Experimental and theoretical (ReaxFF) study of manganese-based catalysts for low-temperature toluene oxidation

This study presents detailed experimental and theoretical investigation of manganese-based metal oxides, MnMO_x (M: Fe, Ni, Cu) as potential catalysts for the low-temperature toluene oxidation. The first part of the paper deals with the detailed characterization of the prepared catalysts and testing of their catalytic activity and stability in the fixed-bed reactor. The MnFeO_x exhibited superior and stable catalytic activity for toluene oxidation (T₉₀ = 419–446 K), comparable with the activity of the commercial Pt–Al₂O₃ catalyst (T₉₀ = 393–423 K). Among the studied catalysts the following order of catalytic activity was determined: MnFeO_x > MnNiO_x ≈ MnCuO_x > MnO_x. The one-dimensional (1D) pseudo-homogeneous model was applied to describe behavior of the fixed bed reactor for the low temperature toluene oxidation over prepared MnFeO_x catalysts. The second part of the paper is focused on theoretical investigation of toluene interaction on the surface of the single metal oxides (Mn₂O₃, MnO₂, Fe₂O₃, NiO and CuO) in the oxygen atmosphere using the ReaxFF method, since they were individual dominant phases in the prepared catalysts. A good correlation between the predicted binding energy of toluene adsorption on the surface of studied metal oxide phases and experimentally determined catalytic activities was observed.     

Improved photoelectrocatalytic degradation of methylene blue by Ti3C2Tx/Bi12TiO20 composite anodes

In order to effectively reduce the high recombination rate of photogenerated carriers when Bi₁₂TiO₂₀ (BTO) was excited by visible light, Ti₃C₂T_x/BTO/fluorine-doped tin oxide photoanodes were conveniently prepared with the aid of mechanical coating by gentle ultrasonic mixing. Systematic characterization and the degradation of methylene blue in a photoelectrochemical cell were performed. The results showed that the Ti₃C₂T_x/BTO composite exhibited a strong light absorption ability and the effective separation of photogenerated carriers. The optimal anode (6 wt% Ti₃C₂T_x/BTO) degraded 85.4% of methylene blue within 120 min at an applied electric field of 1 V, with a reaction rate that was 3.5 times that of BTO. It was proved that Ti₃C₂T_x, as a useful co-catalyst, creates an internal electric field at the contact interface with BTO and an external electric field, which are responsible for the enhanced photoelectrocatalytic degradation capacity of the composite anode materials.     

Mechanistic aspects of the oxidative dehydrogenation of propane over an alumina-supported VCrMnWOx mixed oxide catalyst

Mechanistic and kinetic aspects of the catalytic oxidative dehydrogenation of propane (ODP) were studied within a wide range of temperatures (673–773 K), partial pressures of oxygen (0–20 kPa), propane (0–40 kPa) and propene (0–4 kPa) under both steady-state ambient-pressure and transient, vacuum conditions in the temporal analysis of products (TAP) reactor. A Mn_0.18V_0.3Cr_0.23W_0.26O_x–Al₂O₃ catalyst was identified as a selective catalyst for ODP by high-throughput experiments. For comprehensive catalyst characterization, XRD, BET, and in situ UV–visible techniques were applied. The results from transient experiments in combination with UV–visible tests reveal that selective and non-selective propane oxidation occurs on the same active surface sites, i.e., lattice oxygen. CO_x formation takes place almost exclusively via consecutive propene oxidation, which involves both lattice and adsorbed oxygen species, with the latter being active in CO formation. However, the adsorbed species play a minor role. CO₂ formation was found to increase in the presence of propene in the reaction feed. Optimized operating conditions for selective propane oxidation were derived and discussed based on the experimental observations with respect to the influence of temperature and partial pressures of O₂, C₃H₆ and C₃H₈ on the reaction. In co-feed mode with a propane to oxygen ratio of 2, optimal catalytic performance is achieved at low partial pressures of oxygen and high temperature. Propene selectivity can be also improved by carrying out the ODP reaction in a periodic mode; that is an alternate feed of propane and air.     

Removal characteristics of nitrogen oxide of high temperature catalytic filters for simultaneous removal of fine particulate and NOx

The CuMnOx catalysts were deep coated into polysulfonamide felts by vacuum suction to simultaneously remove the particulate and nitrogen oxides. This filter consists of a high temperature foam layer as a surface layer, a catalytic pleated felt as a medium layer and glassfiber fabric layer with high temperature phenol resin as a final layer. In this study, the effects of catalyst loading on the pleated felt, operating temperature on nitrogen oxides reduction with NH₃ were mainly investigated. Tests were conducted at operating temperature range from 150 to 250 °C and at face velocity of 1 m/min. Within these ranges, NO removal efficiency was over 90% at the catalyst loading of 350 g/m² and 200 °C.     

Mn-substituted Ca–La–hexaaluminate nanoparticles for catalytic combustion of methane

Mn-substituted Ca–La–hexaaluminate rod-like nanoparticles (Ca_1−xLa_xMnAl₁₁O_19−α) with high surface area ranging from 47 to 80 m²/g for catalytic combustion of methane have been prepared using alumina sol as the (NH₄)₂CO₃ coprecipitation precursor and a supercritical drying (SCD) method. Ca substitution gave rise to the maximum combustion activity (T_10% = 459 °C) at x = 0 owing to the highest surface area. Meanwhile, Ca substitution affects the oxygen sorption property and the oxidation state of Mn ions in the hexaaluminate lattice. Ca_0.6La_0.4MnAl₁₁O_19−α catalyst with high catalytic activities was obtained owing to the excellent performance of activating oxygen.     

Catalytic oxidation for carbon-black simulating diesel particulate matter over promoted Pt/Al2O3 catalysts

Catalytic oxidation activity of carbon-black (CB) simulating the soot of diesel particulate matters to CO₂ over 3Pt/Al₂O₃, 3Pt5Mn/Al₂O₃ and 3Pt/30Ba–Al₂O₃ catalysts is investigated with model gases of diesel emission. In case of the large amount of CB compared to the amount of catalyst (3/1, w/w) in the mixture sample, insufficient oxygen at the point of sudden increase in the amount of CO₂ is leaded to the partial oxidation using the lattice oxygen of the catalyst. And the peaks of CO₂ after the first peak were attributed to the regional combustion of the CB, which was not in contact with catalyst particles. The fresh 3Pt5Mn was estimated to the oxidation states on the catalyst surface by XPS. For used sample at 700 °C, the BEs of Pt 4d5 was revealed to metallic state Pt(0) (314.4 eV) in a predominant levels compared with Pt(II) (317.3 eV). While BEs of Mn 2p were similar to that obtained from the fresh 3Pt5Mn. It is suggested that Pt is in charge of the roles in CB-oxidation, using the lattice oxygen of the catalyst. Two-stage catalytic system with the strategies of promoting the soot oxidation and NO_x reduction, simultaneously, were composed of the CB oxidation catalyst and the diesel oxidation catalyst. The catalytic oxidation of CB was accelerated by activated oxidants and exothermic reaction resulted from the diesel oxidation catalyst, which lies in upstream of two-stage. But the system with the CB oxidation catalyst sited in the upstream showed the initiation of CB oxidation at a lower temperature than the other case. Two-stage catalytic system composed of 3Pt5Mn with CB in the upstream and DOC in the downstream showed high oxidation activity with 95% consumption rate of CB to the total loaded CB in the range of 100–500 °C during the TPR process.     

Cryogenic magnetic properties and magnetocaloric effects (MCE) in B-site disordered RE2CuMnO6 (RE = Gd,Dy, Ho and Er) double perovskites (DP) compounds

In this paper, a detailed investigation with respect to the structural, cryogenic magnetic properties and magnetocaloric performances of RE₂CuMnO₆ (RE = Gd, Dy, Ho and Er) double perovskite (DP) compounds has been performed. All the RE₂CuMnO₆ compounds are confirmed to B-site disordered and crystallized in the GdFeO₃-type structure (Pnma space group, N 62, oP20). The magnetic transition temperatures (T_M) are found to be ~7.5 K for Gd₂CuMnO₆, ~12.1 K for Dy₂CuMnO₆, ~12.2 K for Ho₂CuMnO₆, and ~3.6 K for Er₂CuMnO₆, respectively. Moreover, for checking the magnetocaloric performances several vital parameters including -ΔS_M^max (peak value of magnetic entropy change, -ΔS_M), TEC (3) (temperature averaged -ΔS_M) and RCP (relative cooling powers) are evaluated to be 7.84, 7.73 J/kgK and 151.1 J/kg for Gd₂CuMnO₆, 5.69, 5.59 J/kgK and 180.9 J/kg for Dy₂CuMnO₆, 7.12, 7.05 J/kgK and 192.4 J/kg for Ho₂CuMnO₆, as well as 9.92, 9.60 J/kgK and 195.9 J/kg for Er₂CuMnO₆ under the magnetic field change ΔH = 5 T, respectively.     

MXene supported rhodium nanocrystals for efficient electrocatalysts towards methanol oxidation

Since conventional Pt/carbon catalysts usually suffer from CO poisoning as well as carbon corrosion issues during the methanol oxidation reaction, it is essential to explore high-efficiency Pt-alternative electrocatalysts supported by a robust matrix in the direct methanol fuel cells. Herein, we report a convenient low-temperature approach to the controllable fabrication of well-dispersive Rh nanocrystals in situ grown on Ti₃C₂T_x MXene nanosheets. The ultrathin lamellar MXene structure reveals unique superiorities on the construction of advanced Rh-based hybrid catalysts, which can not only provide a large number of efficient anchoring sites for immobilizing small-sized Rh nanocrystals with abundant exposed catalytic crystal planes, but also enable direct electronic interaction with Rh for strong synergistic effects and facilitate the fast charge transportation during the catalytic process. As a consequence, the resulting Rh/Ti₃C₂T_x hybrid exhibits prominent electrocatalytic properties towards methanol oxidation reaction, such as a large electrochemical active surface area of 71.6 m² g^?1, a high mass activity of 600.2 mA mg^?1, and good long-term stability, all of which are much better than those of conventional carbon-supported Rh as well as Pt/C and Pd/C catalysts.     

Low-temperature catalytic combustion of chlorobenzene over MnOx–CeO2 mixed oxide catalysts

MnO_x–CeO₂ mixed oxide catalysts prepared by sol–gel method were tested for the catalytic combustion of chlorobenzene (CB), as a model of chlorinated aromatic volatile organic compounds (CVOCs). MnO_x–CeO₂ catalysts with the different ratio of Mn/Ce + Mn were found to possess high catalytic activity for catalytic combustion of CB, and MnO_x(0.86)–CeO₂ was the most active catalyst, on which the complete combustion temperature (T_90%) of chlorobenzene was 236 °C. The stability of MnO_x–CeO₂ catalysts in the CB combustion was investigated. MnO_x–CeO₂ catalysts with high Mn/Ce + Mn ratios present high stable activity, which is related to their high ability to remove Cl species adsorbed and a large amount of active surface oxygen.     

Catalytic activity of nanometer La1−xSrxCoO3 (x = 0, 0.2) perovskites towards VOCs combustion

Combustive oxidation of volatile organic compounds (VOCs), such as propyl alcohol, toluene and cyclohexane, were studied. The combustion was catalyzed by nanoparticles of La_1−xSr_xCoO₃ (x = 0, 0.2) perovskites prepared by a co-precipitation method. The results showed high activities of the perovskite catalysts. Compared to LaCoO₃, in particular, La_0.8Sr_0.2CoO₃ was much higher in catalytic ability. The total oxidation of VOCs followed the increasing order: cyclohexane < toluene < propyl alcohol. The T_99% of cyclohexane was 40 °C lower than that of toluene, which appeared to be determined by the bond strengths of the weakest C–H and C–C bonds. The 100-h stability experiments showed that La_1−xSr_xCoO₃ (x = 0, 0.2) perovskite was highly stable.     

Low-temperature continuous wet oxidation of trichloroethylene over CoOx/TiO2 catalysts

TiO₂-supported metal oxides such as CoO_x, CuO_x, NiO_x and FeO_x have been used for catalytic wet oxidation of trichloroethylene (TCE) in a continuous flow type fixed-bed reactor system, and the most promising catalyst for this wet catalysis has been characterized using XPS and XRD techniques. All the supported catalysts gave relatively low conversions for the wet oxidation at 36 °C, except for 5 wt% CoO_x/TiO₂ which exhibited a steady-state conversion of 45% via a transient activity behavior up to 1 h on stream. XPS measurements yielded that a Co 2p_3/2 main peak at 779.8 eV appeared with the 5 wt% CoO_x/TiO₂ catalyst after the continuous wet TCE oxidation at 36 °C for ca. 6 h (spent catalyst) and this binding energy value was equal to that of Co₃O₄ among reference Co compounds used here, while the catalyst calcined at 570 °C (fresh catalyst) possessed a main peak at 781.3 eV, very similar to that for CoTiO_x species such as CoTiO₃ and Co₂TiO₄. Only characteristic reflections for Co₃O₄ were indicated upon XRD measurements even with the fresh catalyst sample. The simplest model, based on these XPS and XRD results, for nanosized Co₃O₄ particles existing with the fresh catalyst could reasonably explain the transient activity behavior observed upon the wet TCE oxidation.     

A new NOx storage-reduction electrochemical catalyst

A new NO_x storage-reduction electrochemical catalyst has been prepared from a polycrystalline Pt film deposited on 8 mol% Y₂O₃-stabilized ZrO₂ (YSZ) solid electrolyte. BaO has been added onto the Pt film by impregnation method. The NO_x storage capacity of Pt-BaO/YSZ system was investigated at 350 °C and 400 °C under lean conditions. Results have shown that the electrochemical catalyst was effective for NO_x storage. When nitric oxides are fully stored, the catalyst potential is high and reaches its maximum. On the other hand, when a part of NO and also NO₂ desorb to the gas phase, the catalyst potential remarkably drops and finally stabilizes when no more NO_x storage occurs but only the reaction of NO oxidation into NO₂. Furthermore, the investigation has clearly demonstrated that the catalyst potential variation versus temperature or chemical composition is an effective indicator for in situ following the NO_x storage-reduction process, i.e. the storage as well as the regeneration phase. The catalyst potential variations during NO_x storage process was explained in terms of oxygen coverage modifications on the Pt.     

Synthesis, characterization and performance of CuO/La2O3 composite catalyst for ammonia catalytic oxidation

This work considers the oxidation of ammonia (NH₃) by selective catalytic oxidation (SCO) over a CuO/La₂O₃ composite catalyst at temperatures between 150 and 400 °C. A CuO/La₂O₃ composite catalyst was prepared by co-precipitation of copper nitrate and lanthanum nitrate at various molar concentrations. This study also considers how the concentration of influent NH₃ (C₀ = 1000 ppm), the space velocity (GHSV = 92,000 l/h), the relative humidity (RH = 12%) and the concentration of oxygen (O₂ = 4%) affect the operational stability and the capacity for removing NH₃. The catalysts that were characterized using FTIR, XRD, UV-Vis, BET and PSA, have shown that the catalytic behavior is related to the copper (II) oxide, while lanthanum (III) oxide may serve only to provide active sites for the reaction during a catalyzed oxidation run. The experimental results show that the extent of conversion of ammonia by SCO in the presence of the CuO/La₂O₃ composite catalyst was a function of the molar ratio. The ammonia was removed by oxidation in the absence of CuO/La₂O₃ composite catalyst, and around 93.0% NH₃ reduction was achieved during catalytic oxidation over the CuO/La₂O₃ (8:2, molar/molar) catalyst at 400 °C with an oxygen content of 4.0%. Moreover, the effect of the reaction temperature on the removal of NH₃ in the gaseous phase was also monitored at a gas hourly space velocity of under 92,000 h^− 1.     

A novel catalyst for diesel soot oxidation

In this study, cobalt and lead based mixed oxide catalysts were tested for their soot oxidation ability. In addition to a mixed oxide formerly marketed as ceramic paint, a home made set was also prepared by incipient wetness impregnation of a cobalt oxide powder with a lead acetate solution and subsequent calcination. The materials investigated in this study were shown to decrease the peak combustion temperature of home made soot from 500 to 385 °C in air. Soot oxidation tests under inert (N₂) atmospheres revealed that the oxidation took place by using the lattice oxygen of the catalyst. Reaction temperature could be further decreased when these mixed oxide catalysts were impregnated with platinum. An optimum platinum loading was determined as 0.5 wt% based on the peak combustion temperature of the soot. The role of Pt was to assist the oxygen transfer from the gas phase to the lattice. It was observed that NO₂ is a better oxidizing agent as compared to air whereas NO had hardly any activity against soot oxidation reaction. When the mixed oxide catalyst was impregnated with platinum, the peak combustion temperature was measured as 310 °C in the presence of NO_x and air. The catalyst's unique performance was in terms of the rate of soot oxidation. Under the experimental conditions studied here, the soot oxidation was so facile that the oxygen in the gas phase was completely depleted. This stream of oxygen depleted and CO enriched gas phase can be used to reduce NO_x in the presence of a downstream or a co-catalyst.     

Oxygen separation from air using Ba0.95La0.05FeO3−δ membranes fitted with porous La1−xSrxFeO3−δ layers

Selective oxygen separation from air was performed using perovskite-type oxide membranes made of Ba_0.95La_0.05FeO_3−δ. We demonstrated that surface modification of Ba_0.95La_0.05FeO_3−δ membranes with La_1−xSr_xFeO_3−δ catalyst layers led to an increase in oxygen permeation fluxes at 700–930 °C. We studied the effects of oxygen vacancy amounts, surface area, particles size, surface treatment of La_1−xSr_xFeO_3−δ on the oxygen permeability of the membranes fitted with La_1−xSr_xFeO_3−δ catalyst layers. Among the catalyst layers tested, the membranes fitted with La_0.9Sr_0.1FeO_3−δ (x=0.1) showed the highest oxygen permeation flux probably because of its higher porosity and uniform morphology without open voids, which would increase the number of surface reaction sites. The obtained results suggest the feasibility of further upgrading the membrane performance by using surface catalyst layers having a homogeneous morphology and a different composition from that of the mother membrane.     

Development and reactivity tests of Ce-Zr-based Claus catalysts for coal gas cleanup

Claus reaction (2H₂S + SO₂ ↔ 3/nS_n + 2H₂O) was used to clean the gasified coal gas and the reactivity of several metal oxide-based catalysts on Claus reaction was investigated at various operating conditions. In order to convert H₂S contained in the gasified coal gas to elemental sulfur during Claus reaction, the catalysts having the high activity under the highly reducing condition with the moisture should be developed. CeO₂, ZrO₂, and Ce_1−xZr_xO₂ catalysts were prepared for Claus reaction and their reactivity changes due to the existence of the reducing gases and H₂O in the fuel gas was investigated in this study. The Ce-based catalysts shows that their activity was deteriorated by the reduction of the catalyst due to the reducing gases at higher than 220 °C. Meanwhile, the effect of the reducing gases on the catalytic activity was not considerable at low temperature. The activities of all three catalysts were degraded on the condition that the moisture existed in the test gas. Specifically, the Ce-based catalysts were remarkably deactivated by their sulfation. The Ce-Zr-based catalyst had a high catalytic activity when the reducing gases and the moisture co-existed in the simulated fuel gas. The deactivation of the Ce-Zr-based catalyst was not observed in this study. The lattice oxygen of the Ce-based catalyst was used for the oxidation of H₂S and the lattice oxygen vacancy on the catalyst was contributed to the reduction of SO₂. ZrO₂ added to the Ce-Zr-based catalyst improved the redox properties of the catalyst in Claus reaction by increasing the mobility of the lattice oxygen of CeO₂.     

Crystal structure,redox properties and catalytic performance of Ga-based mixed oxides for NO reduction by C3H6

A comparative study between LaGa_1−xCu_xO₃ perovskites and ZnGa₂O₄ was conducted to clarify the correlation between crystal structure and redox properties as well as catalytic performance for the reduction of NO by C₃H₆. The oxidation ability of the prepared catalysts decreases following the order LaGa_0.8Cu_0.2O₃ > LaGaO₃ > ZnGa₂O₄. Perovskites, with the general composition of LaGa_1−xCu_xO₃, were found to be suitable materials for NO reduction under scarce oxygen conditions, whereas excess oxygen (O₂ > 1%) led to a significant decline in N₂ yield. On the contrary, the presence of O₂ is necessary for NO conversion to N₂ over the ZnGa₂O₄ spinel, whose SCR activity was moderately enhanced at higher oxygen concentrations. The poor oxidation ability of ZnGa₂O₄ makes it as a promising candidate for lean NO reduction.     

Promoting catalytic performances of Ni-Mn spinel for NH3-SCR by treatment with SO2 and H2O

Ni(0.4)-MnO_x catalyst was prepared by citrate combustion, which showed high catalytic performance for NH₃-SCR reaction. After the resistance tests of SO₂ and H₂O, Ni(0.4)-MnO_x-SH showed better NH₃-SCR activity than that of Ni(0.4)-MnO_x, when the temperature was > 240 °C. The characterizations suggest that Ni(0.4)-MnO_x-SH has more acid sites for ammonia adsorption and far weaker oxidation capacity for NH₃, which resulted in the high catalytic activity at middle-temperature.     

Novel Pt/La1−xBixOF/SBA-16 catalysts for liquid-phase phenol oxidation

Novel catalysts of Pt/La_1−xBi_xOF/SBA-16 (SBA-16: Santa Barbara Amorphous No. 16) were synthesized, and their catalytic activities for phenol decomposition in the liquid phase were investigated. Lanthanum oxyfluoride (LaOF) was selected as the promoter due to its contribution to the smooth migration of oxygen species in the lattice and the acceleration of phenol adsorption on the catalyst surface. Reducible Bi³⁺ ions were introduced in the LaOF lattice to provide oxygen supply ability to LaOF. Among the prepared catalysts, the highest activity was obtained for the 7 wt% Pt/16 wt% La_0.99Bi_0.01OF/SBA-16 catalyst, which could remove 97% of phenol after 5 h of reaction at 80°C in an open-air atmosphere.     

Layered NdBaCo2−xNixO5+δ perovskite oxides as cathodes for intermediate temperature solid oxide fuel cells

The effect of Ni substitution on the crystal chemistry, thermal and electrochemical properties, and catalytic activity for oxygen reduction reaction of the layered NdBaCo_2−xNi_xO_5+δ perovskite oxides has been investigated for 0 ≤ x ≤ 0.6. The oxygen content (5 + δ) and oxidation state of the (Co, Ni) ions in the air-synthesized NdBaCo_2−xNi_xO_5+δ samples decrease with increasing Ni content, accompanied by a structural transition from tetragonal (0 ≤ x ≤ 0.4) to orthorhombic (x = 0.6). Similarly, the thermal expansion coefficient (TEC) and electrical conductivity also decrease with increasing Ni content. The x = 0.2 and 0.4 samples exhibit slightly improved performance as cathodes in single cell solid oxide fuel cell (SOFC) compared to the x = 0 sample, which is in accordance with the ac-impedance data. Among the samples studied, the x = 0.4 sample exhibits a combination of low thermal expansion and high catalytic activity for the oxygen reduction reaction in SOFC.