Catalytic activity of H2O2 by goethite and lepidocrocite: Insight from 5-bromosalicylic acid removal mechanism and density functional theory calculation (ID:CHEM114760).

We have compared the elimination of 5-bromosalicylic acid (BSA) in the systems of goethite (α-FeOOH)/H2O2 and lepidocrocite (γ-FeOOH)/H2O2. The results demonstrated that BSA (10 mg L-1) could be successfully adsorbed on α- and γ-FeOOH (0.5 g L-1) and then effectively degraded after the addition of H2O2 (14.7 mM). BSA adsorption on both α- and γ-FeOOH followed pseudo-second order adsorption kinetic models, with γ-FeOOH having greater adsorption ability than α-FeOOH. In the α-FeOOH/H2O2 system, BSA degradation was well fitted with the pseudo-second order kinetics, whereas the oxidation in γ-FeOOH/H2O2 system had a two-stage pseudo-first order kinetics. Electron paramagnetic resonance (EPR) results for these two systems revealed the presence of •OH and •OOH, and further tests with radical captures demonstrated their dominance in degrading BSA. Based on the electronic structure analysis, electrons were more easily transferred from the H2O2 molecule to the Fe atoms of α-FeOOH, explaining the density functional theory (DFT) calculation results, which showed that α-FeOOH performed better in catalyzing the decomposition of H2O2. However, the free radicals are more likely to desorb from γ-FeOOH, which made the γ-FeOOH/H2O2 system more efficient in degrading BSA.

Unexpected Intrinsic Catalytic Function of Porous Boron Nitride Nanorods for Highly Efficient Peroxymonosulfate Activation in Water Treatment.

Porous boron nitride (BN) nanorods, which were synthesized via a one-stage pyrolysis, exhibited excellent catalytic performance for organics' degradation via peroxymonosulfate (PMS) activation. The origin of the unexpected catalytic function of porous BN nanorods was proposed, in which non-radical oxidation driven by the defects on porous BN dominated the sulfamethoxazole degradation via the generation of singlet oxygen (1O2). The adsorption energy between PMS and BN was calculated via density functional theory (DFT), and the PMS activation kinetics were further investigated using an electrochemical methodology. The evolution of 1O2 was verified by electron spin resonance (ESR) and chemical scavenging experiments. The observed non-radical oxidation presented a high robustness in different water matrices, combined with a series of much less toxic intermediates. The used BN was easily regenerated by heating in air, in which the B-O bond was fully recovered. These findings provide new insights for BN as a non-metal catalyst for organics' degradation via PMS activation, in both theoretical and practical prospects.

Tailoring Fe2O3-Al2O3 catalyst structure and activity via hydrothermal synthesis for carbon nanotubes and hydrogen production from polyolefin plastics.

Fe2O3-Al2O3 catalysts applied for conversion of polyolefin plastic waste into multi-walled carbon nanotubes (MWCNTs) and H2 are typically produced by impregnation, co-precipitation or sol-gel synthesis at atmospheric pressure and temperatures below 100 °C. This study utilized hydrothermal conditions and established the role of precipitating agents (urea, N-methylurea and N,N'-dimethylurea) on properties and catalytic activity of Fe2O3-Al2O3 catalysts (Fe-u, Fe-mu and Fe-dmu, respectively). The precipitating agent played a key role in tailoring the properties, such as crystallization degree, surface area and reducibility. The precipitating agents influenced the yield and outer diameters of MWCNTs but did not affect graphitization degree. Among the synthesized catalysts, Fe-u had the largest surface area and preferential formation of the highly reducible α-Fe2O3 crystalline phase. As a result, Fe-u had the highest activity during conversion of pyrolysis gas from low-density polyethylene (LDPE) into MWCNTs, yielding 0.91 g·g-1-catalyst MWCNTs at 800 °C as compared to 0.42 and 0.14 g·g-1-catalyst using Fe-dmu and Fe-mu, respectively. Fe-dmu favored the growth of MWCNTs with smaller outer diameters. Fe-u demonstrated high efficiency during operation using a continuous flow of pyrolysis gas from a mixture of polyolefins (70 wt% polypropylene, 6 wt% LDPE and 24 wt% high density polyethylene) producing 4.28 g·g-1-catalyst MWCNTs at 3.2% plastic conversion efficiency and a stable H2 flow for 155 min (25-32 vol%). The obtained data demonstrate that the selection of an appropriate precipitating agent for hydrothermal synthesis allows for the production of highly active Fe2O3-Al2O3 catalysts for the upcycling of polyolefin plastic waste into MWCNTs and H2.

Polyoxometalates for bifunctional applications: Catalytic dye degradation and anticancer activity.

Improving the efficiencies of organic compound degradations by catalytic materials is a challenging materials research field. In our research, we successfully synthesized cobalt-based polyoxometalates (CoV-POMs) via a simple crystallization-driven self-assembly method. The incorporation of the newly synthesized CoV-POMs into peroxymonosulphate (PMS), forming a mixture, greatly enhancing the catalytic activation for a complete degradation of dye solution. The positive synergic effect between CoV-POMs and PMS was substantiated by a relatively meager degradation of less than 10% in the system without CoV-POMs, in which CoV-POMs played a vital role to activate PMS towards free radicals generation for dye degradation. Methylene blue (MB) and rhodamine B (RB) dyes were completely decolorized under 60 min with the presence of 40 mg/L CoV-POMs and 150 mg/L PMS. The CoV-POMs/PMS system was pH dependance with a lower dye degradation efficiency at elevated pH. The effect of pH was more prominent in RB dye, in which the degradation efficiency dropped drastically from 93.3% to 41.12% with the increase in the solution pH from 7 to 11. The quenching tests suggested that sulfate radicals were the dominant active species involving in the dye degradation reaction. Besides MB and RB dyes, CoV-POMs/PMS system also showed significant activity towards the degradation of phenol red (PR) and methyl orange (MO) dyes. In the biological test, CoV-POMs exhibited non-toxic behavior towards normal cells that reduced safety concern for the large-scale wastewater treatment application. In addition, the testing divulged the anticancer property of CoV-POMs with more than 35 % of A549 lung adenocarcinoma and MDA-MB-231 breast adenocarcinoma were killed with 250 mg/L CoV-POMs. The selective lethality of CoV-POMs towards cancer cells was found to be caused by different extents of cellular apoptosis. In overall, the synthesized bifunctional CoV-POMs manifested superior activities in the examined applications, specifically dye degradation and anticancer.

Temperature-dependent synthesis of multi-walled carbon nanotubes and hydrogen from plastic waste over A-site-deficient perovskite La0.8Ni1-xCoxO3-δ.

Thermochemical conversion of plastic wastes into carbon nanotubes (CNTs) and hydrogen is a promising management option to eliminate their hazardous effect. The yields and morphologies of CNTs strongly depend on the catalyst design and reaction conditions. To boost the efficiency, tuning of bimetallic nanoparticles as catalyst is an effective approach. For that reason, A-site-deficient perovskite La0·8Ni1-xCoxO3-δ (LN1-xCx, x = 0.15, 0.5, 0.85) was developed and used as a catalyst precursor to achieve in situ formation of bimetallic Ni-Co nanoparticles. At an optimized Ni-to-Co ratio, the LN0.5C0.5 exhibited the highest yields of multi-walled CNTs, namely 840 and 853 mg/gcatalyst from high density polyethylene and polypropylene, respectively. This could be attributed to the higher catalytic capability of LN0.5C0.5 catalyst for the decomposition of hydrocarbons into hydrogen and carbon. In both cases, multi-walled CNTs had regular shapes when the reaction temperature was 700 °C. At higher reaction temperatures, the morphological changes of carbon products were observed from multi-walled CNTs to carbon nano-onions. The Raman spectra showed that compared with the commercial multi-walled CNTs, the as-prepared multi-walled CNTs had a lower degree of defects.

Multi-heteroatom-doped carbocatalyst as peroxymonosulfate and peroxydisulfate activator for water purification: A critical review.

Catalytic activation of peroxymonosulfate (PMS) and peroxydisulfate (PDS) (or collectively known as persulfate, PS) using carbocatalyst is increasingly gaining attention as a promising technology for sustainable recalcitrant pollutant removal in water. Single heteroatom doping using either N, S, B or P is widely used to enhance the performance of the carbocatalyst for PS activation. However, the performance enhancement from single heteroatom doping is limited by the type of heteroatom used. To further enhance the performance of the carbocatalyst beyond the limit of single heteroatom doping, multi-heteroatom doping can be conducted. This review aims to provide a state-of-the-art overview on the development of multi-heteroatom-doped carbocatalyst for PS activation. The potential synergistic and antagonistic interactions of various heteroatoms including N and B, N and S, N and P, and N and halogen for PS activation are evaluated. Thereafter, the preparation strategies to develop multi-heteroatom-doped carbocatalyst including one-step and multi-step preparation approaches along with the characterization techniques are discussed. Evidence and summary of the performance of multi-heteroatom-doped carbocatalyst for various recalcitrant pollutants removal via PS activation are also provided. Finally, the prospects of employing multi-heteroatom-doped carbocatalyst including the need to study the correlation between different heteroatom combination, surface moiety type, and amount of dopant with the PS activation mechanism, identifying the best heteroatom combination, improving the durability of the carbocatalyst, evaluating the feasibility for full-scale application, developing low-cost multi-heteroatom-doped carbocatalyst, and assessing the environmental impact are also briefly discussed.

Universal and Switchable Omni-Repellency of Liquid-Infused Surfaces for On-Demand Separation of Multiphase Liquid Mixtures.

Mixtures of immiscible liquids are commonly found in the scenarios of environmental protection and many industrial applications. Compared to widely explored water-oil mixtures, small differences in the surface energy of organic liquids, especially for those in multiphase mixtures, make their separation a formidable challenge. Here, a family of versatile coatings based on the reactions between plant polyphenols and 3-aminopropyl triethoxysilane is introduced to regulate the wetting behavior of substrates by forming stable liquid-infused interfaces. The key finding is that when a coated substrate is prewetted with a liquid forming a stable liquid-infused interface, it becomes repellent to any other immiscible liquids. This phenomenon is independent of the surface energy of the initial wetting liquid. This exclusive wetting behavior can lead to distinctive repellency toward almost any liquid by the infusion of an immiscible liquid, even if the difference of surface energy and dielectric constant of a liquid pair is as small as 2.0 mJ m-2 and 1.8, respectively, resulting in universal and switchable omni-repellency. Of particular importance is that the as-prepared coating makes possible the on-demand separation of multiphase liquid mixtures by both continuous membrane filtration and static absorption, presenting a green and cost-effective approach to addressing this major environmental and industrial challenge.

Weakening the strong Fe-La interaction in A-site-deficient perovskite via Ni substitution to promote the thermocatalytic synthesis of carbon nanotubes from plastics.

The variation of metal-support interaction (MSI) plays a key role in the synthesis of carbon nanotubes (CNTs) based on chemical vapor deposition process. This work concentrates on weakening the interaction of Fe-La in an A-site-deficient perovskite (La0.8FeO3-δ) via Ni partial substitution. After reductive treatment, the catalysts were employed for thermocatalytic synthesis of CNTs from plastics. Following the structural, morphological and chemical changes, the catalytic activities of the reductive La0.8NixFe1-xO3-δ (H-LNxF1-x, x = 0, 0.15, 0.5, 0.85) were correlated with the degree of MSI. Compared with H-LF sample, the H-LN0.15F0.85 sample exhibited the highest catalytic activity, which was attributable to the highest surface coverage of metals as well as the synergistic effect of Fe and Ni species. The yield of CNTs produced from low density polyethylene was 1.44 g/gcatalyst over the H-LN0.15F0.85 sample, which was much higher than that over H-LF sample (0.38 g/gcatalyst).

Hierarchical Graphene/Metal-Organic Framework Composites with Tailored Wettability for Separation of Immiscible Liquids.

Membrane filtration is a promising technology for the separation of organic immiscible liquids. Surface topography has a direct impact on the wettability of membranes, and it remains largely unexplored. Here, we introduce on-demand liquid separation by coating porous graphene/metal-organic framework (MOF) composites with tunable wettability on porous substrates. Our results have shown that polydopamine (PDA) coating mediates the controlled growth of MOF nanostructures and subsequent fluorination on the porous graphene framework. Surface topography of the graphene frameworks strongly depends on the loading content of MOF nanostructures. The concurrent control of surface coverage of MOF and surface chemistry allows tailoring of the trapped air fraction underneath the porous graphene frameworks in the range of 0.97 to 0.8. As a result, the surface energy of the graphene/MOF coatings can be programmed to afford the change in surface properties from superamphiphobicity to lyophobicity and the selective penetration of low-surface-energy (SE) liquids and the interception of high-SE liquids were achieved. The tailored wettability of graphene/MOF coatings allows for the separation of liquid mixtures of different ranges of SE, making it a general strategy for complex liquid treatment and chemical purification.

Spatial confinement of cobalt crystals in carbon nanofibers with oxygen vacancies as a high-efficiency catalyst for organics degradation.

Catalytic activation of peroxymonosulfate (PMS) to generate radicals has received considerable and increasing attention in the environmental catalysis for treatment of recalcitrant pollutants. In the current study, a series of highly porous, cobalt-loaded activated carbon nanofibers (Co/CNFs) were prepared by one-pot electrospinning followed by thermal treatment. Observations showed that the limited addition of Co (≤8%) had no obvious effect on the morphology of the resulted CNFs, but it did affect the surface area and porosity of the CNFs as well as the carbon graphitic process during the carbonization. The applicability of this confined nanoreactor used in sulfate-radical based advanced oxidation processes (SR-AOPs) was systematically investigated. The effect of pH on the radical generation and organics removal was examined. The oxygen species on the CNFs played an important role in the activation of PMS. The carbon layer encapsulated on the Co crystal surface inhibited the Co leaching during the reaction and increased the catalytic efficiency due to the enhanced interfacial charge transfer. Meanwhile, the carbon layer could synchronously function as the adsorptive active sites during the degradation of organics. Results showed that the Co/CNFs possessed the highest catalytic efficiency under neutral pH, corresponding to the sulfate radical generation. The Co leaching and XPS results showed that the Co served as the main active site in PMS activation.

Insights into the speciation of heavy metals during pyrolysis of industrial sludge.

The purpose of this study was to determine the mechanisms in heavy metals immobilisation during pyrolysis of industrial sludge (IS). Pyrolysis was conducted in a fixed-bed unit at the temperature range between 400 and 800°C. Conventional and advanced analytical techniques were employed to assess the influencing parameters on the transformation of heavy metals during pyrolysis process. The examined heavy metals (i.e. Mn, Ni, Cu, Zn, Cd, and Pb) were effectively immobilised in the char derived at ≤600°C. In contrast, for the char derived at ≥700°C, Mn, Cu, and Zn leaching efficiencies were significantly increased. According to BCR sequential extraction procedure (SEP) results, pyrolysis of IS conducted at ≤600°C transformed heavy metals into stable fractions (i.e. associated with Fe-Mn nodules, and organics and sulphides), while Mn, Cu, and Zn bound in these fractions decomposed into easily soluble forms at higher temperatures. Advanced analytical characterisation (XRD, EDX, XPS, and FTIR) of the derived char and anion concentrations in the leachate have demonstrated that the increase in metal leaching was probably due to the formation of metal halides.

UV direct photolysis of halogenated disinfection byproducts: Experimental study and QSAR modeling.

UV direct photolysis has been used as a promising process to remove halogenated disinfection byproducts (DBPs) generated in water. In this study, experimental studies and modeling approaches were applied to investigate the UV direct photolysis rate constants for 40 kinds of halogenated DBPs. The fluence-based pseudo-first-order rate constants for the removal of halogenated DBPs under UV photolysis spanned more than 2 orders of magnitude, with a range of (0.23-29.84) × 10-4 cm2 mJ-1. DBPs with higher number of halogenated substituents featured higher photolysis rate constants. The degradation efficiencies of DBPs were also affected by the species of halogen substituents, which followed the trend of iodo- > bromo- > chloro- DBPs. A quantitative structure-activity relationship (QSAR) model was established on the basis of the observed degradation rate constant values, which contained a quantum-chemical descriptor (ELUMO-EHOMO) and a molecular descriptor (Eta_C). The calculated parameters of the developed model indicated its good robustness and high reliability. The developed QSAR model can predict the degradation rate constants for DBPs within factors of 1/3 to 3. The model was validated using application domain and visualized in a Williams plot. The selected descriptors for QSAR model can explain the reaction mechanism for UV direct photolysis.

A novel real-time monitoring and control system for waste-to-energy gasification process employing differential temperature profiling of a downdraft gasifier.

A novel, cost-effective and real-time process monitoring and control system was developed to maintain stable operation of waste-to-energy gasification process. It comprised a feedback loop control that utilized the differential temperatures of the oxidation and reduction zones in the gasifier to determine the regional heat-flow (endothermic or exothermic), to assess the availability of oxidizing agent (for instance, air or O2) at the char bed and to calculate the fuel feeding rate. Based on the correlations developed, the air-to-fuel ratio or the equivalence air ratio (ER) for air gasification could be instantaneously adjusted to maintain stable operation of the gasifier. This study demonstrated a simplification of complex reaction dynamics in the gasification process to differential temperature profiling of the gasifier. The monitoring and control system was tested for more than 70 h of continuous operation in a downdraft fixed-bed gasifier with refuse-derived fuel (RDF) prepared from municipal solid wastes (MSW). With the system, fuel feeding rate could be adjusted accurately to stabilize the operating temperature and ER in the gasifier and generate syngas with consistent properties. Significant reductions in the fluctuations of temperature profiles at oxidation and reduction zones (from higher than 100 °C to lower than 50 °C), differential temperatures (from ±200 to ±50 °C) in gasifier and the flow rate (from 16 ±â€¯6.5 to 12 ±â€¯1.8 L/min), composition of main gas components, LHV (from 6.2 ±â€¯3.1 to 5.7 ±â€¯1.6 MJ/Nm3) and tar content (from 8.0 ±â€¯9.7 to 7.5 ±â€¯4.2 g/Nm3) of syngas were demonstrated. The developed gasifier monitoring and control system is adaptable to various types (updraft, downdraft, and fluidized-bed) and scales (lab, pilot, large scale) of gasifiers with different types of fuel.

A comprehensive performance evaluation of heterogeneous Bi2Fe4O9/peroxymonosulfate system for sulfamethoxazole degradation.

In this study, a Bi2Fe4O9 catalyst with nanoplate morphology was fabricated using a facile hydrothermal method. It was used as a catalyst to activate peroxymonosulfate (PMS) for aqueous sulfamethoxazole (SMX) removal. A comprehensive performance evaluation of the Bi2Fe4O9/PMS system was conducted by investigating the effects of pH, PMS dosage, catalyst loading, SMX concentration, temperature, and halides (Cl- and Br-) on the degradation of SMX. The Bi2Fe4O9/PMS system demonstrated a remarkable catalytic activity with >95% SMX removal within 30 min (conditions: pH 3.8, [Bi2Fe4O9] = 0.1 g L-1, [SMX]:[PMS] mol ratio =1:20). It was found that both Cl- and Br- can lead to the formation of PMS-induced reactive halide species (i.e. HClO, HBrO, and Br2) which can also react with SMX forming halogenated SMX byproducts. Based on the detected degradation byproducts, the major SMX degradation pathway in the Bi2Fe4O9/PMS system is proposed. The SMX degradation by Bi2Fe4O9/PMS system in the wastewater secondary effluent (SE) was also investigated. The results showed that SMX degradation rate in the SE was relatively slower than in the deionized water due to (i) reactive radical scavenging by water matrix species found in SE (e.g.: dissolved organic matters (DOCs), etc.), and (ii) partial deactivation of the catalyst by DOCs. Nevertheless, the selectivity of the SO4•- towards SMX degradation was evidenced from the rapid SMX degradation despite the high background DOCs in the SE. At least four times the dosage of PMS is required for SMX degradation in the SE to achieve a similar SMX removal efficiency to that of the deionized water matrix.

Pyrolysis derived char from municipal and industrial sludge: Impact of organic decomposition and inorganic accumulation on the fuel characteristics of char.

A comprehensive study was conducted to evaluate the fuel properties of the char produced from pyrolysis of municipal sludge (MS) and industrial sludge (IS) at different pyrolysis temperatures (500-700 °C). A detailed characterisation of the char was performed to investigate the impact of the decomposition and the accumulation of organic and inorganic compounds during pyrolysis on the fuel properties of the derived char. Increase in pyrolysis temperature increased the fuel ratios especially in the MS-derived char. On the other hand, ash accumulation resulted in decreased higher heating values (HHVs). Dehydration and decarboxylation were the main reactions, which caused the decomposition of the organic compounds in raw sludge during pyrolysis. Thermogravimetric analysis results showed that high temperature pyrolysis could improve the thermal stability of the derived char. The accumulation of catalytic inorganic compounds improved the combustion reactivity of both the IS and MS-derived char. The MS-derived char showed higher slagging and ash fouling indices compared to the IS-derived char despite the lower ash content. However, slagging and ash fouling indices of the char were comparable to that of raw sludge samples. The results indicate that the accumulation and physicochemical transformations of heavy metals during pyrolysis process would not be significantly affected during combustion of the char. For practical application in combustion, the MS-derived char has a greater potential due to considerable HHVs, improved thermal stability, efficient combustion characteristics, lower heavy metals leaching and comparable ash related issues.

Elucidation of stoichiometric efficiency, radical generation and transformation pathway during catalytic oxidation of sulfamethoxazole via peroxymonosulfate activation.

In this work, nano-bimetallic Co/Fe oxides with different stoichiometric Co/Fe ratios were prepared using a novel one-step solution combustion method. The nano-bimetallic Co/Fe oxides were used for sulfamethoxazole (SMX) degradation via peroxymonosulfate (PMS) activation. The stoichiometric efficiencies of the as-prepared nano-bimetallic catalysts were calculated and compared for the first time. The radical generation was identified by electron paramagnetic resonance (EPR) as well as chemical quenching experiments, in which different scavengers were used and compared. The catalytic PMS activation mechanism in the presence of catalyst was examined by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The results showed that besides SO4•- and •OH, •OOH was also detected in the PMS/CoFeO2.5 system. Meanwhile, in addition to the previously proposed radical oxidation pathway, the results showed that SMX degradation also involved a non-radical oxidation, which could be verified by the degradation experiment without catalyst as well as the detection of 1O2. In the PMS activation process, cobalt functioned as the active site on CoFeO2.5 while Fe oxide functioned as the adsorption site. The electron transfer mechanism was proposed based on the XPS and metal leaching results. Additionally, via the detection of transformation products, different SMX transformation pathways involving nitration, hydroxylation and hydrolysis in the PMS/CoFeO2.5 system were proposed.

High-sulfur capacity and regenerable Zn-based sorbents derived from layered double hydroxide for hot coal gas desulfurization.

The Zn-Al mixed metal oxide (ZnAl-MMO) with a plate-like structure was derived from Zn-Al layered double hydroxide. The ZnAl-MMO with a Zn/Al molar ratio of 3:1 exhibits superior absorption ability for H2S in a simulated coal gas at 600 ℃ due to the special structure of the ZnAl-MMO. Besides ZnS, elemental sulfur is also produced during the desulfurization process. The deactivation model could well simulate the absorption behavior of H2S. The sulfidation reaction over the sorbent shows large initial reaction rate constants (1110-5390 m3 min-1 kg-1) and low activation energy (29.5 kJ mol-1). The regeneration rate of the used sorbent can reach 99.8% under the optimum conditions. The regenerated sorbents still show high sulfur capacity (ca. 30%), implying its great application potential for industrial-scale desulfurization of the hot coal gas.

One-step construction of heterostructured metal-organics@Bi2O3 with improved photoinduced charge transfer and enhanced activity in photocatalytic degradation of sulfamethoxazole under solar light irradiation.

A facile one-step assembly method was developed for the preparation of metal-organics @Bi2O3 composites for photocatalysis. Two kinds of metal-organics (Ti-bdc and Cu-btc)@Bi2O3 composites were synthesized via the coordination of btc3-/bdc2- and metal ions (Ti4+/Cu2+) as well as OH on the surface of Bi2O3. Compared with pure Bi2O3, Ti-bdc@Bi2O3 shows a 1.7 times higher photocatalytic activity in the degradation of sulfamethoxazole (SMX) under a simulated solar irradiation with a cumulative removal of 62% within 60 min. The high photocatalytic activity could be attributed to the high charge separation, enhanced electron transfer as well as the low recombination rate of photo-generated electrons and holes due to the construction of hetero-structures. The stability test showed that Ti-bdc@Bi2O3 is more stable in water than Cu-btc@Bi2O3. Furthermore, through the radical-trapping experiments and main intermediates detection, it is demonstrated that the photo-generated holes as well as the OH and O2- formed dominate the photocatalytic decomposition of SMX. These findings demonstrate the potential usage of a facile method to synthesize metal-organics and metal oxides composites, some of which possess high water stability and thus could be employed for water treatment.

Controllable mullite bismuth ferrite micro/nanostructures with multifarious catalytic activities for switchable/hybrid catalytic degradation processes.

In this work, controllable preparation of micro/nanostructured bismuth ferrites (BFOs) were used to investigate multifarious heterogeneous catalyses, including Fenton/Fenton-like reaction, photocatalysis, photo-Fenton oxidation, and peroxymonosulfate (PMS) activation. Results showed that BFO can be used asa novel catalyst to activate switchable catalytic degradation of organic matters. Additionally, a novel catalytic system for degradation of organic pollutants, which integrating all-above heterogeneous catalyses is denoted as BFO/H2O2/PMS hybrid reaction, is introduced for the first time. BFO/H2O2/PMS system effectively degraded>99% for both methyl orange (MO) and sulfamethoxazole (SMX) within 60min, which shows better efficiency than above BFO-driven catalyses. The major SMX degradation pathway in BFO/H2O2/PMS system is proposed via detecting intermediates using LC/MS/MS. It was found that catalytic activities of BFOs are in the order of BFO-L (co-precipitation, micro/nanosize, single crystals exposing facet (001))>BFO-H (hydrothermal, nanocluster with a higher surface area than other BFOs)>BFO-C (fabricated using calcination process, microsize), which demonstrated that crystallographic orientation is more significant in heterogeneous catalyses than specific surface area at micro/nanoscale. Besides, the required H2O2 consumption for achieving 99% TOC removal was identified in BFO-driven photo-Fenton oxidation. The other effects on degradation efficiency, such as H2O2 dosage and pH, were investigated as well. In Fenton/Fenton-like reaction, reaction conditions suggested are ∼61.5mM H2O2 dosage and pH≥4.5 to avoid quenching of HO into HO2 by excessive H2O2 and Fe leaching.

Acetic acid-assisted fabrication of hierarchical flower-like Bi2O3 for photocatalytic degradation of sulfamethoxazole and rhodamine B under solar irradiation.

With the assistance of acetic acid (CH3COOH), a novel 3D flower-like Bi2O3 was synthesized via hydrothermal process followed by calcination. For the first time, the role of CH3COOH as a capping agent in the formation of flower-like structure was investigated. The as-prepared flower-like Bi2O3 had a high activity on the degradation of sulfamethoxazole (SMX) under simulated solar light irradiation due to the narrow band gap of 2.69eV, high percentage of ß-Bi2O3 as well as high intensity of polar facets (120) and (200). Meanwhile, the photocatalytic degradation followed apparent pseudo-first-order kinetics. The rate constant (k) increased from 0.7×10-2 to 3.0×10-2min-1 with the catalyst loading varying from 0.5 to 2.0gL-1. Increasing pH values from 3 to 11 led to the decrease of k from 2.2×10-2 to 0.2×10-2min-1, which could be attributed to the electrostatic adsorption between SMX molecules and Bi2O3. The radical quenching experiments showed both direct (h+) and indirect oxidation (OH and O2-) happened in this process.