Heterogeneous Catalytic Oxidation Research Articles

Heterogeneous catalytic aerobic oxidation of primary amines to amides using unsupported nanoporous palladium catalyst

An efficient and highly selective heterogeneous catalyst system for aerobic oxidation of primary amines was developed using unsupported palladium nanopores (PdNPore). A variety of aromatic, aliphatic, and heterocyclic primary amines were oxidized to the corresponding amides in satisfactory to excellent yields using ambient air as an oxidant. No palladium was leached from PdNPore during the oxidation reaction. The catalyst could be readily recovered and reused without a decrease in catalytic activity. The kinetic studies and control experiments demonstrated that nitrile acts as an intermediate, which undergo hydration to afford amide as the final product.

Visible-light-driven photocatalytic degradation of ibuprofen by Cu-doped tubular C3N4: Mechanisms, degradation pathway and DFT calculation

The copper-modified tubular carbon nitride (CTCN) with higher specific surface area and pore volume was prepared by a simple in-situ hydrolysis and self-assembly. Increased ∼4.7-fold and ∼2.3-fold degradation rate for a representative refractory water pollutant (Ibuprofen, IBP) were achieved with low-energy light source (LED, 420 ± 10 nm), as compared to graphitic carbon nitride (GCN) and tubular carbon nitride (TCN), respectively. The high efficiency of IBP removal was supported by narrow band gap (2.15 eV), high photocurrent intensity (1.10 μA/cm2) and the high surface -OH group (14.75 μg/cm3) of CTCN. According to analysis of the various reactive species in the degradation, the superoxide radical (•O2−) played a dominant role, followed by •OH and h+, responsible for IBP degradation. Furthermore, Fukui functions were employed to predict the active sites of IBP, and combined with the HPLC-MS/MS results, possible mechanisms and pathways for photocatalytic degradation were indicated. This study will lay an important scientific foundation and a possible new approach for the treatment of emerging aromatic organic pollutants in visible-light-driven heterogeneous catalytic oxidation environment.

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Triphenylamine and its derivatives (TPAs) are promising for the photocatalytic oxidative coupling of thiols to disulfides, but suffer from the easy polymerization and difficult separation. In this paper, by immobilizing the TPAs into MOF with photoredox inert Sr nodes, the photo‐generated electrons were successfully controlled to transfer from the excited TPAs to O2, and finally realize the heterogeneous catalytic oxidation of thiols to disulfides. More details are discussed in the article by Zhang et al. on page 1093—1099.image

Insight into the role of reactive species on catalyst surface underlying peroxymonosulfate activation by P–Fe2MnO4 loaded on bentonite for trichloroethylene degradation

In this study, bentonite supporting phosphorus-doped Fe2MnO4 (BPF) was synthesized and applied for PMS activation to degrade TCE. Morphology and structure characterization results indicated the successfully synthesized of BPF, and the BPF/PMS system not only featured high TCE removal (97.4%) but also high reaction rate constant (kobs = 0.0554 min−1) and PMS utilization (70.4%, kobs = 0.0228 min−1). According to the results of various experiments, massive oxygen vacancies on P–Fe2MnO4 alter its charge balance and facilitate the electron transfer process named adjacent transfer (direct electron capture by adsorbed PMS from adjacent TCE). Mn(III) is the main adsorption site for PMS, and the hydroxyl groups on the catalyst (Fe sites of P–Fe2MnO4, Si and Al sites of bentonite) can also offer binding sites for PMS. The hydrogen-bonded PMS on Fe(III) and Mn(III) sites will subsequently accept the discharged electrons to generate free radicals and high-valent metal species. Meanwhile, electron loss of HSO5− that chemically bonded to hydroxyl groups on bentonite will generate SO5•−, which will further produce 1O2 through self-bonding. the active species on the catalyst surface contribute 65% of TCE degradation in the heterogeneous catalytic oxidation system.

Activation energy of heterogeneous catalytic oxidation of methanol in oscillatory regime

Activation energy of heterogeneous catalytic oxidation of methanol in oscillatory regime

Research into arsenic (III) effective catalytic oxidation in an aqueous solution on a new active manganese dioxide in a flow column

Groundwater in many places on Earth contains arsenic compounds. Arsenic (III) compounds must be oxidised to purify water containing arsenic effectively. The subject of this study is oxidation of arsenic (III) compounds in an aqueous solution. Today’s most common industrial arsenic oxidation method using aggressive oxidising agents such as chlorine or ozone has a number of serious disadvantages. The most problematic of these include extremely high risks to human health and the environment, the cost and overall complexity of the process. Catalytic oxidation of arsenic (III) compounds using atmospheric oxygen is an alternative free from the above disadvantages, yet, to date, no information about effective catalysts for this process has been presented in the literature. The arsenic (III) catalytic oxidation process is studied in an aqueous solution on a new active manganese dioxide (NAMD) synthesised by the author. A comparative experimental analysis is performed with other known modifications of manganese dioxide. It is shown that the new active manganese dioxide (NAMD) has high catalytic activity towards arsenic (III), this being confirmed experimentally in both a limited volume and a flow column mode. Some theoretical aspects of the mechanism for catalytic oxidation of arsenic (III) with oxygen on active manganese dioxide in an aqueous solution are also discussed on the basis of the research results. Experimental work is required at pilot plants in the field for successful industrial implementation of the technology for catalytic oxidation of arsenic (III) compounds on NAMD. Further laboratory research is necessary for developing a detailed theoretical basis for catalytic oxidation of arsenic in aqueous solutions. The results of this research are of interest to industrial companies specialising in removing arsenic compounds from water, to scientists and researchers studying catalytic oxidation of arsenic (III), as well as heterogeneous catalytic oxidation with oxygen in general.

A Water-Stable Boronate Ester Cage.

The reversible condensation of catechols and boronic acids to boronate esters is a paradigm reaction in dynamic covalent chemistry. However, facile backward hydrolysis is detrimental for stability and has so far prevented applications for boronate-based materials. Here, we introduce cubic boronate ester cages 6 derived from hexahydroxy tribenzotriquinacenes and phenylene diboronic acids with ortho-t-butyl substituents. Due to steric shielding, dynamic exchange at the Lewis acidic boron sites is feasible only under acid or base catalysis but fully prevented at neutral conditions. For the first time, boronate ester cages 6 tolerate substantial amounts of water or alcohols both in solution and solid state. The unprecedented applicability of these materials under ambient and aqueous conditions is showcased by efficient encapsulation and on-demand release of β-carotene dyes and heterogeneous water oxidation catalysis after the encapsulation of ruthenium catalysts.

Role of the In-Situ-Formed Surface (Pt-S-O)-Ti Active Structure in SO2-Promoted C3H8 Combustion over a Pt/TiO2 Catalyst.

Typically, SO2 unavoidably deactivates catalysts in most heterogeneous catalytic oxidations. However, for Pt-based catalysts, SO2 exhibits an extraordinary boosting effect in propane catalytic oxidation, but the promotive mechanism remains contentious. In this study, an in situ-formed tactful (Pt-S-O)-Ti structure was concluded to be a key factor for Pt/TiO2 catalysts with a substantial SO2 tolerance ability. The experiments and theoretical calculations confirm that the high degree of hybridization and orbital coupling between Pt 5d and S 3p orbitals enable more charge transfer from Pt to S species, thus forming the (Pt-S-O)-Ti structure with the oxygen atom dissociated from the chemisorbed O2 adsorbed on oxygen vacancies. The active oxygen atom in the (Pt-S-O)-Ti active structure is a robust site for C3H8 adsorption, leading to a better C3H8 combustion performance. This work can provide insights into the rational design of chemical bonds for high SO2 tolerance catalysts, thereby improving economic and environmental benefits.

Regulating the Flexibility to Assemble Porous Single-Atom Fe-Coordinated Metallopolymers for Efficient Heterogeneous Catalytic Oxidations.

Metallopolymers as organic-inorganic hybrid materials formulated by metal embedding organic polymers show great potential for novel heterogeneous catalysis, in terms of the facile structural design and tunability. Herein, the disadvantage of nonporous stacking of one-dimensional (1D) structures has been suppressed by chain modulation of the 1D metallopolymers, allowing for the convenient construction of porous assemblies with single-atom dispersion and accessible active sites. By postmodification, the Fe/CM-1 catalyst readily synthesized by coordinating the Fe(II) to the twisted chain of 1D Schiff-base polymer possesses expedient flexibility, showing the highest porosity, remarkable heterogeneous recyclability, and thus prominent catalytic activity for the selective oxidation of benzylamine and alcohols. Moreover, control experiments supported by computational studies demonstrated that the unique pincer structure of Fe/CM-1 effectively maintains the valence state of the anchored single-atom iron, facilitating single-electron transfer and promoting efficient iron redox cycling during the catalytic process. Notably, these 1D metallopolymers have the advantage of cost-effectiveness, easy preparation in gram-scale, and utilization in continuous reaction, providing inspirations for facile synthesis of efficient heterogeneous catalysts from the well-developed 1D metallopolymers.

Theory-guided unraveling of the mechanism underlying Cu1.0/Mn1.0-ZnO with dual reaction centers for enhanced peroxymonosulfate activation

Developing efficient catalytic systems for water contamination removal is a topic of great interest. However, the use of heterogeneous catalysts faces challenges due to insufficient active sites and electron cycling. In this study, results from first-principles calculations demonstrate that dual reaction centers (DRCs) are produced around the Cu and Mn sites in Cu1.0/Mn1.0-ZnO due to the electronegativity difference. Experimental results reveal the material with DRCs greatly enhances electron transfer efficiency and significantly impacts the oxidation and reduction of peroxymonosulfate (PMS). In addition, the self-consistent potential correction (SCPC) method was introduced to correct the energy and charge of charged periodic systems simulating a catalytic process, resulting in more precise catalytic results. Specifically, the material exhibits a preference for adsorbing negatively charged PMS anions at electron-deficient Mn sites, facilitating PMS oxidation for the generation of 1O2, and PMS reduction around the electron-rich Cu for the formation of •OH and SO4•−. The major reactive oxygen species is 1O2, showcasing effective performance in various degradation systems. Overall, our work provides novel insights into the persulfate-based heterogeneous catalytic oxidation process, paving the way for the development of high-performance catalytic systems for water purification.

Ce-doped CuCoO2 delafossite with switchable PMS activation pathway for tetracycline degradation

Heterogeneous Fenton-like catalytic oxidation has exhibited great potential in eliminating recalcitrant organic pollutants. Nevertheless, a precise modulation of intrinsic catalytic pathways (radical or nonradical) remains challenging. Herein, Ce-doped CuCoO2 hexagonal nanosheets (CCCO-x) were designed via a facile coprecipitation method toward peroxymonosulfate activation. The doped Ce optimized the interaction between CCCO-x and PMS and enhanced the interfacial electron transfer ability, tunning the catalytic pathway from radical role (57.4%) to nonradical role (69.2%). More than 96% of tetracycline (TC) could be degraded after Ce doping, accompanied by a first-order kinetic constant that is 2.5 times higher than that of pristine CuCoO2. Meanwhile, the introduction of Ce(III) not only significantly enlarged the specific surface area of the catalyst, but also effectively enhanced the synergistic effect of Co(III) and Cu(I) sites, which further accelerated the PMS decomposition. Besides, synergy of radical-nonradical mixed pathways (SO4•−, •OH, 1O2, and electron transfer pathway) for TC removal was verified by electron paramagnetic resonance (EPR) spectra, quenching tests, and electrochemical measurements. The degradation intermediates and possible degradation pathway of TC were also proposed. This work provides new insights and routes to modulate catalytic pathway in Fenton-like oxidation, especially broadening the application potential of delafossite-based (ABO2) catalysts in water treatment.

Heterogeneous catalytic oxidation of furfural with hydrogen peroxide over a niobia catalyst

Oxidation of furfural was conducted using niobia as a heterogeneous catalyst, which displayed an unconventional behavior, giving 2,3-dihydroxybutanedioic acid (tartaric acid) as the main oxidation product.

Effect of log Kow on the degradation of pharmaceutically active compounds in a heterogeneous catalytic persulfate activation system

In heterogeneous catalytic advanced oxidation processes (HC-AOP), enhancing the reaction rate is the biggest challenge. To enhance the reaction rate, it is necessary to increase the mass transfer rate of reactants toward the catalyst surface and the number of active sites that will provide better contact with the reactants and higher mass transfer. The hydrophobicity of the reactant is an important parameter that affects the transport of molecules toward solid surfaces. In this study, the effect of log Kow, an indicator of hydrophobicity, on enhancing the catalytic activity in persulfate (PS) activation for pharmaceutic compounds (PCs) degradation was investigated. For this purpose, some PCs with different log Kow were selected and their adsorption and degradation behaviors were investigated depending on the PS concentration, catalyst dosage, contact time, pH, and temperature in HC-AOP. Adsorption percentages increased significantly with increasing log Kow value. PCs with higher log Kow were completely degraded at the end of the shorter contact times in the presence of lower catalyst and PS. PCs were significantly degraded by the triple catalytic effect of AC, Fe, and temperature. The pseudo-first-order kinetic model was the best fit for the degradation reaction for all PCs. The higher apparent rate constants and lower activation energy values of the PCs belonging to high log Kow confirmed that log Kow is an effective parameter in enhancing the catalytic activity.

Rapid oxidation and deep As(III) purification from water using gelatin-supported iron-based metal-organic framework aerogel coupled with H2O2: Preparation, performance and mechanism

Metal-organic frameworks (MOFs) are considered a reliable adsorbent for controlling arsenic contamination. However, developing rapid and efficient MOF adsorbents with the capability of easy recovery is still challenging. Herein, we prepared a three-dimensional porous MIL-88A-Fe/gelatin aerogel (PMGA) with macroscopic size and coupled it with H2O2 to fabricate a heterogeneous catalytic oxidation adsorption system to remove As(III) in water. The green synthesis strategy of this catalyst by foaming and low-temperature carbonization not only avoided the use of toxic chemical crosslinkers but also endowed PMGA with a rich hierarchical porous structure and exposed more active sites. Thus, the PMGA/H2O2 system was able to reduce the concentration of As(III) from 1106 to below 10 µg/L and simultaneously realize the complete oxidation of As(III) to As(V) in only 120 min. Meanwhile, the system exhibited an excellent saturation adsorption capacity (24.863 mg/g) for As(III), superior to most similar bio-based or iron-based materials. Quenching experiments, EPR and DFT calculations showed that the active species (surface •OOH and surface •OH) generated by the Fenton-like interaction between the exposed (100) facet of MIL-88A-Fe in PMGA and H2O2 played an essential role in promoting the oxidative removal of As(III). Moreover, the reaction system could work efficiently for As(III) in a wide pH range and was hardly affected by other substances such as chlorides, sulfates, carbonates, silicates, and humic acids. Simultaneously, the fixed bed column filled with PMGA could stably and continuously treat As(III) in groundwater. Therefore, this study not only broadens the horizon for the development and design of 3D functional materials but also provides a new strategy in water purification to eliminate arsenic pollutants using Fe-MOF aerogels.

Synthesis of magnetic biochar-supported Fe-Cu bimetallic catalyst from pulp and paper mill wastes for the Fenton-like removal of rhodamine B dye

Treating the wastes generated from pulp and paper mills, such as black liquor and Fenton sludge is challenging. In this study, the biochar-supported Fe-Cu bimetallic catalysts were synthesized by a one-step pyrolysis method using Fenton sludge as iron source, acid-precipitated black liquor (APBL) as carbon source and copper nitrate as copper source. The catalysts were used to remove rhodamine B (RhB) dye from aqueous solution by Fenton-like reaction. The optimal catalyst (FeCu@BC600-2) was pyrolyzed at 600 °C with an Fe/Cu mixing ratio of 2 and consisted of mesoporous biochar supported nanoscale Fe3O4 and Cu0. It had a specific surface area of 104.6 m2·g−1 and a saturation magnetization of 33.3 emu·g−1. In the FeCu@BC600-2/H2O2 system, RhB dye (10 mg·L-1) was completely removed within 60 min at acidic pH (initial pH 3, 0.2 g·L-1 catalyst, 1 mM H2O2) or 6 h at neutral pH (initial pH 7, 0.25 g·L-1 catalyst, 25 mM H2O2) at 30 °C. Moreover, the FeCu@BC600-2 exhibited good magnetic separation ability, low metal leaching, excellent reusability and broad applicability to other synthetic dyes. The dye removal mechanism involved the synergistic effect of adsorption and catalytic oxidation (especially heterogeneous catalytic oxidation). At acidic pH, RhB degradation was due to •OH radical, which was generated from the activation of H2O2 by ≡Cu(I) or Cu(I) oxidized from Cu0 and ≡Fe(II) in Fe3O4. At neutral pH, RhB degradation was mainly due to •OH and 1O2 with the former being produced by ≡Cu(I) and ≡Fe(II). Furthermore, Cu(I) oxidized from Cu0 and the active functional groups (such as sp2 C = C) in the biochar facilitated the reduction of Fe(III) to Fe(II), resulting in a high catalytic oxidation efficiency.

Enhanced Oxidation of Organic Compounds by the Ferrihydrite-Ferrate System: The Role of Intramolecular Electron Transfer and Intermediate Iron Species.

Previous studies mostly held that the oxidation capacity of ferrate depends on the involvement of intermediate iron species (i.e., FeIV/FeV), however, the potential role of the metastable complex was disregarded in ferrate-based heterogeneous catalytic oxidation processes. Herein, we reported a complexation-mediated electron transfer mechanism in the ferrihydrite-ferrate system toward sulfamethoxazole (SMX) degradation. A synergy between intermediate FeIV/FeV oxidation and the intramolecular electron transfer step was proposed. Specifically, the conversion of phenyl methyl sulfoxide (PMSO) to methyl phenyl sulfone (PMSO2) suggested that FeIV/FeV was involved in the oxidation of SMX. Moreover, based on the in situ Raman test and chronopotentiometry analysis, the formation of the metastable complex of ferrihydrite/ferrate was found, which possesses higher oxidation potential than free ferrate and could achieve the preliminary oxidation of organics via the electron transfer step. In addition, the amino group of SMX could complex with ferrate, and the resulting metastable complex of ferrihydrite/ferrate would combine further with SMX molecules, leading to intramolecular electron transfer and SMX degradation. The ferrate loss experiments suggested that ferrihydrite could accelerate the decomposition of ferrate. Finally, the effects of pH value, anions, humic acid, and actual water on the degradation of SMX by ferrihydrite-ferrate were also revealed. Overall, ferrihydrite demonstrated high catalytic capacity, good reusability, and nontoxic performance for ferrate activation. The ferrihydrite-ferrate process may be a green and promising method for organic removal in wastewater treatment.

Reliability analysis of NaN3 as quencher of 1O2 in heterogeneous persulfate catalytic oxidation system

At present, more and more scholars have questioned the reliability of NaN3 as a quench agent of 1O2 in heterogeneous persulfate catalytic oxidation system. In this study, we first compared the decomposition kinetics of PMS in the presence of CuO (CuOMgO), different concentrations of NaN3, and CuO (CuOMgO) with different concentrations of NaN3, respectively. Subsequently, the catalytic performance of common catalysts was compared. These results confirmed that the addition of NaN3 will significantly affect the decomposition process of PMS in heterogeneous persulfate catalytic oxidation system, so it is not suitable to be used as quench agent of 1O2.

Carbon nitride with a tailored electronic structure toward peroxymonosulfate activation: A direct electron transfer mechanism for organic pollutant degradation

The persulfate-based nonradical reaction process has gained increasing attention in removing organic contaminants, and the process dramatically needs affordable, robust, high-performance heterogeneous catalysts. Herein, dimethyl formamide (DMF) incorporated graphitic carbon nitride (DCN) was synthesized. The molecular engineering of the heptazine unit in DCN improves the electron mobility, strengthens the built-in electric field, and provides abundant active sites, thus enabling DCN to efficiently activate PMS for organic degradation, with 100 % removal of BPA within 12 min. The investigation of the reactive species and electrochemical properties confirmed the direct electron transfer in the PMS activation for organic degradation over DCN. More importantly, DCN can be used as a membrane catalyst in a flowing catalytic unit, enabling continuous water purification and catalyst regeneration. This work provides novel guidance for metal-free catalyst design and profound insights into the persulfate-based heterogeneous catalytic oxidation process for water decontamination technology.

Synthesising nanocomposite Co2SnO4@rGO for peroximonosulphate activation in a hybrid ozonation system to effectively degrade cefalexin from wastewater

This study successfully developed Co2SnO4@rGO nanocomposites at various composite ratios of Co2SnO4 and rGO using the sol-gel method. These nanocomposites were then used as heterogeneous catalysts to activate PMS in the heterogeneous catalytic oxidation of Co2SnO4@rGO/PMS as well as the hybrid ozonation system O3/Co2SnO4@rGO/PMS to degrade cefalexin (CFX). The physical-chemical characteristics of the fabricated catalysts were evaluated through nitrogen adsorption-deadsorption, SEM images, EDS mapping, and XRD. The catalytic activity of the nanocomposite was investigated in a degradation reaction of CFX from an aqueous solution. Besides this, CFX degradation kinetics were determined by fitting experimental data with a first-order model. The results showed that at the composite ratio of 2-Co2SnO4 and 1-rGO for CFX degradation had the highest efficiency reaching 95.07 and 99.07% for Co2SnO4@rGO/PMS and O3/Co2SnO4@rGO/PMS systems, respectively. The degradation of CFX in the O3/Co2SnO4@rGO/PMS system was higher than that of Co2SnO4@rGO/PMS. The results were due to a remarkable increase in SBET in 2-Co2SnO4@1-rGO compared to both Co2SnO4 and rGO, facilitating a catalytic reaction occurring on the catalyst’s surface. Moreover, the coupling between O3 and Co2SnO4@rGO/PMS generated a synergetic effect leading to the generation of more *SO4- and *OH radicals, which enhanced the CFX degradation rate in the hybrid ozonation system. These primary findings illustrated that the nanocomposite catalyst 2-Co2SnO4@1-rGO was feasible for the activation of PMS in hybrid ozonation to effectively degrade antibiotic residues from wastewater.

Heterogeneous catalytic oxidation for lignin valorization into aromatic compounds over acid-redox bifunctional polyoxometalates

Lignin, as the largest renewable aromatic resource on the planet, has significant potential for the production of value-added platform chemicals. In this work, we synthesized a series of cesium-exchanged acid-redox bifunctional polyoxometalates (POMs) and evaluated their performance as catalysts for the depolymerization of birch lignin into low molecular weight aromatic compounds. The Cs3H2PMOV2O40 catalyst exhibited the highest activity, resulting in a monomer yield of approximately 13.6 %. Gel permeation chromatography (GPC), heteronuclear single quantum coherence (HSQC) spectroscopy, and gas chromatography-mass spectrometry (GC-MS) analysis confirmed the effective cleavage of β-O-4, β-5, and β-β linkages in the lignin polymer. The proposed reaction mechanism for the lignin depolymerization over cesium-exchanged POMs was also discussed. Our results demonstrate the potential of cesium-exchanged POMs as effective catalysts for the conversion of lignin into value-added chemicals, thereby contributing to the complete sustainable utilization of lignocellulose.