Efficient ozone decomposition in high humidity environments using novel iron-doped OMS-2-loaded activated carbon material.

This study effectively addresses the rapid deactivation of manganese-based catalysts in humid environments during ozone decomposition by introducing iron-doped manganese oxide octahedral molecular sieve (Fe-OMS-2) catalysts supported on activated carbon (AC). By optimizing the doping ratio of Fe-OMS-2, the Fe-OMS-20.5/AC catalyst achieves nearly 100% ozone decomposition efficiency across a wide range of relative humidity levels (0 to 60%), even at elevated air flow rates of 800 L·g-1·h-1, outperforming standalone AC, Fe-OMS-2, or a simple mixture of OMS-2 and AC. The Fe-OMS-20.5/AC catalyst features a porous surface and a mesoporous structure, providing a substantial specific surface area that facilitates the uniform distribution of the Fe-OMS-2 active phase on the AC surface. The incorporation of Fe3+ ions enhances electron transfer between valence state transitions of Mn, thereby improving the catalyst's efficiency in ozone decomposition. Additionally, the AC component protects catalytic sites and enhances the catalyst's humidity resistance. In conclusion, this research presents a novel strategy for developing highly efficient and cost-effective ozone decomposition catalysts that enhance dehumidification, significantly contributing to industrial ozone treatment technologies and advancing environmental protection.

Enhancing CO catalytic oxidation performance over Cu-doping manganese oxide octahedral molecular sieves catalyst.

The CO oxidation catalytic activity of catalysts is strongly influenced by the oxygen vacancy defects (OVDs) concentration and the valence state of active metal. Herein, a defect engineering approach was implemented to enhance the oxygen vacancy defects and to modify the valence of metal ions in manganese oxide octahedral molecular sieves (OMS-2) by the introduction of copper (Cu). The characterization and theoretical calculation results reveal that the incorporation of Cu2+ ion into the OMS-2 structure led to a rise in specific surface area and pore volume, weakening of Mn-O bonds, higher proportion of the low-coordinated oxygen species adsorbed in oxygen vacancies (Oads) and an increase in the average oxidation state of manganese. These structural modifications were discovered to considerably reduce the apparent activation energy (Ea), thus ultimately significantly enhancing the CO oxidation activity (T99 at 148 ℃at GHSV = 13,200 h-1) than the original OMS-2 (T99 = 215 ℃ at GHSV = 13,200 h-1). Furthermore, In-situ diffuse reflectance infrared Fourier transform (DRIFT) and In-situ near-ambient pressure X-ray photoelectron spectroscopy (in situ NAP-XPS) results indicate that the bimetallic synergy enhanced by doping strategy accelerates the conversion of oxygen to chemisorbed oxygen species and the reaction rate of CO oxidation through Mn3++Cu2+↔Mn4++Cu+ redox cycle. The findings of this study offer novel perspectives on the design of catalysts with exceptional performance in CO oxidation.

Highly Active and Water-Resistant Cu-Doped OMS-2 Catalysts for CO Oxidation: The Importance of the OMS-2 Synthesis Method and Cu Doping.

Porous cryptomelane-type Mn oxide (OMS-2) has an outstanding redox property, making it a highly desirable substitute for noble metal catalysts for CO oxidation, but its catalytic activity still needs to be improved, especially in the presence of water. Given the strong structure-performance correlation of OMS-2 for oxidation reactions, herein, OMS-2 is synthesized by solid state (OMS-2S), reflux (OMS-2R), and hydrothermal (OMS-2H) methods, aiming to improve its CO oxidation performance through manipulating synthesis parameters to tailor its particle size, morphology, and crystallinity. Characterization shows that OMS-2S has the highest CO oxidation activity in the absence of water due to its low crystallinity, high specific surface area, large oxygen vacancy content, and good redox property, but the presence of water can greatly reduce its CO oxidation activity. Doping Cu into an OMS-2 can not only improve its CO oxidation activity but also greatly improve its water tolerance. The Cu-doped OMS-2S catalyst with ∼4 wt % Cu can achieve a T90 of 49 °C (1% CO/10% O2/N2 and WHSV = 60,000 mL·g-1·h-1), ranking among the lowest reported T90 values for Mn oxide-based CO oxidation catalysts, and it can maintain nearly 100% CO conversion in the presence of 5 vol % water for over 50 h. In situ DRIFTs characterization indicates that the good water resistance of Cu-doped OMS-2S can be attributed to the significantly suppressed surface hydroxyl group generation because of Cu doping. This work demonstrates the importance of the synthesis method and Cu doping in determining the CO oxidation activity and water resistance of OMS-2 and will provide guidance for synthesizing highly active and water-resistant CO oxidation catalysts.

Catalytic destruction of chlorobenzene over K-OMS-2: Inhibition of high toxic byproducts via phosphate modification.

In the process of catalytic destruction of chlorinated volatile organic compounds (CVOCs), the catalyst is prone to chlorine poisoning and produce polychlorinated byproducts with high toxicity and persistence, bringing great risk to atmospheric environment and human health. To solve these problems, this work applied phosphate to modify K-OMS-2 catalysts. The physicochemical properties of catalysts were determined by using X-ray powder diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), hydrogen temperature programmed reduction (H2-TPR), pyridine adsorption Fourier-transform infrared (Py-IR) and water temperature programmed desorption (H2O-TPD), and chlorobenzene was selected as a model pollutant to explore the catalytic performance and byproduct inhibition function of phosphating. Experimental results revealed that 1 wt.% phosphate modification yielded the best catalytic activity for chlorobenzene destruction, with the 90% conversion (T90) at approximately 247°C. The phosphating significantly decreased the types and yields of polychlorinated byproducts in effluent. After phosphating, we observed significant hydroxyl groups on catalyst surface, and the active center was transformed into Mn(IV)-O…H, which promoted the formation of HCl, and enhanced the dechlorination process. Furthermore, the enriched Lewis acid sites by phosphating profoundly enhanced the deep oxidation ability of the catalyst, which promoted a rapid oxidation of reaction intermediates, so as to reduce byproducts generation. This study provided an effective strategy for inhibiting the toxic byproducts for the catalytic destruction of chlorinated organics.

Thermal-Driven Optimization of the Strong Metal-Support Interaction of a Platinum-Manganese Oxide Octahedral Molecular Sieve to Promote Toluene Oxidation: Effect of the Interface Pt2+-Ov-Mnδ.

Strong metal-support interactions (SMSIs) have a significant effect on the performance of supported noble-metal catalysts for volatile organic compound (VOC) elimination. Herein, the strength of the SMSI of Pt/OMS-2 between Pt and the OMS-2 support is regulated by simply changing calcination temperatures, and the catalyst calcined at 300 °C (Pt/OMS-2-300) performs the best in the catalytic combustion of toluene. Through systematic structural characterizations, it is revealed that much more Pt2+-Ov-Mnδ+ species are formed in Pt/OMS-2-300, which can help facilitate the generation of more reactive oxygen species and promote lattice oxygen mobility. Moreover, the results of in situ DRIFTS experiments further confirm that abundant Pt2+-Ov-Mnδ+ species at the Pt-MnO2 interface on Pt/OMS-2-300 can better enhance the adsorption and activation of toluene, thus boosting the catalytic performance in toluene combustion. This newly developed strategy of thermal-driven regulation of the SMSI provides a novel perspective for constructing highly efficient catalysts for VOC emission control.

Enhanced degradation and mineralization of estriol over ZrO2/OMS-2 nanocomposite: Kinetics, pathway and mechanism.

Although remarkable progresses have been achieved in the exploration of new and efficient catalytic systems for efficient degradation of estriol, there are only very few available reports providing high mineralization of estriol. Hence, it is still a serious challenge to develop the novel and efficient methods for enhanced degradation and mineralization of estriol due to its serious threat to environment and human health. Herein, this study proposes a series of ZrO2 modified manganese oxide octahedral molecular sieve (ZrO2/OMS-2) nanocomposites as efficient catalysts for enhanced degradation and mineralization of estriol via PMS activation at 30 °C. Among them, ZrO2/OMS-2-27% provided the highest degradation efficiency (95%) and mineralization degrees (70.1%), which exceeded most reported catalytic systems, in the catalytic degradation of estriol. These quenching tests and EPR analysis had confirmed that O2•- and 1O2 were primary reactive oxygen species (ROS) in the ZrO2/OMS-2-27%/PMS system, contrary to the OMS-2/PMS system for which SO4•- and OH• are primary ROS. This might be due to the abundant O-containing surface functional groups of ZrO2/OMS-2-27%. This work not only provides a facile and high-efficiency methodology for the construction of Mn-based nanomaterial, but also proposes a new and efficient nano-catalyst for estriol removal.

Insights into selective hydrogenation of levulinic acid using copper on manganese oxide octahedral molecular sieves.

Selective hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) was studied using copper on manganese oxide octahedral molecular sieve (OMS-2) as catalysts. A range of copper supported on OMS-2 catalysts was prepared using the modified wet-impregnation technique and characterized thoroughly using powder X-ray diffraction, inductively coupled plasma optical emission spectroscopy metal analysis, Fourier transform infrared, high-resolution transmission electron microscopy and N2 sorption analyses. Process parameters for selective hydrogenation of LA to GVL were optimized using the design of experiment (DoE) approach with response surface methodology comprising a central composite design. Using the optimized conditions (190°C reaction temperature, 20 bar H2 pressure and 20 wt% Cu loading on OMS-2), up to 98% yield of GVL could be achieved in water as a solvent. Based on DoE, H2 pressure had the most influence on GVL selectivity followed by catalyst loading used for the hydrogenation of LA. The response surface methodology model also showed synergistic effect of reaction temperature and H2 pressure on the yield of GVL. 20 wt% Cu/OMS-2 catalysts were re-used up to four cycles and showed noticeable loss of activity after the first cycle due to observed leaching of loose Cu species, thereafter the activity loss diminished during subsequent recycles.

Comprehensive evaluation of cobalt incorporated cryptomelane-type manganese oxide molecular sieve as an efficient adsorbent for enhanced removal of europium from wastewater systems.

Extraction of radionuclide contaminants from wastewater systems has recently drawn widespread attention, and then developing a novel and green extracting technology has also become an enormous challenge. Herein, a facile hydrothermal method was employed to fabricate cobalt-incorporated cryptomelane-type manganese oxide molecular sieve (Co-OMS-2) for extraction Eu(III) from wastewater under diverse experimental conditions. All kinds of characterized techniques, such as SEM, TEM, XRD, FTIR, BET, EDS and XPS had verified the qualified synthesis process and splendid structural features of the Co-OMS-2. The maximum adsorption capacity of Co-OMS-2 was 7.62 × 10-4 mol/g for Eu(III) at 298 K, which was superior than primarily traditional materials reported previous literatures. The high adsorption capacity of Eu(III) onto Co-OMS-2 was primarily attributed to high specific surface area and abundant surface functional groups, and the interactions were mainly contributed to strong surface complexation and electrostatic attraction. Under the condition of low pH, the outer-sphere surface complexation and cation exchange were primary mechanisms to Eu(III) adsorption onto Co-OMS-2 composites, while inner-sphere surface complexation was mainly assigned to Eu(III) adsorption onto Co-OMS-2 under the high pH sections. The Co-OMS-2 composite achieved equilibrium in a relatively short time, and this excellent performance was conducive to the treatment of Eu(III) under the extreme emergency conditions. In view of the extraordinary adsorption capacity and recycled reusability, the Co-OMS-2 composites can be as prospective adsorbents adopted for the extraction of Eu(III) in real wastewater management.

An investigation on catalytic performance and reaction mechanisms of Fe/OMS-2 for the oxidation of carbon monoxide, ethyl acetate, and toluene.

The octahedral molecular sieve (OMS-2)-supported Fe (xFe/OMS-2: x = 1, 3, 5, and 10) catalysts were prepared using the pre-incorporation method. Physicochemical properties of the as-synthesized materials were characterized by means of various techniques, and their catalytic activities for CO, ethyl acetate, and toluene oxidation were evaluated. Among all of the samples, performed the best, with the reaction temperature required to achieve 90% conversion (T90%) being 160°C for CO oxidation, 210°C for ethyl acetate oxidation, and 285°C for toluene oxidation. Such a good catalytic performance of 5Fe/OMS-2 was associated with its high (Mn3+ + Mn2+) content and adsorbed oxygen species concentration, and good low-temperature reducibility and lattice oxygen mobility as well as strong interaction between Fe and OMS-2. In addition, catalytic mechanisms of the oxidation of three pollutants over the 5Fe/OMS-2 catalyst were also studied. It was found that CO, ethyl acetate or toluene was first adsorbed, then the related intermediates were formed, and finally the formed intermediates were completely converted into CO2 and H2O.

Boosting Oxygen Reduction Activity of Manganese Oxide Through Strain Effect Caused By Ion Insertion.

Transition-metal oxides with a strain effect have attracted immense interest as cathode materials for fuel cells. However, owing to the introduction of heterostructures, substrates, or a large number of defects during the synthesis of strain-bearing catalysts, not only is the structure-activity relationship complicated but also their performance is mediocre. In this study, a mode of strain introduction is reported. Transition-metal ions with different electronegativities are intercalated into the cryptomelane-type manganese oxide octahedral molecular sieves (OMS-2) structure with K ions as the template, resulting in the octahedral structural distortion of MnO6 and producing strains of different degrees. Experimental studies reveal that Ni-OMS-2 with a high compressive strain (4.12%) exhibits superior oxygen reduction performance with a half-wave potential (0.825 V vs RHE) greater than those of other reported manganese-based oxides. This result is related to the increase in the covalence of MnO6 octahedral configuration and shifting down of the eg band center caused by the higher compression strain. This research avoids the introduction of new chemical bonds in the main structure, weakens the effect of eg electron filling number, and emphasizes the pure strain effect. This concept can be extended to other transition-metal-oxide catalysts.

Trace holmium assisting delaminated OMS-2 catalysts for total toluene oxidation at low temperature.

In this study, octahedral molecular sieve (OMS-2) is successfully delaminated by using trace holmium (Ho) via a facile redox co-precipitation route, which exhibits high performance for the total toluene oxidation at low temperature. High resolution transmission electron microscope (HRTEM), X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) analyses verify that abundant multi-phase interfaces and lattice dislocations are formed on the obtained delaminated OMS-2 by the Ho (Ho-OMS-2), which can induce more active oxygen species. In particular, the delaminated OMS-2 with a trace Ho amount has a high Oads/Olatt ratio with a balanced ratio of Mn3+ and Mn4+, demonstrating much higher activity (T100% of 228 °C even under 5 vol% H2O vapor over 0.5% Ho-OMS-2) than the parent OMS-2 (T100% of 261 °C) for the total toluene oxidation. Furthermore, the positive effect of the introduction of H2O on catalytic activity, especially the enhancement of the conversion of intermediates into CO2 and H2O, is verified by the in situ diffuse reflection infrared Fourier transform spectroscopy (DRIFTS). Based on these results, the reaction mechanism for toluene oxidation over the OMS-2 based catalyst is proposed. It is expected to provide an effective preparation method to obtain high-performance catalysts for the VOCs oxidation at low temperatures.

The post plasma-catalytic decomposition of toluene over K-modified OMS-2 catalysts at ambient temperature: Effect of K+ loading amount and reaction mechanism.

The present work is devoted to study the post plasma-catalytic (PPC) degradation of toluene using packed-bed discharge (PBD) plasma over K-modified manganese oxide octahedral molecular sieve (OMS-2) catalysts at ambient temperature. Compared to plasma alone, PPC can significantly improve the toluene degradation and mineralization performance simultaneously, and the generation of discharge byproducts and organic intermediates is suppressed. The catalytic capacity of OMS-2 for toluene degradation is greatly promoted by tuning potassium ions (K+) content in OMS-2 tunnel, which might be owing to the formation of more surface active oxygen species derived from weak Mn-O bonds, plenty of oxygen vacancies, as well as more superior low-temperature reducibility. Highest toluene degradation efficiency (89.4%) and COx selectivity (88.9%) can be achieved in plasma-catalysis system over K-modified OMS-2 sample with K/Mn molar ratio of 2 at the SIE of 658 J/L. A long-term stability test has also been successfully carried out to evaluate the stability of K-modified OMS-2 with the assistance of plasma. Possible reaction mechanism for plasma-catalytic degradation of toluene on K-modified OMS-2 catalyst has been proposed based on the plasma diagnosis, catalysts characterization, and organic intermediates identification. This work aims to gaina deeperunderstandingof plasma-catalytic degradation mechanism and provides an environmentally friendly and energy-efficient method for practical volatile organic compounds (VOCs) abatement in PPC process.

Synergistic Effects of Ternary PdO-CeO2-OMS-2 Catalyst Afford High Catalytic Performance and Stability in the Reduction of NO with CO.

We developed a robust ternary PdO-CeO2-OMS-2 catalyst with excellent catalytic performance in the selective reduction of NO with CO using a strategy based on combining components that synergistically interact leading to an effective abatement of these toxic gases. The catalyst affords 100% selectivity to N2 at the nearly full conversion of NO and CO at 250 °C, high stability in the presence of H2O, and a remarkable SO2 tolerance. To unravel the origin of the excellent catalytic performance, the structural and chemical properties of the PdO-CeO2-OMS-2 nanocomposite were analyzed in the as-prepared and used state of the catalyst, employing a series of pertinent characterization methods and specific catalytic tests. The experimental as well as theoretical results, based on density-functional theory calculations suggest that CO and NO follow different reaction pathways, CO is preferentially adsorbed and oxidized at Pd sites (PdII and Pd0), while NO decomposes on the ceria surface. Lattice oxygen vacancies at the interfacial perimeter of PdO-CeO2 and PdO-OMS-2, and the diffusion of oxygen and oxygen vacancies are proposed to play a critical role in this multicenter reaction system.

The positive effect of Ca2+ on cryptomelane-type octahedral molecular sieve (K-OMS-2) catalysts for chlorobenzene combustion.

Herein, K-OMS-2 catalysts with different levels of Ca2+ loading were synthesized to investigate the influence of Ca2+ deposition on the catalytic oxidation of CB. The micromorphology, redox ability, oxygen species, and surface acidity of the prepared catalysts were analyzed via SEM, HR-TEM, H2-TPR, O2-TPD, Py-IR, and GC-MS. After the Ca addition, CB conversion on the catalyst was achieved at <220 °C and the polychlorinated by-product yield decreased significantly. Although CaCO3 formation on the catalyst surface from Ca2+ caused a decline in number and fluidity of the surface lattice oxygen species, no significant impact on surface adsorbed oxygen species content was observed. Furthermore, CaCO3 reacted with dissociated chlorine species (HCl and polychlorinated products generated in situ), which inhibited chlorine poisoning of the active phase.

The remarkable effect of alkali earth metal ion on the catalytic activity of OMS-2 for benzene oxidation.

Cryptomelane-type octahedral molecular sieve (OMS-2) is one of the most promising catalysts for VOCs oxidation, and introduction of metal ions in OMS-2 tunnel is widely used for tailoring its catalytic activity. Here, different types of alkali earth metal ions with the same X/Mn atomic ratio of approximately 0.012 (X represents Mg2+, Ca2+, and Sr2+) were successfully introduced into OMS-2 tunnel by a one-step redox reaction. The catalytic test showed that introducing alkali earth metal ions into tunnels had a considerable effect on the catalytic performance of OMS-2 for benzene oxidation. The Sr2+ doped OMS-2 catalyst exhibited the better catalytic activity compared with those of Mg-OMS-2 and Ca-OMS-2 samples, and was also superior to a commercial 0.5% Pt/Al2O3 catalyst, as evidenced by its low reaction temperatures of T50 = 200 °C and T90 = 223 °C (corresponding to benzene conversions at 50% and 90%, respectively). The origin of the considerable effect of alkali earth metal doping on the catalytic activity of OMS-2 catalysts was experimentally and theoretically investigated by an 18O2 isotopic labeling experiment, CO temperature-programmed reduction, O2 temperature-programmed oxidation, and density functional theory calculations. The greatest catalytic activity of Sr-OMS-2 compared with those of Mg-OMS-2 and Ca-OMS-2 samples was attributed to its highest lattice oxygen activity as well as its largest surface area. By introducing alkali earth metal ions into the OMS-2 tunnel, we developed a low-cost and highly efficient catalyst that could be used as alternative to noble metal catalysts.

Lewis acids promoted organic pollutants degradation in aqueous solution with peroxymonosulfate and MnO2: New insights into the activation mechanism.

Nonredox metal ions have been widely recognized to be important in a wide range of biological and chemical oxidations as Lewis acids (LA). However, the role of LA in peroxymonosulfate (PMS) activation for wastewater treatment has not been considered until now. This study shows that oxidizing power of PMS can be promoted after binding nonredox metal ions such as Ca2+ as LA, leading to the easier reduction of the oxidant to radicals and substantial enhancement of dye degradation by employing manganese oxides OMS-2 as model catalysts. Increased with Lewis acidity of the metal ion, the rate of PMS decomposition enhanced linearly, while the dye degradation rate first increased and then declined due to the formation of a larger amount of dioxygen. The interactions between Ca2+ and PMS were further investigated by Raman, cyclic voltammetry and XPS; and the detailed mechanism of PMS activation was proposed. The performance of Ca2++OMS-2/PMS system under different conditions was also studied. The findings indicate the importance of LA in PMS activation reaction and their role must be considered in other transition metal oxides/PMS systems. It will be also helpful to design new and highly active catalysts for the reactions.

Enhancing Water Resistance of a Mn-Based Catalyst for Low Temperature Selective Catalytic Reduction Reaction by Modifying Super Hydrophobic Layers.

OMS-2 catalysts exhibit excellent selective catalytic reduction (SCR) activity at low temperature but weak H2O resistance restricts its industrial application. To remarkably improve the water resistance of Mn-based catalysts is a key technical problem. In this work, the H2O endurance and self-cleaning properties of OMS-2 catalysts are remarkably improved by the facile process, construction of hydrophobic coating. The performance of the hydrophobic layer on the bulk OMS-2 catalyst surface could be effectively controlled by adjusting the polydimethylsiloxane (PDMS) vapor deposition temperature. It is discovered that the 200 °C catalyst obtained super hydrophobic properties and formed with a contact angle of 160.3°, which not only exhibited satisfactory NH3-SCR activity at low temperatures (140-300 °C) but also dramatically improved H2O endurance and self-cleaning performance. Moreover, the mechanism of improving H2O resistance and stability of the 200 °C catalyst was investigated in detail through a series of characterizations. Although the SCR activity of the 200 °C catalyst decreased slightly because of the combination of some active species (Oα and Mn3+) with PDMS, the H2O passivation of the active species was eliminated. The advantage of self-cleaning was confirmed by the analysis of surface species and simulation experiments, which could avoid the accumulation of intermediates on the surface and promote the stability of the OMS-2 catalyst for NH3-SCR at low temperature. This method of constructing special coating might be a huge step to remarkably improve the H2O endurance properties of the catalyst and provided a new concept for future industrial application.

OMS-2-based catalysts with controllable hierarchical morphologies for highly efficient catalytic oxidation of formaldehyde.

Cryptomelane-type octahedral molecular sieve (OMS-2) catalysts are currently attracting tremendous attention due to their low-cost and remarkable thermo-catalytic activity. However, it is still difficult for OMS-2 catalysts to completely degrade formaldehyde at relatively low or even ambient temperature. In this work, OMS-2 catalysts with different ratios of length to diameter were prepared and the OMS-2-s with the minim ratio of length to diameter (1-3) exhibited the best catalytic performance than the other samples. Then, the optimized OMS-2-s nanorods were loaded on the SiO2 nanofibers via a simultaneous electrospining-spray strategy. The evaluation for the dynamic catalytic activities of the samples showed that, the T50 (HCHO conversion reached to 50%) for the OMS-2/SiO2 nanofibrous membranes was decreased by 24 °C than the OMS-2-s nanorods. Furthermore, in the static experiment of HCHO decomposition, the composite membrane could achieve a catalytic efficiency of 52.3% at 25 °C, much higher than that of the OMS-2-s nanorods (45.9%). This work offers a new strategy to improve the catalytic efficiency of OMS-2 by controlling the morphology and loading of OMS-2 nanorods, and also designs a kind of advanced nano OMS-2-based nanofibrous membranes with hierarchical nanostructures for the highly efficient formaldehyde elimination during the practical application.

Room-temperature synthesis of OMS-2 hybrids as highly efficient catalysts for pollutant degradation via peroxymonosulfate activation.

Due to low cost and low toxicity, manganese oxides have been extensively explored to reduce organic pollutants in wastewater via peroxymonosulfate (PMS) activation; but the development of manganese-based catalysts with facile synthesis process at low temperatures and high efficiency is still of significant practical interest. In this paper, a simple room temperature method has been successfully developed to synthesize cryptomelane-type manganese octahedral molecular sieves (OMS-2) from KMnO4 and MnSO4 in the presence of carbon nanotubes (CNTs). The redox reaction between amorphous manganese oxide and CNTs results the decrease of manganese valences and the formation of OMS-2 phase at a low temperature of 25 °C. The changes of synthesis time, temperature and CNTs dosage altered the characteristics of the prepared materials. Compared with CNTs, OMS-2 and other manganese oxides hybrids, the synthesized catalysts demonstrated a remarkable efficiency for PMS activation to degrade organic dyes and a superior reusability during ten successive cycles. Sulfate radicals were formed as the active species in the system from the oxidation of low valent Mn species by PMS. This study not only provides a simple method to synthesize OMS-2 at room temperature, but also improves the understanding of PMS activation on manganese-based catalysts for pollutants degradation.

Tuning manganese (III) species in manganese oxide octahedral molecular sieve by interaction with carbon nanofibers for enhanced pollutant degradation in the presence of peroxymonosulfate.

The development of environmental-benign, efficient, and durable Mn based catalysts is of great importance for remediation of organic pollutants. In this study, a series of cryptomelane-type octahedral molecular sieve (OMS-2) and carbon nanofibers (CNFs) nanocomposites (OC) were synthesized by a facile refluxing approach under different conditions, and the catalytic activity was evaluated for Acid Orange 7 degradation under neutral conditions via peroxymonosulfate activation. It was revealed that the composites were more efficient than the pure OMS-2 and CNFs, due to the higher amounts of Mn(II) and Mn(III) species and the synergistic effects between OMS-2 and CNFs. The OC catalysts presented long-term stability without the leaching of Mn ions during seven consecutive cycles. Radical scavenger and EPR experiments indicated that the low valent Mn species in the composites were oxidized by PMS to produce sulfate radicals to degrade dyes. However, the structure and performance of OC were influenced significantly by CNFs dosage and refluxing time. Under a high CNFs ratio or a long refluxing time, OMS-2 was damaged and lost its catalytic activity completely. This study provides important implications for turning of the valence of Mn species in manganese oxides, and widens the practical applications of the manganese oxides/ carbon materials in wastewater treatment.