H2 Temperature-programmed Reduction Research Articles

Salt assistant bimetallic sludge-derived porous carbon for efficient peroxymonosulfate activation

The development of cost-effective, environmentally benign, and high-performance peroxymonosulfate (PMS) activation towards wastewater treatment is still considered a challenge. In this work, the sludge-derived porous carbon loaded with bimetal oxides (DSC-FeMn) was fabricated by molten salt assistant strategy using the combination of zinc chloride, metal ions and Fe containing sludge. The obtained DSC-FeMn exhibited high catalytic activity for nearly 100 % 4-chlorophenol (4-CP) removal within 30 min with the k of 0.304 min−1, which was 1.07 and 11.94 times that of the single Fe and Mn-sludge-derived carbon (DSC-Fe, DSC-Mn), respectively. Quenching experiments, electron paramagnetic resonance tests (EPR), X-ray photoelectron spectroscopy (XPS), H2-temperature programmed reduction (H2-TPR) and electrochemical experiments proved that the radical pathway, dominated by OH and SO4−, led to the excellent degradation performance of DSC-FeMn, which was attributed to the redox cycling between Fe and Mn. This study provides a new idea for sludge resource utilization, and it deepens the understanding of the mechanism of PMS activation by the synergistic interaction between bimetal.

Catalytic upgrading of Naomaohu coal pyrolysis volatiles over NiAl and NiLiAl oxides

Catalytic upgrading of volatiles is an essential technology to improve the product distribution of pyrolysis for the clean and efficient utilization of low-rank coals. In this work, novel acid-base bifunctional catalysts composed of Ni/Li/Al oxides were designed and prepared using LDH precursors with tunable chemical composition and structural properties. The catalysts were systematically characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), physisorption, NH3-temperature programmed desorption (NH3-TPD), CO2-temperature programmed desorption (CO2-TPD), H2-temperature programmed reduction (H2-TPR), and scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS). A two-stage fixed bed reactor was employed to evaluate the performance of the catalysts. Characterization results suggest that the crystal size of NiO and the surface area of the catalyst decreased with increasing Li content and decreasing Ni content in the catalyst, while the pore volume and pore diameter were positively correlated with Li content. Moreover, the addition of Li reduced the amount of weak acid sites and raised the amount of total basic sites. Consequently, the bifunctional catalysts boosted the yield of light tar and the contents of aromatics and phenols in tar. Specifically, with the highest total acid sites (569 μmol/g) promoting the cracking of heavy pitch components, Ni2.5Li0.5Al1 decreased the content of pitch in tar to 23.8 wt%, representing a 42.7 % drop from the corresponding non-catalytic pyrolysis. Accordingly, it improved the light tar yield to 7.2 wt%, which was 18 % higher than non-catalytic pyrolysis. 450 °C is identified as a suitable temperature for the catalytic upgrading of volatiles from Naomaohu coal; higher catalysis temperatures at 500 °C and 550 °C led to lower tar yield and lower phenols content, along with higher gas yield and more carbon deposition.

Magnesium borate whiskers/La2-XCeXZr2O7 catalysts preparation on cordierite honeycomb ceramic surfaces for soot catalytic oxidation͏

Magnesium borate whiskers were used to prepare a hierarchical microstructure on cordierite ceramic substrate through the precipitation-molten salt method. The La2-XCeXZr2O7 catalyst was then loaded onto the magnesium borate whiskers to form the hierarchical microstructure. The Ce-doped catalysts exhibited a significant improvement in the catalytic activity of soot combustion compared to the La2Zr2O7 catalyst. The study employed various techniques to characterize the structural morphology and phase composition, including scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), Fourier transform-infrared spectroscopy (FT-IR), and X-ray diffraction (XRD). The growth of Magnesium borate whiskers (Mg2B2O5) with diameters of 100–200 nm and lengths of 2–5 μm were grown and tightly bonded to the cordierite ceramic substrate to mimic the structure of human respiratory system cilia. This could improve the filtration efficiency of soot in car exhaust. BET analysis showed that the specific surface area of cordierite increased from 0.684 m2/g to 1.363 m2/g after whisker growth. The study confirmed that the whiskers were firmly attached to the cordierite ceramic substrate, as demonstrated by the binding strength experiments. The addition of Ce metal has been found to significantly enhance soot combustion due to the presence of more active oxygen species and superior mobility of lattice oxygen species with more oxygen vacancies. The catalyst's intrinsic redox property was characterized using X-ray photoelectron spectroscopy (XPS) and H2 temperature-programmed reduction (H2-TPR). The semi-quantitative thermogravimetric analysis (TG-DTG) and the temperature-programmed oxidation (TPO) of catalysts showed that Z-La1.9Ce0·1Zr2O7 exhibited the highest catalytic activity for soot combustion, with an ignition temperature of 268 °C, a peak temperature of 418 °C, and a temperature of 90 % soot conversion of 464 °C. Furthermore, cyclic stability experiments demonstrate that the Z-La1.9Ce0·1Zr2O7 catalyst exhibits excellent structural stability and consistent catalytic performance. This distinctive microstructure holds great potential for applications in the field of DPF.

Revealing the effect of synthetic method on integrated CO2 capture and conversion performance of Ni-Na2ZrO3 bifunctional materials

Integrated CO2 capture and utilization by reverse water gas shift (ICCU-RWGS) reaction for syngas production for C1 chemical industry has gained increasing attention. Designing highly active bifunctional materials that enables CO2 adsorption and in-situ conversion is essential. In this work, Ni-Na2ZrO3 bifunctional materials are prepared by different synthetic methods for ICCU-RWGS. N2 physisorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), CO2 temperature-programmed desorption (CO2-TPD) and H2 temperature-programmed reduction (H2-TPR) analysis reveals that Ni-Na2ZrO3-CP prepared by the co-precipitation (CP) method shows small Ni crystalline size, moderate surface basicity, and excellent reducibility. ICCU-RWGS performance is investigated under isothermal conditions of 650 °C, 10 %CO2 and 35 %H2. The results indicate that Ni-Na2ZrO3-CP demonstrates excellent performance in ICCU-RWGS, with a notable CO2 capture capacity of 3.76 mmol CO2/g and a CO production rate of 3.10 mmol CO/g. Additionally, it exhibits relatively good operational stability. Detailed reaction paths of the ICCU-RWGS procedure for the Ni-Na2ZrO3 bifunctional materials are proposed. The findings will shed new perspectives on the design of synthetic bifunctional catalysts for ICCU-RWGS.

Interpretation of H2-TPR from Cu-CHA Using First-Principles Calculations.

Temperature-programmed reduction and oxidation are used to obtain information on the presence and abundance of different species in complex catalytic materials. The interpretation of the temperature-programmed reaction profiles is, however, often challenging. One example is H2 temperature-programmed reduction (H2-TPR) of Cu-chabazite (Cu-CHA), which is a material used for ammonia assisted selective catalytic reduction of NOx (NH3-SCR). The TPR profiles of Cu-CHA consist generally of three main peaks. A peak at 220 °C is commonly assigned to ZCuOH, whereas peaks at 360 and 500 °C generally are assigned to Z2Cu, where Z represents an Al site. Here, we analyze H2-TPR over Cu-CHA by density functional theory calculations, microkinetic modeling, and TPR measurements of samples pretreated to have a dominant Cu species. We find that H2 can react with Cu ions in oxidation state +2, whereas adsorption on Cu ions in +1 is endothermic. Kinetic modeling of the TPR profiles suggests that the 220 °C peak can be assigned to Z2CuOCu and ZCuOH, whereas the peaks at higher temperatures can be assigned to paired Z2Cu and Z2CuHOOHCu species (360 °C) or paired Z2Cu and Z2CuOOCu (500 °C). The results are in good agreement with the experiments and facilitate the interpretation of future TPR experiments.

Perovskite-Derivative Ni-Based Catalysts for Hydrogen Production via Steam Reforming of Long-Chain Hydrocarbon Fuel

Large-scale hydrogen production by the steam reforming of long-chain hydrocarbon fuel is highly desirable for fuel-cell application. In this work, LaNiO3 perovskite materials doped with different rare earth elements (Ce, Pr, Tb and Sm) were prepared by a sol-gel method, and the derivatives supported Ni-based catalysts which were successfully synthesized by hydrogen reduction. The physicochemical properties of the as-prepared catalysts were characterized by powder X-ray diffraction, high-resolution transmission electron microscopy, N2 adsorption–desorption isotherms, H2 temperature-programmed reduction, and X-ray photoelectron spectroscopy. The catalytic performance of the as-prepared catalysts for hydrogen production was investigated via the steam reforming of n-dodecane. The results showed that the catalyst forms perovskite oxides after calcination with abundant mesopores and macropores. After reduction, Ni particles were uniformly distributed on perovskite derivatives, and can effectively reduce the particles’ sizes by doping with rare earth elements (Ce, Pr, Tb and Sm). Compared with the un-doped catalyst, the activity and hydrogen-production rate of the catalysts are greatly improved with rare earth element (Ce, Pr, Tb and Sm)-doped catalysts, as well as the anti-carbon deposition performance. This is due to the strong interaction between the uniformly distributed Ni particles and the support, as well as the abundant oxygen defects on the catalyst surface.

Modification of SmMn2O5 Catalyst with Silver for Soot Oxidation: Ag Loading and Metal–Support Interactions

A series of Ag-modified manganese-mullite (SmMn2O5) catalysts with different Ag contents (1, 3, and 6 wt.%) were prepared via a citric acid sol–gel method for catalytic soot oxidation. The catalysts were characterized by powder X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), Raman spectroscopy, transmission electron microscopy (TEM), high-resolution transmission electron microscopy analysis (HRTEM), X-ray photoelectron spectroscopy (XPS), and H2 temperature-programmed reduction (H2-TPR). The soot oxidation activity of the mullite was significantly promoted by the addition of silver and affected by the loading amount of the metal. Herein, the influences of silver loading on the metal size distribution and its interactions with the mullite were studied. Based on these characterizations, a possible soot oxidation reaction mechanism was proposed for silver-modified SmMn2O5.

The pivotal role of oxygen vacancy and surface hydroxyl in the adsorption and activation of CO2 on ceria-zirconia mixed oxide

Ceria-zirconia mixed metal oxide along with pure ceria and zirconia were prepared by the co-precipitation method and characterized by N2-Physisorption, X-ray diffraction (XRD), H2-temperature programmed reduction (H2-TPR), CO-TPR with mass spectroscopy (CO-TPR/MS), oxygen storage capacity (OSC), CO and CO2-temperature programmed desorption with MS (TPD/MS), Raman spectroscopy, XPS, and diffuse reflectance infrared Fourier transform Spectroscopy (DRIFTS) techniques. Furthermore, Density Functional Theory (DFT) calculations were performed to acquire molecular insights into the role of oxygen vacancies and surface hydroxyl species in CO2 adsorption and subsequent activation. Our experimental and theoretical results corroborated the fact that the incorporation of zirconium ions into the ceria matrix enhanced the overall CO2 adsorption and activation by forming thermally stable surface species, which were eventually detected by DRIFTS. Additionally, DFT calculations revealed the oxygen vacancy mediated change in the electronic structure of ceria-zirconia mixed oxide, which had been argued to improve its catalytic activity. Furthermore, the oxygen vacancy formation energy (OVFE), oxygen storage capacity (OSC) and CO2 adsorption energies were correlated to augment the importance of these properties.

Selective hydrodeoxygenation of guaiacol to phenol over CoFe/reduced graphene oxide

A reduced graphene oxide (rGO)-supported CoFe bimetallic catalyst (CoFe/rGO) was synthesized and used for hydrodeoxygenation of guaiacol to phenol (Ph). The CoFe/rGO catalyst without reduction pretreatment showed excellent catalytic performance, achieving 94.0 mol% conversion and 70.8 mol% selectivity to Ph at mild reaction temperature and low H2 pressure. The microstructure and chemical composition of the CoFe/rGO catalyst were characterized by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Raman spectroscopy, and H2 temperature-programmed reduction (H2-TPR) characterization analysis. Co and Fe are supported on rGO in forms of the isolated metal atoms embedded in the rGO matrix and the CoFe oxide nanoparticles attached on rGO surface. Fe as a promoter weakens the hydrogenation activity of Co to benzene ring and dramatically improves the selectivity to Ph. The unique of rGO on constructing catalytic active sites and the synergistic effect of Co and Fe bimetals make CoFe/rGO an excellent catalyst.

Mechanisms and site requirements for NO and NH3 oxidation on Cu/SSZ-13

Two series of Cu/SSZ-13 catalysts were synthesized via aqueous solution and solid-state ion exchange using SSZ-13 supports of varying Si/Al ratios. The isolated and multinuclear Cu content of these catalysts were determined by H2 temperature programmed reduction (H2-TPR). Multinuclear Cu in these catalysts, including in situ Cu-dimers formed from ZCuIIOH coupling and permanent CuO clusters, are active species for dry NO oxidation. NH3 oxidation on these catalysts follows an internal SCR (i-SCR) mechanism, i.e., a portion of NH3 is first oxidized to NO, then NO is selectively reduced by the remaining NH3 to N2. NH3 oxidation displays distinct kinetic behavior below ∼300 °C and above ∼400 °C. At low temperature the results indicate that NH3-solvated mobile Cu-ions are the active centers. CuO clusters, when present, also contribute to the low temperature activity by catalyzing NH3 oxidation to NO. At high temperature, in situ Cu-dimers and CuO clusters catalyze NH3 oxidation to NO, and isolated Cu-ions catalyze SCR to realize the cascade turnovers. For both NO and NH3 oxidation, Cu-dimers balanced by framework charges of close proximity appear to be more active than Cu-dimers balanced by distant framework charges. However, the former Cu-dimers are less stable than the latter and tend to split into monomers in the presence of vicinal Brønsted acid sites. Via density functional theory (DFT) calculations, the i-SCR mechanism for low temperature NH3 oxidation, i.e., the energetic favorability for the involvement of the NO intermediate, is justified. The DFT results also agree with experimental data that the formation of Cu-dimers from ZCuIIOH dimerization is essential for NH3 oxidation at high temperature.

Cu modified VOx/Silicalite-1 catalysts for propane dehydrogenation in CO2 atmosphere

Propane dehydrogenation in CO2 atmosphere (PDH-CO2) is of interest with a potential to raise propane conversion. Here the catalytic performance of Cu modified 10VOx/Silicalite-1(S-1) for PDH-CO2 is presented for the first time. The initial propane conversion of 68.8% on 0.5Cu-10VOx/S-1 was reached from 59.3% on 10VOx/S-1, along with the CO2 conversion of 44.5% from 32.4%. The role of S-1 support and Cu modification were elucidated by means of X-ray diffraction (XRD), ultraviolet–visible diffuse reflection (UV–Vis), NH3/CO2 temperature-programmed desorption (NH3/CO2-TPD), H2 temperature-programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS) characterization. While dispersing VOx, non-acidic S-1 minimized the side reactions usually occurring on the strong acidic sites. Cu modification promoted the dispersion of VOx and enabled 10VOx/S-1 exposing more weak acidic sites and basic sites, boosting respectively the adsorption of propane and CO2, for concurrently accelerating the reverse water gas shift (RWGS). Moreover, the highly dispersed V5+ was formed on the surface whereas the percentage of inactive V3+ decreased.

Double-stable Ce-based oxide: Capturing atomic precious metals via Ostwald ripening for multicomponent three-way catalysts construction

Precious metal catalysts have been widely used to catalyze various reactions, particularly three-way catalysts for automobile exhaust purification. Pt, Pd, and Rh, which are dispersed on Ce-based oxides that store and release oxygen, serve as the active center of a catalyst. However, methods to construct multifunctional three-way catalysts to maximize their efficiency and stabilize them are lacking. In this study, Ce-based oxides with a double-stable mode were synthesized to capture and stabilize the precious metals Pt and Rh migrated by Ostwald ripening (OR), and a multicomponent three-way catalyst was accurately synthesized, which showed good catalytic activity and thermal stability. The origin of Ce-based oxides with a dual-stable mode was studied by TEM, XRD, oxygen storage/release capacity and rate test, and XPS. AC-STEM, EXAFS, in situ diffuse reflectance Fourier transform infrared, and H2 temperature-programmed reduction studied the OR migration of precious metals and the composition change after aging. Results showed that in the lean/rich oxygen alternating shift atmosphere containing CO, the proportion of OR migration of Pt and Rh precious metals whose initial state is single atoms can reach 100 %. This discovery provides a basic understanding of the sintering mechanism of precious metals, which is of great importance for the development and industrial application of three-way catalysts.

Cobalt catalyzed ethane dehydrogenation to ethylene with CO2: Relationships between cobalt species and reaction pathways

TiO2, ZrO2 and a series of TiO2-ZrO2 (TxZ1, x means the atomic ratio of Ti/Zr = 10, 5, 1, 0.2 and 0.1) composite oxide supports were prepared through co-precipitation, and then 3 wt% Co was loaded through wetness impregnation methods. The obtained 3 wt% Co/TiO2 (3CT), 3 wt% Co/ZrO2 (3CZ) and 3 wt% Co/TxZ1 (3CTxZ1) catalysts were evaluated for the oxidative ethane dehydrogenation reaction with CO2 (CO2-ODHE) as a soft oxidant. 3CT1Z1 catalyst exhibits excellent catalytic properties, with C2H4 yield, C2H6 conversion and CO2 conversion about 24.5 %, 33.8 % and 18.0 % at 650 °C, respectively. X-Ray Diffraction (XRD), in-situ Raman, UV–vis diffuse reflectance spectra (UV–vis DRS), H2 temperature-programmed reduction (H2-TPR), Electron paramagnetic resonance (EPR) and quasi in-situ X-ray Photoelectron Spectroscopy (XPS) have been utilized to thoroughly characterize the investigated catalysts. The results revealed that 3CT1Z1 produced TiZrO4 solid solution with more metal defect sites and oxygen vacancies (Ov), promoting the formation of Co2+-TiZrO4 structure. Furthermore, the presence of Ov and Ti3+can facilitate the high dispersion and stabilization of Co2+, as well as suppressing the severe reduction of Co2+, leading to superior ethane oxidative dehydrogenation activity. Besides, less Co0 is beneficial to ODHE reaction, because of its promotion effects for reverse water gas shift reaction; however, more Co0 results in dry reforming reaction (DRE). This work will shed new lights for the design and preparation of highly efficient catalysts for ethylene production.

Controlling Product Distribution of Polyethylene Hydrogenolysis Using Bimetallic RuM3 (M = Fe, Co, Ni) Catalysts.

Plastic hydrogenolysis is an attractive approach for producing value-added chemicals due to its mild reaction conditions, but controlling product distribution is challenging due to the formation of undesired CH4. This work reports several bimetallic RuM3/CeO2 (M = Fe, Co, Ni) catalysts that shift the product of low-density polyethylene hydrogenolysis toward longer-chain hydrocarbons. These catalysts were characterized by using X-ray absorption fine structure spectroscopy, electron microscopy imaging, and H2 temperature-programmed reduction. The combined catalytic evaluation and characterization results revealed that the product distribution was regulated by the formation of bimetallic alloys. A model compound, n-hexadecane, was selected to further understand the differences in hydrogenolysis over the Ru-based catalysts. Although a longer reaction time shifted the product toward smaller molecules, the bimetallic (RuCo3/CeO2) catalyst limited the further conversion of C2-C5 into CH4. This work highlights the role of bimetallic alloys in tailoring the interaction with hydrocarbons, thereby controlling the product distribution of polymer hydrogenolysis.

Redox regulation of Ni hydroxides with controllable phase composition towards biomass-derived polyol electro-refinery.

Electrocatalytic refinery from biomass-derived glycerol (GLY) to formic acid (FA), one of the most promising candidates for green H2 carriers, has driven widespread attention for its sustainability. Herein, we fabricated a series of monolithic Ni hydroxide-based electrocatalysts by a facile and in situ electrochemical method through the manipulation of local pH near the electrode. The as-synthesized Ni(OH)2@NF-1.0 affords a low working potential of 1.36 VRHE to achieve 100% GLY conversion, 98.5% FA yield, 96.1% faradaic efficiency and ∼0.13 A cm-2 of current density. Its high efficiency on a wide range of polyol substrates further underscores the promise of sustainable electro-refinery. Through a combinatory analysis via H2 temperature-programmed reduction, cyclic voltammetry and in situ Raman spectroscopy, the precise regulation of synthetic potential was discovered to be highly essential to controlling the content, phase composition and redox properties of Ni hydroxides, which significantly determine the catalytic performance. Additionally, the 'adsorption-activation' mode of ortho-di-hydroxyl groups during the C-C bond cleavage of polyols was proposed based on a series of probe reactions. This work illuminates an advanced path for designing non-noble-metal-based catalysts to facilitate electrochemical biomass valorization.

Catalytic Hydrogenation Property of Methyl Benzoate to Benzyl Aldehyde over Manganese-Based Catalysts with Appropriate Oxygen Vacancies

The synthesis of benzaldehyde, a compound widely utilized in food, medicine, and cosmetics, was achieved through a one-step catalytic hydrogenation using the cost-effective raw material, methyl benzoate. This process aligns with the principles of atom economy and green production. Despite the development of numerous high-performance catalysts by scholars, the challenge remains in achieving lower reaction temperatures, ideally below 400 °C. In this study, a series of MnOx/γ-Al2O3 catalysts were meticulously prepared using the precipitation-impregnation method. These catalysts featured supports calcined at various temperatures and distinct manganese active components. Characterization techniques such as X-ray diffraction (XRD), N2 physical adsorption, Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), H2 temperature programmed reduction (H2-TPR), and NH3 temperature-programmed desorption (NH3-TPD) were employed to analyze the structure and surface properties of the catalysts. Notably, the optimized reaction temperature was found to be 360 °C. The catalyst exhibited the most favorable performance when the calcination temperature of the support was 500 °C and the Mn/Al molar ratio reached 0.18. Under these conditions, the catalyst demonstrated the most suitable oxygen vacancy concentration, yielding impressive results: a conversion rate of 87.90% and a benzaldehyde selectivity of 86.1%. These achievements were attained at 360 °C, atmospheric pressure, a hydrogen to methyl benzoate molar ratio of 40:1, and a Gas Hourly Space Velocity (GHSV) of 800 h−1. This research underscores the potential for optimizing catalysts to enhance the efficiency and sustainability of benzaldehyde synthesis.

Structure-Function Relationship of Highly Reactive CuOx Clusters on Co3 O4 for Selective Formaldehyde Sensing at Low Temperatures.

Designing reactive surface clusters at the nanoscale on metal-oxide supports enables selective molecular interactions in low-temperature catalysis and chemical sensing. Yet, finding effective material combinations and identifying the reactive site remains challenging and an obstacle for rational catalyst/sensor design. Here, the low-temperature oxidation of formaldehyde with CuOx clusters on Co3 O4 nanoparticles is demonstrated yielding an excellent sensor for this critical air pollutant. When fabricated by flame-aerosol technology, such CuOx clusters are finely dispersed, while some Cu ions are incorporated into the Co3 O4 lattice enhancing thermal stability. Importantly, infrared spectroscopy of adsorbed CO, near edge X-ray absorption fine structure spectroscopy and temperature-programmed reduction in H2 identified Cu+ and Cu2+ species in these clusters as active sites. Remarkably, the Cu+ surface concentration correlated with the apparent activation energy of formaldehyde oxidation (Spearman's coefficient ρ = 0.89) and sensor response (0.96), rendering it a performance descriptor. At optimal composition, such sensors detected even the lowest formaldehyde levels of 3 parts-per-billion (ppb) at 75°C, superior to state-of-the-art sensors. Also, selectivity to other aldehydes, ketones, alcohols, and inorganic compounds, robustness to humidity and stable performance over 4 weeks are achieved, rendering such sensors promising as gas detectors in health monitoring, air and food quality control.

Low temperature oxidation of diesel soot particles over one-dimensional 2 × 3 tunnel-structured Na2Mn5O10 catalysts

Tunnel-structured manganese oxides have drawn widespread research attention due to their excellent oxidation properties for the soot oxidation reaction. In this study, a series of romanechite Na2Mn5O10 catalysts with a 2 × 3 tunnel structure were synthesized via a facile hydrothermal method. The as-synthesized catalysts were investigated using X-ray diffraction, scanning and transmission electron microscopy, H2 and soot temperature-programmed reduction, O2 temperature-programmed desorption, NO temperature-programmed oxidation, X-ray photoelectron spectroscopy, and other measurements. Among all the catalysts, the Na1MnyOδ-120 catalyst exhibited the best catalytic performance for soot combustion, with T10, T50, and T90 values of 281 ℃, 317 ℃, and 343 ℃, respectively, which were considerably reduced to 271 ℃, 310 ℃, and 335 ℃ in the existence of 10% H2O. The results of multiple characterization methods indicated that the Na2Mn5O10 catalysts exhibit good reducibility, strong oxygen adsorption and activation capacity, and NO to NO2 oxidation ability. Moreover, the active sites (Mn and oxygen vacancies) and reaction mechanism (Langmuir–Hinshelwood) were also revealed by in-situ DRIFT and density functional theory calculations results. This study details a new strategy for the design and synthesis of efficient soot oxidation catalysts with practical application prospects.

Hydrothermal Synthesis of MnO2 Microspheres and Their Degradation of Toluene.

Various urchin-like MnO2 materials were obtained with a facile hydrothermal method through controlling the Mn precursor, reaction time, and reaction temperature. The property of MnO2 materials was characterized by scanning electron microscopy, X-ray diffraction, and H2 temperature-programmed reduction. The results showed that the Mn precursor could significantly impact the morphology of as-prepared MnO2. When the precursor was Mn(CH3COO)2·4H2O, the MnO2 morphology consisted of tennis-like microspheres assembled by nanorods. While the precursor was MnCl2·4H2O, the sample morphology was a chestnut shell, and the samples were sea urchin microspheres, as the precursor was MnSO4·H2O. At the same time, the morphology of MnO2 was affected by hydrothermal time and temperature. The nanoneedles on the microsphere surface gradually lengthened with increasing hydrothermal time and hydrothermal temperature, until nanowires were formed. MnO2 crystallinity was also influenced by hydrothermal temperature. It was γ-MnO2 as the temperature was 50 and 80 °C while evolved to be α-MnO2 and β-MnO2 when the temperature increased to 140 °C. As MnO2 (MnO2-1 h, MnO2-2 h, MnO2-4 h, and MnO2-6 h) was prepared to degrade toluene, all the samples could completely catalyze toluene at the temperature of 225 °C. However, the MnO2-4 h showed the best catalytic effect at a lower temperature.

Ce doped V-W/Ti as selective catalytic reduction catalysts for cement kiln flue gas denitration.

In cement industry, the selection of catalyst temperature window and the inhibition effect of dust composition in flue gas on catalyst are the key issues of flue gas denitrification. In this article, a pilot study with Ce doped V-W/Ti catalyst on the removal of NOx by selective catalytic reduction with ammonia (NH3-SCR) from the cement kiln flue gas was presented. Cement kiln dust loading on catalysts obviously decreased the NO conversion in the absence of SO2 and H2O, while the denitration efficiency restored from 75 to 98% at 280 ℃ after SO2 and H2O introduced into the reaction system, which mainly because the SO2 may enhance the acidic site on the catalyst surface, and prefer to be bonded with the coordinated Ca species, releasing the active sites poisoned by dust. The NH3-temperature programmed desorption (NH3-TPD), X-ray photoelectron spectroscopy (XPS), and H2-temperature programmed reduction (H2-TPR) detections were performed to reveal that the appropriate Ce and W ratios catalyst contributed better denitrification activity. The optimum ratio of Ce doped catalyst was amplified to form the standard honeycomb monomer catalyst, and then, the activity of catalyst was verified on the side line of cement kiln. The effect of temperature and space velocity on denitrification efficiency was investigated, and the denitration efficiency reached to 92.5% at 300℃ and 3000h-1 space velocity. Moreover, the life of catalyst was verified and predicted by GM (1,1) grey model. The study realized the innovation from the laboratory data rules to the industrial pilot application, providing positive promoting value for the industrial large-scale demonstration application of the catalyst.