α‐FeOOH−MoO3 Nanorod for Effective Photo‐Fenton Degradation of Dyes and Antibiotics at a Wide Range of pH

It's highly significant to develop a novel catalyst, which can be active at a wide range of pH, for an effective photo‐Fenton reaction. In this work, α‐FeOOH?MoO₃ nanorod was prepared by a one‐step hydrothermal method and applied in photo‐Fenton degradation of organic pollutants. Benefit from the electron migration mechanism of Z‐scheme and excellent photoelectric performance, the catalyst exhibited superior photo‐Fenton activity in degradation of organic pollutants. In addition, the catalyst holds good stability after 5 recycles. These results demonstrated that this catalyst has wide application prospect in organic wastewater treatment.     

Heterogeneous Fenton Degradation of Organic Pollutants in Water Enhanced by Combining Iron-type Layered Double Hydroxide and Sulfate

Water pollution derived from organic pollutants is one of the global environmental problems. The Fenton reaction using Fe²⁺ as a homogeneous catalyst has been known as one of clean methods for oxidative degradation of organic pollutants. Here, a layered double hydroxide (Fe²⁺Al³⁺-LDH) containing Fe²⁺ and Al³⁺ in the structure was used to develop a “heterogeneous” Fenton catalyst capable of mineralizing organic pollutants. We found that sulfate ion (SO₄²⁻) immobilized on the Fe²⁺Al³⁺-LDH significantly facilitated oxidative degradation (mineralization) of phenol as a model compound of water pollutants to carbon dioxide (CO₂) in a heterogeneous Fenton process. The phenol conversion and mineralization efficiency to CO₂ reached >99% and ca. 50%, respectively, even with a reaction time of only 60 min.     

Investigation of photocatalytic mineralisation of Acridine Yellow G dye by BaCrO4 in the presence of eco-friendly LEDs irradiation

Degradation of toxic organic pollutants and dyes from industrial wastewater by photocatalysis is an environmentally friendly technique. The degradation of Acridine Yellow G (AYG) was investigated in aqueous solutions employing BaCrO₄ as a heterogeneous photocatalyst under eco-friendly LED irradiation. We studied the mineralisation kinetics of AYG by monitoring the dye concentration and chemical oxygen demand (COD) as a function of time. The impact of pH, concentrationdye, reactants, catalyst, Fenton reagent, salt effect, and temperature on the kinetics were investigated. The initial addition of optimal amounts of hydrogen peroxide and potassium persulfate increased the degradation rate, while NaCl and Na₂CO₃ retarded the reaction. The efficiency of visible light, LED (12 ?W) irradiation, compared with the traditional visible light source, the halogen lamp (500 ?W). At the optimum pH 10, the AYG degradation obeyed pseudo-first-order kinetics. With BaCrO₄ asa heterogeneous photocatalyst, complete mineralisation of AYG was achieved in 35 ?min. This process is green, eco-friendly, and the catalyst is easily recoverable and reusable five times without loss of catalytic efficiency.     

Engineering FeS2 nanoparticles on tubular g-C3N4 for photo-Fenton treatment of paint wastewater

An efficient photo-Fenton catalyst （Fe S₂@HTCN） was designed by maximizing the synergistic effect of Fe S₂nanoparticles and hollow tubular g-C₃N₄（HTCN）.Molecule self-assembly and molten salts-assisted calcination were used to engineering the hollow structured g-C₃N₄before anchoring Fe S₂nanoparticles on the walls of HTCN via reflux method.Compared to bulk g-C₃N₄,the unique structure of HTCN and het...     

CoFe2O4 with MoS2-xOy Nanosheets as a Co-catalyst for Enhanced Activation of Peroxydisulfate in Advanced Oxidation Processes

The application of advanced oxidation processes (AOPs) based on sulfate radicals for degrading persistent organic pollutants faces challenges due to the inefficient activation of peroxydisulfate (PDS) oxidant. Herein, a composite CoFe₂O₄/MoS_2-xO_y (CFM) catalyst consisting of CoFe₂O₄ nanoparticles uniformly dispersed on the nanosheets of oxygen-incorporated MoS₂ (MoS_2-xO_y) with flower-like morphology are fabricated through a facile two-step hydrothermal method, which results in the enhanced activation of PDS and a highly efficient degradation of phenolic pollutants. The oxygen-doping in MoS_2-xO_y leads to unsaturated sulfur and active sites on the surface of MoS₂ for accelerating the rate limiting step of Fe^III/Fe^II reduction cycle in PDS-CFM reaction. Aiming at the refractory organic pollutants in actual coking wastewater, CFM co-catalyst is introduced into a hydrogel made up of polyvinyl alcohol (PVA) and coal-tar pitch oxides (PO) to construct a multifunctional CFM@PO/PVA hydrogel. Upon hybrid CFM@PO/PVA, the coupling of the enhanced AOP with solar-driven interfacial vapor generation (SIVG) technology contributes to the degradation efficiency, the removal rate of phenol in solution and the total organic carbon in coking wastewater can reach 98 % and 91 %, respectively. The integration of heterogeneous AOPs with SIVG system provides a feasible strategy for the eco-friendly efficient purification of industrial wastewater.     

Efficient removal of tetracycline by H2O2 activated with iron-doped biochar: Performance,mechanism, and degradation pathways

In this study,novel iron-doped biochar（Fe-BC） was produced using a simple method,and it was used as an H₂ O₂ activator for tetracycline（TC） degradation.Generally,iron loading can improve the separation performance and reactivity of biochar（BC）.In the Fe-BC/H₂ O₂ system,92% of the TC was removed within 30 min with the apparent rate constant(k_obs) of 0.155 min^-1,which was 23.85 times that in the case of the BC/H₂ O_2<...     

Atomic Layer Deposition of Iron Sulfide and Its Application as a Catalyst in the Hydrogenation of Azobenzenes

The atomic layer deposition (ALD) of iron sulfide (FeS_x ) is reported for the first time. The deposition process employs bis(N ,N′ ‐di‐tert‐butylacetamidinato)iron(II) and H₂S as the reactants and produces fairly pure, smooth, and well‐crystallized FeS_x thin films following an ideal self‐limiting ALD growth behavior. The FeS_x films can be uniformly and conformally deposited into deep narrow trenches with aspect ratios as high as 10:1, which highlights the broad applicability of this ALD process for engineering the surface of complex 3D nanostructures in general. Highly uniform nanoscale FeS_x coatings on porous γ‐Al₂O₃ powder were also prepared. This compound shows excellent catalytic activity and selectivity in the hydrogenation of azo compounds under mild reaction conditions, demonstrating the promise of ALD FeS_x as a catalyst for organic reactions.     

Susceptibility of FeS2 hydrogen evolution performance to sulfide poisoning

The imminent depletion of fossil fuels raises concern over the need for next-generation clean energy. Of numerous alternatives, electrochemical water splitting is a promising method to store energy in the form of hydrogen. In order to benefit from this system, technological advancement in the development of affordable and efficient electrocatalysts for hydrogen evolution reaction is necessary. Transition-metal electrocatalysts composing of earth-abundant elements, specifically natural FeS₂, has demonstrated excellent performance for hydrogen evolution reaction. However, previous studies on platinum surfaces highlighted the detrimental effect toward hydrogen evolution performance upon poisoning of the active sites. In this work, we examine the susceptibility of natural FeS₂ toward sulfide poisoning. Our findings showed that the degradation effect from the introduction of sulfide to natural FeS₂ was not as severe as that observed on platinum. The overpotential (at a current density of 10 mA/cm²) for natural FeS₂ and platinum increased by approximately 20 and 110 mV, respectively.     

Mechanochemical Immobilisation of Metathesis Catalysts in a Metal–Organic Framework

A simple, one‐step mechanochemical procedure for immobilisation of homogeneous metathesis catalysts in metal–organic frameworks was developed. Grinding MIL‐101‐NH₂(Al) with a Hoveyda–Grubbs second‐generation catalyst resulted in a heterogeneous catalyst that is active for metathesis and one of the most stable immobilised metathesis catalysts. During the mechanochemical immobilisation the MIL‐101‐NH₂(Al) structure was partially converted to MIL‐53‐NH₂(Al). The Hoveyda–Grubbs catalyst entrapped in MIL‐101‐NH₂(Al) is responsible for the observed catalytic activity. The developed synthetic procedure was also successful for the immobilisation of a Zhan catalyst.     

Synthesis and catalytic study of open metal site metal–organic frameworks of Cu3(BTC)2 microbelts in selective organic sulfide oxidation

The synthesis of open metal site metal–organic frameworks of Cu₃(BTC)₂ with microbelt morphology and a study of the catalytic oxidation of organic sulfides are reported. This CuBTC was found to be an efficient, selective and waste‐free green heterogeneous co‐catalyst for the green H₂O₂ catalytic oxidation of sulfides. The catalyst can be isolated from the reaction mixture and reused at least five times. Copyright © 2016 John Wiley & Sons, Ltd.     

Highly dispersed Mn2O3−Co3O4 nanostructures on carbon matrix as heterogeneous Fenton-like catalyst

This work reports the synthesis of various carbon (Vulcan XC-72 R) supported metal oxide nanostructures, such as Mn₂O₃, Co₃O₄ and Mn₂O₃−Co₃O₄ as heterogeneous Fenton-like catalysts for the degradation of organic dye pollutants, namely Rhodamine B (RB) and Congo Red (CR) in wastewater. The activity results showed that the bimetallic Mn₂O₃−Co₃O₄/C catalyst exhibits much higher activity than the monometallic Mn₂O₃/C and Co₃O₄/C catalysts for the degradation of both RB and CR pollutants, due to the synergistic properties induced by the Mn−Co and/or Mn (Co)−support interactions. The degradation efficiency of RB and CR was considerably increased with an increase of reaction temperature from 25 to 45°C. Importantly, the bimetallic Mn₂O₃−Co₃O₄/C catalyst could maintain its catalytic activity up to five successive cycles, revealing its catalytic durability for wastewater purification. The structure–activity correlations demonstrated a probable mechanism for the degradation of organic dye pollutants in wastewater, involving •OH radical as well as Mn²⁺/Mn³⁺ or Co²⁺/Co³⁺ redox couple of the Mn₂O₃−Co₃O₄/C catalyst.     

A Pyridinium-Pyridinium Zinc(II) Porphyrin Ion Porous Organic Polymer as Efficient Heterogeneous Catalyst for Cycloaddition of Epoxides with CO2

A zinc(II)porphyrin-based ion porous organic polymer (ZnTPyPBr₄-iPOP) is successfully synthesized from newly designed pyridinium-functionalized cationic Zn-porphyrin monomer (ZnTPyPBr₄) by free radical self-polymerization, and is employed as an efficient bifunctional heterogeneous catalyst for CO₂ cycloaddition reaction with epoxides. The ZnTPyPBr₄-iPOP exhibits excellent catalytic performance and good substrate expansion in CO₂ cycloaddition reaction under solvent-free and cocatalyst-free conditions with a TOF as high as 15,500 h⁻¹ for the cycloaddition of CO₂ and epichlorohydrin. The synergistic effect of zinc(II)porphyrin as the Lewis acidic site and the Br⁻ anion as the nucleophile in ZnTPyPBr₄-iPOP responds to the high catalytic activity. Moreover, ZnTPyPBr₄-iPOP can easily be recovered and reused at least seven times without the loss of activity. This work provides a valuable approach for the synthesis of novel and efficient heterogeneous catalyst for CO₂ cycloaddition.     

COD reduction of waste water streams of active pharmaceutical ingredient – Atenolol manufacturing unit by advanced oxidation-Fenton process

Active pharmaceutical intermediates (API) in waste waters have adverse effects on aquatic life and environment. The API have high COD value and low BOD₃ and hence difficult to treat biologically. In this study, advanced oxidation processes (AOPs) utilizing the H₂O₂/Fe⁺², Fenton reactions were investigated in lab-scale experiments for the degradation of Atenolol containing waste water streams. The experimental results showed that the Fenton process using H₂O₂/Fe⁺² was the most effective treatment process. With Fenton processes, COD reduction of wastewater can be achieved successfully. It is suggested that Fenton processes are viable techniques for the degradation of Atenolol from the waste water stream with relatively low toxic by-products in the effluent which can be easily biodegraded in the activated sludge process. Hence, the Fenton process with H₂O₂/Fe⁺² is considered a suitable pretreatment method to degrade the active pharmaceutical molecules and to improve the biodegradability of waste water.     

Towards a Practical Development of Light‐Driven Acceptorless Alkane Dehydrogenation

The efficient catalytic dehydrogenation of alkanes to olefins is one of the most investigated reactions in organic synthesis. In the coming years, an increased supply of shorter‐chain alkanes from natural and shale gas will offer new opportunities for inexpensive carbon feedstock through such dehydrogenation processes. Existing methods for alkane dehydrogenation using heterogeneous catalysts require harsh reaction conditions and have a lack of selectivity, whereas homogeneous catalysis methods result in significant waste generation. A strong need exists for atom‐efficient alkane dehydrogenations on a useful scale. Herein, we have developed improved acceptorless catalytic systems under optimal light transmittance conditions using trans‐[Rh(PMe₃)₂(CO)Cl] as the catalyst with different additives. Unprecedented catalyst turnover numbers are obtained for the dehydrogenation of cyclic and linear (from C₄) alkanes and liquid organic hydrogen carriers. These reactions proceed with unique conversion, thereby providing a basis for practical alkane dehydrogenations.     

CuFe2O4@GO nanocomposite as an effective and recoverable catalyst of peroxymonosulfate activation for degradation of aqueous dye pollutants

Recently, heterogeneous activation of peroxymonosulfate (PMS) to oxidatively degrade organic pollutants has been a hotspot. In the present work, copper ferrite-graphite oxide hybrid (CuFe₂O₄@GO) was prepared and used as catalyst to activate PMS for degradation of methylene blue (MB) in aqueous solution. A high degradation efficiency (93.3%) was achieved at the experimental conditions of 20 mg/L MB, 200 mg/L CuFe₂O₄@GO, 0.8 mmol/L PMS, and 25 °C temperature. Moreover, CuFe₂O₄@GO showed an excellent reusability and stability. The effects of various operational parameters including pollutant type, solution pH, catalyst dosage, PMS dosage, pollutant concentration, temperature, natural organic matter (NOM), and inorganic anions on the catalytic degradation process were comprehensively investigated and elucidated. The further mechanistic study revealed the Cu(II)/Cu(I) redox couple on CuFe₂O₄@GO played the dominant role in PMS activation, where both hydroxyl and sulfate radicals were generated and proceeded the degradation of pollutants. In general, CuFe₂O₄@GO is a promising heterocatalyst for PMS-based advanced oxidation processes (AOPs) in wastewater treatment.     

Fe-Mn-Cu-Ce/Al2O3 as an efficient catalyst for catalytic ozonation of bio-treated coking wastewater: Characteristics,efficiency, and mechanism

It is important to develop a catalyst that has high catalytic activity and can improve the degradation efficiency of refractory organic pollutants in the catalytic ozonation process. In this study, Fe-Mn-Cu-Ce/Al₂O₃ was synthesised via impregnation calcination for catalytic ozonation of bio-treated coking wastewater. The physical and chemical characteristics of the catalysts were analysed using X-ray diffraction (XRD), X-ray fluorescence spectrometry (XRF), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and Brunauer–Emmett–Teller nitrogen adsorption–desorption methods. The effects of catalyst dosage, pH, and reflux ratio on the degradation efficiency of wastewater were examined in laboratory-scale experiments. The chemical oxygen demand (COD) removal rate of bio-treated coking wastewater was estimated to be 52.76 % under optimal conditions. The experiments on the catalytic mechanism demonstrated that the surface hydroxyl formed by the Lewis acid sites on the surface of the catalyst can react with ozone as the active site forming the active oxygen (·OH, ·O₂^–, and ¹O₂), thereby efficiently degrading the organic pollutants in coking wastewater. Furthermore, a pilot-scale experiment on the catalytic ozonation of bio-treated coking wastewater was carried out using an Fe-Mn-Cu-Ce/Al₂O₃ catalyst, while the effects of the initial pollutant concentration, ozone concentration, and gas flow on the COD removal rate were studied on a pilot scale. It was found that the COD removal rate of the wastewater was ～ 60 % under optimal parameters. After the treatment, the wastewater steadily reached the coking wastewater discharge standard (COD < 80 mg/L), while the operating cost of catalytic ozonation reached ～ 0.032$/m³, thereby paving the way toward economic engineering applications. The COD degradation kinetics in the bio-treated coking wastewater followed pseudo-second-order kinetics. Three-dimensional fluorescence and gas chromatography–mass spectrometry revealed that macromolecular organic pollutants in the bio-treated coking wastewater were greatly degraded. In summary, Fe-Mn-Cu-Ce/Al₂O₃ exhibited good reusability, high catalytic activity, and low cost and has a wide application prospect in the treatment of coking wastewater.     

非均相Fenton催化剂的组成结构设计与性能优化

非均相Fenton催化技术解决了均相Fenton反应存在的问题,具有pH适用范围广以及催化剂易于回收利用等优点,因而成为水处理领域的研究热点。本文首先介绍了非均相Fenton反应用于降解有机污染物的发展、反应机理以及机理的研究方法。总结了非均相Fenton催化剂的种类,主要包括铁氧化物、其它金属氧化物、金属有机框架材料。重点讨论了提高非均相Fenton催化剂活性及稳定性的方法,包括通过调控催化剂的形貌、尺寸、孔结构使催化剂具有更高的比表面积,将活性组分负载在具有高比表面积的载体上,通过与其它金属复合以及引入光、超声、微波等外场。最后,对非均相Fenton催化技术的发展进行了展望。     

Heterogeneous Fenton-like reactions with a novel hybrid Cu–Mn–O catalyst for the degradation of benzophenone-3 in aqueous media

This study focuses on the heterogeneous Fenton-like reaction performed over a novel hybrid Cu–Mn–O catalyst for the degradation of a model compound benzophenone-3 (BP-3) in aqueous media. The hybrid Cu–Mn–O catalysts with different Cu/Mn molar ratios were synthesized using co-precipitation and hydrothermal methods, and their composition and morphology were characterized using XRD and SEM analyses. Key parameters including the Cu/Mn ratio in the synthesis, pH and titration of H₂O₂ were shown to significantly influence the degradation of BP-3. A hybrid catalyst with a chemical composition of Cu_1.4Mn_1.6O₄, Mn₃O₄, and Mn₂O₃ exhibiting a morphology of nanofibers and nanoparticles demonstrated the highest catalytic activity in the degradation of BP-3. After 240 min of degradation, 81.5% of BP-3 was removed, which could be mostly related to the presence of hydroxyl radicals (˙OH). Unlike the conventional Fenton reaction that performs well under highly acidic conditions, BP-3 can be degraded in a wider pH range (2.6–7.1) in the Fenton-like reaction presented herein. Considering the mild conditions used for this Fenton-like system, this novel hybrid catalyst remains promising for wastewater treatment.     

Combustion synthesis of mesoporous CoAl2O4 for peroxymonosulfate activation to degrade organic pollutants

A mesoporous cobalt aluminate (CoAl₂O₄) spinel is synthesized through a combustion method and adopted for the activation of peroxymonosulfate (PMS) to degrade organic pollutants. Multiple characterization procedures are conducted to investigate the morphology and physicochemical properties of the CoAl₂O₄ spinel. Due to its mesoporous structure, large surface area, and high electrical conductivity, the obtained CoAl₂O₄ exhibits remarkable catalytic activity for Rhodamine B (RhB) degradation. Its RhB degradation rate is 89.0 and 10.5 times greater than those of Co₃O₄ and CoAl₂O₄ spinel prepared by a precipitation method, respectively. Moreover, the mesoporous CoAl₂O₄ spinel demonstrates a broad operating pH range and excellent recyclability. The influence of several parameters (catalyst amount, PMS concentration, initial pH, and coexisting inorganic anions) on the oxidation of RhB is evaluated. Through quenching tests and electron paramagnetic resonance experiments, sulfate radicals are identified as the predominant reactive species in RhB degradation. This paper provides new insights for the development of efficient, stable, and reusable cobalt-based heterogeneous catalysts and promotes the application of persulfate activation technology for the treatment of refractory organic wastewater.     

Fe3O4 as a magnetically reusable Fenton nanocatalyst for the oxidation of thiols to sulfonic acid and sulfides to sulfoxides and sulfones

In this study, the oxidation of thiols to sulfonic acids and sulfides to sulfoxides and sulfones was carried out in the presence of Fe₃O₄/H₂O₂ as an efficient heterogeneous Fenton system. The products were obtained in good to excellent yields and short reaction times. Further results showed that the heterogeneous catalyst could be recovered easily using an external magnetic field and reused several times without any loss of its catalytic activity.