that Au/13X prepared from a gold solution with an initial chloroauric acid solution concentration of 1.5 × 10^-3 mol·L^-1 gold solution pH of 6, solution temperature of around 90°C, and a calcination temperature of 300°C provides optimum catalytic activity for CO oxidation.     

Effect of Cu-ZSM-5 catalysts with different CuO particle size on selective catalytic oxidation of N,N-Dimethylformamide

● A series of Cu-ZSM-5 catalysts were tested for DMF selective catalytic oxidation. ● Cu-6 nm samples showed the best catalytic activity and N₂ selectivity. ● Redox properties and chemisorbed oxygen impact on DMF catalytic oxidation. ● Isolated Cu²⁺ species and weak acidity have effects on the generation of N₂. N, N-Dimethylformamide (DMF), a nitrogen-containing volatile organic compound (NVOC) with high emissions from the spray industry, has attracted increasing attention. In this study, Cu-ZSM-5 catalysts with different CuO particle sizes of 3, 6, 9 and 12 nm were synthesized and tested for DMF selective catalytic oxidation. The crystal structure and physicochemical properties of the catalyst were studied by various characterization methods. The catalytic activity increases with increasing CuO particle size, and complete conversion can be achieved at 300–350 °C. The Cu-12 nm catalyst has the highest catalytic activity and can achieve complete conversion at 300 °C. The Cu-6 nm sample has the highest N₂ selectivity at lower temperatures, reaching 95% at 300 °C. The activity of the catalysts is determined by the surface CuO cluster species, the bulk CuO species and the chemisorbed surface oxygen species. The high N₂ selectivity of the catalyst is attributed to the ratio of isolated Cu²⁺ and bulk CuO species, and weak acidity is beneficial to the formation of N₂. The results in this work will provide a new design of NVOC catalytic oxidation catalysts.     

Effects of a diesel oxidation catalyst on gaseous pollutants and fine particles from an engine operating on diesel and biodiesel

The effects of a diesel oxidation catalytic (DOC) converter on diesel engine emissions were investigated on a diesel bench at various loads for two steady-state speeds using diesel fuel and B20. The DOC was very effective in hydrocarbon (HC) and CO oxidation. Approximately 90%–95% reduction in CO and 36%–70% reduction in HC were realized using the DOC. Special attention was focused on the effects of the DOC on elemental carbon (EC) and organic carbon (OC) fractions in fine particles (PM_2.5) emitted from the diesel engine. The carbonaceous compositions of PM_2.5 were analyzed by the method of thermal/optical reflectance (TOR). The results showed that total carbon (TC), OC and EC emissions for PM_2.5 from diesel fuel were generally reduced by the DOC. For diesel fuel, TC emissions decreased 22%–32% after the DOC depending on operating modes. The decrease in TC was attributed to 35%–97% decrease in OC and 3%–65% decrease in EC emissions. At low load, a significant increase in the OC/EC ratio of PM_2.5 was observed after the DOC. The effect of the DOC on the carbonaceous compositions in PM_2.5 from B20 showed different trends compared to diesel fuel. At low load, a slight increase in EC emissions and a significant decrease in OC/EC ratio of PM_2.5 after DOC were observed for B20.     

Catalytic oxidation of o-chlorophenol over Co2XAl (X= Co,Mg, Ca,Ni) hydrotalcite-derived mixed oxide catalysts

• Superior catalytic activity observed for o-chlorophenol oxidation on Co₂MgAlO. • The reducibility, oxygen species and basicity influenced catalytic activity. • The organic by-products were generated in o-chlorophenol catalytic oxidation. A cobalt-based hydrotalcite-like compound was prepared using a constant-pH coprecipitation method. Cobalt-transition metal oxides (Co₂XAlO, X= Co, Mg, Ca and Ni) were investigated for the deep catalytic oxidation of o-chlorophenol as a typical heteroatom contaminant containing chlorine atoms. The partial substitution of Co by Mg, Ca or Ni in the mixed oxide can promote the catalytic oxidation of o-chlorophenol. The Co₂MgAlO catalyst presented the best catalytic activity, and could maintain 90% o-chlorophenol conversion at 167.1°C, compared only 27% conversion for the Co₃AlO catalyst. The results demonstrated that the high activity could be attributed to its increased low-temperature reducibility, rich active oxygen species and excellent oxygen mobility. In the existence of acid and base sites, catalysts with strong basicity also showed preferred activity. The organic by-products generated during the o-chlorophenol catalytic oxidation over Co₂MgAlO catalyst included carbon tetrachloride, trichloroethylene, 2,4-dichlorophenol, and 2,6-dichloro-p-benzoquinon, et al. This work provides a facile method for the preparation of Co-based composite oxide catalysts, which represent promising candidates for typical chlorinated and oxygenated volatile organic compounds.     

Size and shape effects of MnFe2O4 nanoparticles as catalysts for reductive degradation of dye pollutants

• Size and shape-dependent MnFe₂O₄ NPs were prepared via a facile method. • Ligand-exchange chemistry was used to prepare the hydrophilic MnFe₂O₄ NPs. • The catalytic properties of MnFe₂O₄ NPs toward dye degradation were fully studied. • The catalytic activities of MnFe₂O₄ NPs followed Michaelis–Menten behavior. • All the MnFe₂O₄ NPs exhibit selective degradation to different dyes. The magnetic nanoparticles that are easy to recycle have tremendous potential as a suitable catalyst for environmental toxic dye pollutant degradation. Rationally engineering shapes and tailoring the size of nanocatalysts are regarded as an effective manner for enhancing performances. Herein, we successfully synthesized three kinds of MnFe₂O₄ NPs with distinctive sizes and shapes as catalysts for reductive degradation of methylene blue, rhodamine 6G, rhodamine B, and methylene orange. It was found that the catalytic activities were dependent on the size and shape of the MnFe₂O₄ NPs and highly related to the surface-to-volume ratio and atom arrangements. Besides, all these nanocatalysts exhibit selectivity to different organic dyes, which is beneficial for their practical application in dye pollutant treatment. Furthermore, the MnFe₂O₄ NPs could be readily recovered by a magnet and reused more than ten times without appreciable loss of activity. The size and shape effects of MnFe₂O₄ nanoparticles demonstrated in this work not only accelerate further understanding the nature of nanocatalysts but also contribute to the precise design of nanoparticles catalyst for pollutant degradation.     

Catalytic activity of cerium-doped Ru/AlO during ozonation of dimethyl phthalate

In this paper, factors influencing the mineralization of dimethyl phthalate (DMP) during catalytic ozonation with a cerium-doped Ru/Al₂O₃ catalyst were studied. The catalytic contribution was calculated through the results of a comparison experiment. It showed that doping cerium significantly enhanced catalytic activity. The total organic carbon (TOC) removal over the doped catalyst at 100 min reached 75.1%, 61.3% using Ru/Al₂O₃ catalyst and only 14.0% using ozone alone. Catalytic activity reached the maximum when 0.2% of ruthenium and 1.0% of cerium were simultaneously loaded onto Al₂O₃ support. Results of experiments on oxidation by ozone alone, adsorption of the catalyst, Ce ion’s and heterogeneous catalytic ozonation confirmed that the contribution of heterogeneous catalytic ozonation was about 50%, which showed the obvious effect of Ru–Ce/Al₂O₃ on catalytic activity.     

Ce0.7Zr0.3O2纳米棒的制备及其对柴油车尾气碳颗粒的催化净化性能

本研究以硝酸铈、硝酸锆为原料使用溶剂热合成法,制备了CeO₂-ZrO₂纳米棒催化剂(Ce_0.7Zr_0.3O₂(NR)),并用于柴油车尾气碳颗粒催化净化.催化活性检测证实:Ce_0.7Zr_0.3O₂(NR)纳米棒催化剂可有效净化柴油车尾气碳烟颗粒.在Ce_0.7Zr_0.3O₂(NR)存在下,碳颗粒净化率为10%、50%和90%时,所需温度分别仅为375℃、414℃和455℃,比商用Ce_0.7Zr_0.3O₂和Ce0.3Zr0.7O2催化剂性能更优.采用氮吸附-脱附、X射线光电子能谱(XPS)、H2程序升温还原(H₂-TPR)、X射线衍射(XRD)、拉曼光谱(Raman)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等技术对催化剂进行表征.XRD和Raman结果证实,Ce_0.7Zr_0.3O₂(NR)主要由立方相CeO₂构成,并掺杂了少量四方相氧化锆.SEM和TEM结果则显示,Ce_0.7Zr_0.3O₂(NR)催化剂颗粒明显由纳米棒堆积而成,特定的纳米形貌会影响其对碳颗粒的催化氧化活性.XPS结果证明Ce_0.7Zr_0.3O₂(NR)催化剂主要具有晶格氧、化学氧和表面吸附氧等氧物种;晶格氧是碳颗粒氧化的活性氧物种,其溢流到催化剂表面可与碳颗粒接触从而提高反应活性;化学氧和表面吸附氧均为表面氧物种,极易与表面固体碳颗粒直接接触,从而可在较低温度下促进碳颗粒的净化.H₂-TPR结果进一步证实了XPS结果,Ce_0.7Zr_0.3O₂(NR)催化剂的低温还原温度比商用Ce_0.7Zr_0.3O₂催化剂更低,且含有更多的易还原氧物种,这些低温易还原氧物种可以在较低温度下参与催化反应,促进柴油车尾气颗粒物的低温催化净化.     

Tailoring the simultaneous abatement of methanol and NOx on Sb-Ce-Zr catalysts via copper modification

● Cu addition enhances CH₃OH oxidation and alleviates its inhibitory effect on SCR. ● Cu addition improves the activation of SCR reactants in the presence of methanol. ● Damaged structure by more Cu addition decreases specific surface area and acidity. ● Excessive Cu addition would lead to the narrowing of SCR temperature window. Simultaneously removal of NO_x and VOCs over NH₃-SCR catalysts have attracted lots of attention recently. However, the presence of VOCs would have negative effect on deNO_x efficiency especially at low temperature. In this study, copper modification onto Sb_0.5CeZr₂O_x (SCZ) catalyst were performed to enhance the catalytic performance for simultaneous control of NO_x and methanol. It was obtained that copper addition could improve the low-temperature activity of both NO_x conversion and methanol oxidation, where the optimal catalyst (Cu_0.05SCZ) exhibited a deNO_x activity of 96% and a mineralization rate of 97% at 250 °C, which are around 10% higher than that of Cu free sample. The characterization results showed that copper addition could obviously enhance the redox capacity of the catalysts. As such, the inhibition effect of methanol incomplete oxidation on NO adsorption and NH₃ activation were then lessened and the conversion of surface formamide species were also accelerated, resulting in the rising of NO_x conversion at low temperature. However, excessive copper addition would damage the Sb-Ce-Zr oxides solid solution structure owing to Cu-Ce strong interactions, decreasing the surface area and acidity. Meanwhile, due to easier over-oxidation of NH₃ with more Cu addition, the temperature window for NO_x conversion would become quite narrow. These findings could provide useful guidelines for the synergistic removal of VOCs over SCR catalyst in real application.     

Enhancement of the electrocatalytic oxidation of antibiotic wastewater over the conductive black carbon-PbO2 electrode prepared using novel green approach

• A novel conductive carbon black modified lead dioxide electrode is synthesized. • The modified PbO₂ electrode exhibits enhanced electrochemical performances. • BBD method could predict optimal experiment conditions accurately and reliably. • The modified electrode possesses outstanding reusability and safety. The secondary pollution caused by modification of an electrode due to doping of harmful materials has long been a big concern. In this study, an environmentally friendly material, conductive carbon black, was adopted for modification of lead dioxide electrode (PbO₂). It was observed that the as-prepared conductive carbon black modified electrode (C-PbO₂) exhibited an enhanced electrocatalytical performance and more stable structure than a pristine PbO₂ electrode, and the removal efficiency of metronidazole (MNZ) and COD by a 1.0% C-PbO₂ electrode at optimal conditions was increased by 24.66% and 7.01%, respectively. Results revealed that the electrochemical degradation of MNZ wastewater followed pseudo-first-order kinetics. This intimates that the presence of conductive carbon black could improve the current efficiency, promote the generation of hydroxyl radicals, and accelerate the removal of MNZ through oxidation. In addition, MNZ degradation pathways through a C-PbO₂ electrode were proposed based on the identified intermediates. To promote the electrode to treat antibiotic wastewater, optimal experimental conditions were predicted through the Box-Behnken design (BBD) method. The results of this study suggest that a C-PbO₂ electrode may represent a promising functional material to pretreat antibiotic wastewaters.     

Catalytic decomposition of low level ozone with gold nanoparticles supported on activated carbon

Highly dispersed gold nanoparticles were supported on coal-based activated carbon (AC) by a sol immobilization method and were used to investigate their catalytic activity for low-level ozone decomposition at ambient temperature. Nitrogen adsorption-desorption, scanning electron microscope (SEM), and X-ray photoelectron spectroscopy (XPS) were used to characterize the catalysts before and after ozone decomposition. The results showed that the supported gold nanoparticles prepared with microwave heating were much smaller and more uniformly dispersed on the activated carbon than those prepared with traditional conduction heating, exhibiting higher catalytic activity for ozone decomposition. The pH values of gold precursor solution significantly influenced the catalytic activity of supported gold for ozone decomposition, and the best pH value was 8. In the case of space velocity of 120000h⁻¹, inlet ozone concentration of 50mg/m³, and relative humidity of 45%, the Au/AC catalyst maintained the ozone removal ratio at 90.7% after 2500min. After being used for ozone decomposition, the surface carbon of the catalyst was partly oxidized and the oxygen content increased accordingly, while its specific surface area and pore volume only decreased a little. Ozone was mainly catalytically decomposed by the gold nanoparticles supported on the activated carbon.     

Catalytic activity of noble metal nanoparticles toward hydrodechlorination: influence of catalyst electronic structure and nature of adsorption

In this study, stabilized Pd, Pt and Au nanoparticles were successfully prepared in aqueous phase using sodium carboxymethyl cellulose (CMC) as a capping agent. These metal nanoparticles were then tested for catalytic hydrodechlorination toward two classes of organochlorinated compounds (vinyl polychlorides including trichloroethylene (TCE), tetrachloroethylene (PCE), and alkyl polychlorides including 1,1,1-trichloroethane (1,1,1-TCA), and 1,1,1,2-tetrachloroethane (1,1,1,2-TeCA)) to determine the rate-limiting steps and to explore the reaction mechanisms. The surface area normalized reaction rate constant, k_SA, showed a systematic dependence on the electronic structure (the density of states at the Fermi level) of the metals, suggesting that adsorption of organochlorinated reactants on the metal catalyst surfaces is the rate-limiting step for catalytic hydrodechlorination. Hydrodechlorination rates of 1,1,1-TCA and 1,1,1,2-TeCA agreed with the bond strength of the first (weakest) dissociated C-Cl bond, suggesting that C-Cl bond cleavage, which is the first step for dissociative adsorption of the alkyl polychlorides, controlled the catalytic hydrodechlorination rate. However, hydrodechlorination rates of TCE and PCE correlated with the adsorption energies of their molecular (non-dissociative) adsorption on the noble metals rather than with the first C-Cl bond strength, suggesting that molecular adsorption governs the reaction rate for hydrodechlorination of the vinyl polychlorides.     

A multi-integrated approach on toxicity effects of engineered TiO2 nanoparticles

The new properties of engineered nanoparticles drive the need for new knowledge on the safety, fate, behavior and biologic effects of these particles on organisms and ecosystems. Titanium dioxide nanoparticles have been used extensively for a wide range of applications, e.g, self-cleaning surface coatings, solar cells, water treatment agents, topical sunscreens. Within this scenario increased environmental exposure can be expected but data on the ecotoxicological evaluation of nanoparticles are still scarce. The main purpose of this work was the evaluation of effects of TiO₂ nanoparticles in several organisms, covering different trophic levels, using a battery of aquatic assays. Using fish as a vertebrate model organism tissue histological and ultrastructural observations and the stress enzyme activity were also studied. TiO₂ nanoparticles (Aeroxide® P25), two phase composition of anatase (65%) and rutile (35%) with an average particle size value of 27.6±11 nm were used. Results on the EC₅₀ for the tested aquatic organisms showed toxicity for the bacteria, the algae and the crustacean, being the algae the most sensitive tested organism. The aquatic plant Lemna minor showed no effect on growth. The fish Carassius auratus showed no effect on a 21 day survival test, though at a biochemical level the cytosolic Glutathione-S-Transferase total activity, in intestines, showed a general significant decrease (p<0.05) after 14 days of exposure for all tested concentrations. The presence of TiO₂ nanoparticles aggregates were observed in the intestine lumen but their internalization by intestine cells could not be confirmed.     

Simultaneous removal of NOx and chlorobenzene on V2O5/TiO2 granular catalyst: Kinetic study and performance prediction

• A V₂O₅/TiO₂ granular catalyst for simultaneous removal of NO and chlorobenzene. • Catalyst synthesized by vanadyl acetylacetonate showed good activity and stability. • The kinetic model was established and the synergetic activity was predicted. • Both chlorobenzene oxidation and SCR of NO follow pseudo-first-order kinetics. • The work is of much value to design of multi-pollutants emission control system. The synergetic abatement of multi-pollutants is one of the development trends of flue gas pollution control technology, which is still in the initial stage and facing many challenges. We developed a V₂O₅/TiO₂ granular catalyst and established the kinetic model for the simultaneous removal of NO and chlorobenzene (i.e., an important precursor of dioxins). The granular catalyst synthesized using vanadyl acetylacetonate precursor showed good synergistic catalytic performance and stability. Although the SCR reaction of NO and the oxidation reaction of chlorobenzene mutually inhibited, the reaction order of each reaction was not considerably affected, and the pseudo-first-order reaction kinetics was still followed. The performance prediction of this work is of much value to the understanding and reasonable design of a catalytic system for multi-pollutants (i.e., NO and dioxins) emission control.     

Catalytic ozonation of organic compounds in water over the catalyst of RuO2/ZrO2-CeO2

This research investigates the performances of RuO₂/ZrO₂-CeO₂ in catalytic ozonation for water treatment. The results show that RuO₂/ZrO₂-CeO₂ was active for the catalytic ozonation of oxalic acid and possessed higher stability than RuO₂/Al₂O₃ and Ru/AC. In the catalytic ozonation of dimethyl phthalate (DMP), RuO₂/ZrO₂-CeO₂ did not enhance the DMP degradation rate but significantly improved the total organic carbon (TOC) removal rate. The TOC removal in catalytic ozonation was 56% more than that in noncatalytic ozonation. However this does not mean the catalyst was very active because the contribution of catalysis to the overall TOC removal was only 30%. The adsorption of the intermediates on RuO₂/ZrO₂-CeO₂ played an important role on the overall TOC removal while the adsorption of DMP on it was negligible. This adsorption difference was due to their different ozonation rates. In the catalytic ozonation of disinfection byproduct precursors with RuO₂/ZrO₂-CeO₂, the reductions of the haloacetic acid and trihalomethane formation potentials (HAAFPs and THMFPs) for the natural water samples were 38%–57% and 50%–64%, respectively. The catalyst significantly promoted the reduction of HAAFPs but insignificantly improved the reduction of THMFPs as ozone reacts fast with the THMs precursors. These results illustrate the good promise of RuO₂/ZrO₂-CeO₂ in catalytic ozonation for water treatment.     

Novel synthetic approaches and TWC catalytic performance of flower-like Pt/CeO2

A novel Ultrasonic Assisted Membrane Reduction （UAMR）-hydrothermal method was used to prepare flower-like Pt/CeO2 catalysts. The texture, physical/chemical properties, and reducibility of the flower-like Pt/CeO2 catalysts were characterized by X-Ray Diffraction （XRD）, Scanning Electron Microscope （SEM）, Transmission Electron Microscope （TEM）, N2 adsorption, and hydrogen temperature programmed reduction （HE-TPR） techniques. The catalytic performance of the catalysts for treating automobile emission was studied relative to samples prepared by the conventional wetness impregnation method. The Pt/CeO2 catalysts fabricated by this novel method showed high specific surface area and metal dispersion, excellent three-way catalytic activity, and good thermal stability. The strong interaction between the Pt nanoparticles and CeO2 improved the thermal stability. The Ce4＋ ions were incorporated into the surfactant chains and the Pt nanoparticles were stabilized through an exchange reaction of the surface hydroxyl groups. The SEM results demonstrated that the Pt/CeO2 catalysts had a typical three-dimensional （3D） hierarchical porous struc- ture, which was favorable for surface reaction and enhanced the exposure degree of the Pt nanoparticles. In brief, the flower-like Pt/CeO2 catalysts prepared by UAMR-hydrothermal method exhibited a higher Pt metal dispersion, smaller particle size, better three-way catalytic activity, and improved thermal stability versus conven- tional materials.     

Visible-light-driven heterostructured g-C3N4/Bi-TiO2 floating photocatalyst with enhanced charge carrier separation for photocatalytic inactivation of Microcystis aeruginosa

• Bi doping in TiO₂ enhanced the separation of photo-generated electron-hole. • The performance of photocatalytic degradation of MC-LR was improved. • Coexisting substances have no influence on algal removal performance. • The key reactive oxygen species were h⁺ and ^•OH in the photocatalytic process. The increase in occurrence and severity of cyanobacteria blooms is causing increasing concern; moreover, human and animal health is affected by the toxic effects of Microcystin-LR released into the water. In this paper, a floating photocatalyst for the photocatalytic inactivation of the harmful algae Microcystis aeruginosa (M. aeruginosa) was prepared using a simple sol-gel method, i.e., coating g-C₃N₄ coupled with Bi-doped TiO₂ on Al₂O₃-modified expanded perlite (CBTA for short). The impact of different molar ratios of Bi/Ti on CBTA was considered. The results indicated that Bi doping in TiO₂ inhibited photogenerated electron-hole pair recombination. With 6 h of visible light illumination, 75.9% of M. aeruginosa (initial concentration= 2.7 × 10⁶ cells/L) and 83.7% of Microcystin-LR (initial concentration= 100 μg/L) could be removed with the addition of 2 g/L CBTA-1% (i.e., Bi/Ti molar ratio= 1%). The key reactive oxygen species (ROSs) in the photocatalytic inactivation process are h⁺ and ^•OH. The induction of the Bi⁴⁺/Bi³⁺ species by the incorporation of Bi could narrow the bandgap of TiO₂, trap electrons, and enhance the stability of CBTA-1% in the solutions with coexisting environmental substances.     

Catalytic urea hydrolysis by composite metal oxide catalyst towards efficient urea-based SCR process: performance evaluation and mechanism investigation

● Bimetallic oxide composite catalyst was designed for the urea-based SCR process. ● Surface chemical state and typical microstructure of catalyst was determined. ● Reaction route was improved based on intermediates and active site identification. ● TiO₂@Al₂O₃ presents an obvious promotion for urea hydrolysis. As a promising option to provide gaseous NH₃ for SCR system, catalytic urea hydrolysis has aroused great attention, and improving surface area and activity of catalysis are the crucial issues to be solved for efficient urea hydrolysis. Therefore, a composite metal oxide (TiO₂@Al₂O₃) catalyst was prepared by a simple hydrothermal method, with mesoporous alumina (γ-Al₂O₃) as substrate. The results verify the mesoporous structure and submicron cluster of TiO₂@Al₂O₃, with exposed crystal faces of (101) and (400) for TiO₂ and γ-Al₂O₃, respectively. The electronegativity difference of Ti⁴⁺ and Al³⁺ changes the charge distribution scheme around the interface, which provides abundant acid/base sites to boost the urea hydrolysis. Consequently, for an optimal proportioning with nano TiO₂ content at 10 wt.%, the hydrolysis efficiency can reach up to 35.2 % at 100 °C in 2 h, increasing by ~7.1 % than that of the blank experiment. ¹³C NMR spectrum measurements provide the impossible intermediate species during urea hydrolysis. Theoretical calculations are performed to clarify the efficient H₂O decomposition at the interface of TiO₂@Al₂O₃. The result offers a favorable technology for energy-efficiency urea hydrolysis.