ABSTRACT
BACKGROUND: Endoscopic rubber band ligation (ERBL) is a nonsurgical technique for the treatment of symptomatic internal hemorrhoids but is limited by recurrence and post-procedural pain. AIM: To evaluate satisfaction, long-term recurrence, and post-procedural pain in managing internal hemorrhoids using a combination of polidocanol foam sclerotherapy and ERBL. METHODS: This was a prospective, multicenter, randomized study. A total of 195 consecutive patients diagnosed with grade II-III internal hemorrhoids were enrolled from four tertiary hospitals and randomly divided into a cap-assisted endoscopic polidocanol foam sclerobanding (EFSB) or an ERBL group. All patients were followed-up for 12 months. Symptom-based severity and post-procedural pain were assessed using a hemorrhoid severity score (HSS) and a visual analog scale (VAS). Continuous variables were reported as medians and interquartile range. RESULTS: One hundred and ninety-five patients were enrolled, with 98 in the EFSB group. HSS was lower in the EFSB group than in the ERBL group at 8 weeks [4.0 (3.0-5.0) vs 5.0 (4.0-6.0), P = 0.003] and 12-month [2.0 (1.0-3.0) vs 3.0 (2.0-3.0), P < 0.001] of follow-up. The prolapse recurrence rate was lower in the EFSB group at 12 months (11.2% vs 21.6%, P = 0.038). Multiple linear regression analysis demonstrated that EFSB treatment [B = -0.915, 95% confidence interval (CI): -1.301 to -0.530, P = 0.001] and rubber band number (B = 0.843, 95%CI: 0.595-1.092, P < 0.001) were negatively and independently associated with the VAS score 24 hours post-procedure. The median VAS was lower in the EFSB group than in the ERBL [2.0 (1.0-3.0) vs 3.0 (2.0-4.0), P < 0.001]. CONCLUSION: Cap-assisted EFSB provided long-term satisfaction and effective relief from the recurrence of prolapse and pain 24 hours post-procedure.
Subject(s)
Hemorrhoids , Polidocanol , Recurrence , Sclerosing Solutions , Sclerotherapy , Humans , Polidocanol/administration & dosage , Polidocanol/therapeutic use , Hemorrhoids/therapy , Hemorrhoids/diagnosis , Hemorrhoids/surgery , Middle Aged , Female , Male , Prospective Studies , Sclerotherapy/methods , Treatment Outcome , Ligation/methods , Sclerosing Solutions/administration & dosage , Adult , Aged , Severity of Illness Index , Pain, Postoperative/etiology , Pain, Postoperative/diagnosis , Patient Satisfaction , Pain Measurement , Polyethylene Glycols/administration & dosage , Polyethylene Glycols/therapeutic useABSTRACT
Generally, sulfur poisoning is considered to be one of the main factors contributing to the deactivation of selective catalytic reduction of NOx by CO (CO-SCR) catalysts, while the promotional effect of SO2 on NO reduction over Ir/SiO2 is observed which is an interesting scientific phenomenon. After the introduction of 20 ppm SO2, NOx conversion increased from â¼ 40 % to â¼ 90 % at 275 °C, and N2 selectivity increased from â¼ 80 % to 100 % at 200 â¼ 300 °C. Furthermore, the promoting effect could remain unchanged after 24 h of continuous reaction. However, the temperature point for achieving complete conversion of CO increased from 225 °C to 275 °C after the introduction of SO2. Experimental characterization and theoretical calculation jointly proved that the inhibition of CO oxidation by the generation of sulfate was the main reason for promoting NO reduction. Under the coexistence of O2 and SO2, SO2 was firstly oxidized to SO3 on the iridium surface and generated sulfate species on surface hydroxyl groups of SiO2. Some active sites for O2 adsorption were covered by the generated surface sulfate, and adsorbed CO was hard to react with adsorbed O2, resulting in Langmuir-Hinshelwood (L-H) reaction pathways for CO oxidation being inhibited. Therefore, unoxidized CO reacted with NO adsorbed species and generated N2O to generate N2 and CO2, improving NO reduction. This new insight has implications for understanding the promotional effect of SO2 on NO reduction with CO in the presence of O2.
ABSTRACT
Vonoprazan, a novel acid suppressant and the first potassium-competitive acid blocker, has the potential to enhance the eradication rate of Helicobacter pylori due to its robust acid-suppressing capacity. This study aimed to compare the efficacy of vonoprazan-based dual therapy (vonoprazan-amoxicillin, VA) with vonoprazan-based bismuth quadruple therapy (VBQT) as a first-line treatment for H pylori infection. This retrospective single-center non-inferiority study was conducted in China. Treatment-naive H pylori-positive patients aged 18 to 80 received one of the 2 treatment regimens at our center. The VA group received vonoprazan 20 mg twice daily and amoxicillin 1000 mg 3 times daily for 14 days, whereas the VBQT group received vonoprazan 20 mg, amoxicillin 1000 mg, clarithromycin 500 mg, and bismuth potassium citrate 220 mg twice daily for 14 days. The eradication rate was evaluated 4 to 6 weeks after treatment using the carbon-13/14 urea breath test. Propensity score matching was used to analyze eradication rates, adverse events (AEs), and patient compliance between the 2 groups. Initially, 501 patients were included, and after propensity score analysis, 156 patients were selected for the study. Intention-to-treat analysis showed eradication rates of 87.2% (95% CI, 79.8-94.6%) for the VA group and 79.5% (95% CI, 70.5-88.4%) for the VBQT group (Pâ =â .195). Per-protocol analysis demonstrated rates of 94.4% (95% CI, 89.2-99.7%) for the VA group and 96.8% (95% CI, 92.4-100%) for the VBQT group (Pâ =â .507). Non-inferiority was confirmed between the 2 groups, with P valuesâ <â .025. The VA group showed a lower rate of AEs (10.3% vs 17.9%, Pâ =â .250) compared to the VBQT group. There were no significant differences in patient compliance between the 2 groups. In treatment-naive patients with H pylori infection, both the 14-day VA and VBQT regimens demonstrated comparable efficacy, with excellent eradication rates. Moreover, due to reduced antibiotic usage, lower rate of AEs, and lower costs, VA dual therapy should be prioritized.
Subject(s)
Helicobacter Infections , Helicobacter pylori , Pyrroles , Sulfonamides , Humans , Helicobacter Infections/drug therapy , Helicobacter Infections/etiology , Bismuth/therapeutic use , Retrospective Studies , Propensity Score , Proton Pump Inhibitors/adverse effects , Drug Therapy, Combination , Anti-Bacterial Agents , Amoxicillin/therapeutic use , Clarithromycin/therapeutic use , Treatment OutcomeABSTRACT
Ischaemic bowel disease (ICBD) is a group of intestinal ischaemia syndromes caused by various aetiologies of reduced intestinal blood flow or vascular occlusion. ICBD can present as abdominal pain, bloody stool, and diarrhoea. This disease often occurs in middle-aged and elderly individuals with cardiovascular and cerebrovascular diseases. The incidence of ischaemic bowel disease has been increasing for decades, and it is difficult to diagnose, resulting in rapid disease progression and a high mortality rate. Therefore, fully understanding this disease, improving the diagnosis rate of this disease, and finding appropriate treatment methods are urgently needed to improve the condition and prognosis of patients. Umbilical cord blood stem cells are accessible, have weak immunogenicity, and have various biological functions, such as angiogenesis, inflammation and immune regulation. Many studies have confirmed that cord blood stem cells can relieve ischaemia, and these cells have attracted tremendous amounts of attention in regenerative medicine in recent years. In this paper, we discuss the clinical characteristics of ICBD, analyse the characteristics of human umbilical cord blood mononuclear cells (HUCB-MNCs), and use its to treat ischaemic bowel disease. Additionally, we compare the clinical manifestations and related indicators before and after treatment to evaluate the efficacy and safety of these methods.
Subject(s)
Fetal Blood , Leukocytes , Aged , Middle Aged , Humans , Leukocytes, Mononuclear , Stem Cells , Ischemia , Umbilical CordABSTRACT
BACKGROUND: The vonoprazan (VPZ)-amoxicillin (AMO) dual therapy (VA) demonstrates a satisfactory eradication rate for Helicobacter pylori (H. pylori ). However, the optimal dosage of AMO in this regimen remains uncertain. The objective of this study is to investigate the efficacy of different doses of AMO in the VA regimen for first-line treatment of H. pylori infection. METHODS: A total of 192 treatment-naive H. pylori -infected patients were randomly assigned to one of three groups: low-dose VA (LD-VA: VPZ 20â mg b.i.d + AMO 750â mg t.i.d), moderate-dose VA (MD-VA:VPZ 20â mg b.i.d + AMO 1000â mg t.i.d), and high-dose VA (HD-VA: VPZ 20â mg b.i.d + AMO 1250â mg t.i.d). All groups received 14 days of treatment. The study evaluated and compared the eradication rates, adverse events (AEs), and patient compliance among the three groups. RESULTS: Eradication rates for LD-VA, MD-VA, and HD-VA were 76.6% (49/64), 79.7% (51/64), and 84.4% (54/64), respectively, as determined by intention-to-treat analysis; 90.6% (48/53), 94.3% (50/53), and 98.1% (53/54) according to per-protocol analysis; 89.1% (49/55), 94.4% (51/54), and 96.4% (54/56) with modified intention-to-treat analysis (all P â >â 0.05). Although not statistically significant, numerically higher eradication rates were observed with the higher dose AMO VA regimen. There were no statistically significant differences in the incidence of AEs and compliance among the three VA regimens. CONCLUSION: Fourteen-day VA regimens with AMO doses exceeding 2 g/day demonstrated satisfactory eradication rates. HD-VA therapy is potentially the most effective regimen. Large-sample clinical trials are required to further validate these findings.
Subject(s)
Amoxicillin , Anti-Bacterial Agents , Drug Therapy, Combination , Helicobacter Infections , Helicobacter pylori , Proton Pump Inhibitors , Pyrroles , Sulfonamides , Humans , Helicobacter Infections/drug therapy , Sulfonamides/administration & dosage , Amoxicillin/administration & dosage , Male , Female , Middle Aged , Helicobacter pylori/drug effects , Anti-Bacterial Agents/administration & dosage , Anti-Bacterial Agents/adverse effects , Prospective Studies , Pyrroles/administration & dosage , Pyrroles/adverse effects , Adult , China , Treatment Outcome , Proton Pump Inhibitors/administration & dosage , Proton Pump Inhibitors/adverse effects , AgedABSTRACT
This study explores the use of large language models (LLMs) in interpreting and predicting experimental outcomes based on given experimental variables, leveraging the human-like reasoning and inference capabilities of LLMs, using selective catalytic reduction of NOx with NH3 as a case study. We implement the chain of thought (CoT) concept to formulate logical steps for uncovering connections within the data, introducing an "Ordered-and-Structured" CoT (OSCoT) prompting strategy. We compare the OSCoT strategy with the more conventional "One-Pot" CoT (OPCoT) approach and with human experts. We demonstrate that GPT-4, equipped with this new OSCoT prompting strategy, outperforms the other two settings and accurately predicts experimental outcomes and provides intuitive reasoning for its predictions.
ABSTRACT
For the drawbacks of phase change materials such as poor shape stability and weak solar-thermal conversion ability, a rotunda-shaped carboxymethylcellulose/carbon nanotube aerogel (CA) with three-dimensional network was constructed by freeze casting with a special mold, and then impregnated with polyethylene glycol (PEG) in this work. The PEG/CA had an enthalpy of 183.21â J/g, and a thermal conductivity of 0.324â W m-1 K-1, which was 57 % higher than the pure PEG. The ability of PEG/CA to convert solar energy to thermal energy was a positive correlation between the inclusion of CNTs and the composite material's thermal conductivity. Under simulated sunlight, its solar-thermal conversion efficiency reaches 94.41 %, and after 10â min of irradiation, the surface temperature can reach 65 °C and the internal temperature can reach 44.67 °C. This rotunda-shaped PEG/CA is promising for the efficient use of renewable solar energy due to its strong solar-thermal conversion and thermal storage capabilities.
ABSTRACT
Catalytic oxidation, an end-of-pipe treatment technology for effectively purifying volatile organic compounds (VOCs), has received widespread attention. The crux of catalytic oxidation lies in the development of efficient catalysts, with their optimization necessitating a comprehensive analysis of the catalytic reaction mechanism. Two-dimensional (2D) ultra-thin nanomaterials offer significant advantages in exploring the catalytic oxidation mechanism of VOCs due to their unique structure and properties. This review classifies strategies for regulating catalytic properties and typical applications of 2D materials in VOCs catalytic oxidation, in addition to their characteristics and typical characterization techniques. Furthermore, the possible reaction mechanism of 2D Co-based and Mn-based oxides in the catalytic oxidation of VOCs is analyzed, with a special focus on the synergistic effect between oxygen and metal vacancies. The objective of this review is to provide valuable references for scholars in the field.
ABSTRACT
Mining the scientific literature, combined with data-driven methods, may assist in the identification of optimized catalysts. In this paper, we employed interpretable machine learning to discover ternary metal oxides capable of selective catalytic reduction of nitrogen oxides with ammonia (NH3-SCR). Specifically, we devised a machine learning framework utilizing extreme gradient boosting (XGB), identified for its optimal performance, and SHapley Additive exPlanations (SHAP) to evaluate a curated database of 5654 distinct metal oxide composite catalytic systems containing cerium (Ce) element, with records of catalyst composition and preparation and reaction conditions. By virtual screening, this framework precisely pinpointed a CeO2-MoO3-Fe2O3 catalyst with superior NOx conversion, N2 selectivity, and resistance to H2O and SO2, as confirmed by empirical evaluations. Subsequent characterization affirmed its favorable structural, chemical bulk properties and reaction mechanism. Demonstrating the efficacy of combining knowledge-driven techniques with experimental validation and analysis, our strategy charts a course for analogous catalyst discoveries.
ABSTRACT
In this work, the phosphomolybdate (HPMo) modification strategy was applied to improve the N2 selectivity of MnCo-BTC@SiO2 catalyst for the selective catalytic reduction of NOx, and further, the mechanism of HPMo modification on enhanced catalytic performance was explored. Among MnCo-BTC@SiO2-x catalysts with different HPMo concentrations, MnCo-BTC@SiO2-0.75 catalyst exhibited not only the highest NH3-SCR performance (â¼95% at 200-300°C) but also the best N2 selectivity (exceed 80% at 100-300°C) due to the appropriate redox capacity, greater surface acidity. X-ray photoelectron spectrometer (XPS) and temperature programmed reduction of H2 (H2-TPR) results showed that the modification with HPMo reduced the oxidation-reduction performance of the catalyst due to electron transfer from Mo5+ to Mn4+/Mn3+ and prevent the excessive oxidation of ammonia adsorption species. NH3 temperature-programmed desorption of (NH3-TPD) results showed that the modification with HPMo could significantly improve the surface acidity and NH3 adsorption, which enhance the catalytic activity and N2 selectivity. In-situ diffused reflectance infrared Fourier transform spectroscopy (in-situ DRIFTS) revealed that modification with HPMo increased significantly the amount of adsorbed NH3 species on the Bronsted acid site and CB/CL, it suppressed the production of N2O by inhibiting the production of NH species, the deep dehydrogenation of ammonia adsorption species. This study provided a simple design strategy for the catalyst to improve the low-temperature catalytic performance and N2 selectivity.
Subject(s)
Ammonia , Silicon Dioxide , Ammonia/chemistry , Oxidation-Reduction , Temperature , Cold Temperature , CatalysisABSTRACT
Chlorinated benzene-containing compounds (CBCs) refer to volatile organic compounds which simultaneously contain benzene rings and Cl atoms. It has been widely believed to cause serious harm to human health and the natural environment due to high toxicity, high persistence, and refractory degradation, thus, it is urgent to develop CBC abatement technology. In this review, several CBCs control techniques are compared, and the catalytic oxidation technology stands out for its good low-temperature activity and chlorine resistance of metal oxide catalysts. Then, the common and individual reaction pathways and water impact mechanisms of CBC catalytic oxidation on transition metal catalysts are concluded. Subsequently, three typical metal oxides (namely, VOx, MnOx, and CeO2-based catalysts) are introduced in the catalytic degradation of CBCs, whose catalytic activity influence factors are also proposed on active components, support properties, surface acidity, and nanostructure (crystal, morphology, etc.). Furthermore, the effective strategies to enhance the REDOX cycle and surface acidic sites are summarized by the doping of metals, the modification of support or/and acidic groups, and the construction of nanostructures. Finally, the key points for efficient catalyst design are speculated. This review may provide ideas for the breakthroughs of activity-enhanced strategies, the design of efficient catalysts, and research on reaction-promoted mechanisms.
ABSTRACT
Ce1-xZrxO2 composite oxides (molar, x = 0-1.0, interval of 0.2) were prepared by a cetyltrimethylammonium bromide-assisted precipitation method. The enhancement of silver-species modification and catalytic mechanism of adsorption-transformation-desorption process were investigated over the Ag-impregnated catalysts for low-temperature selective catalytic oxidation of ammonia (NH3-SCO). The optimal 5 wt.% Ag/Ce0.6Zr0.4O2 catalyst presented good NH3-SCO performance with >90% NH3 conversion at temperature (T) ≥ 250°C and 89% N2 selectivity. Despite the irregular block shape and underdeveloped specific surface area (â¼60 m2/g), the naked and Ag-modified Ce0.6Zr0.4O2 solid solution still obtained highly dispersed distribution of surface elements analyzed by scanning electron microscope-energy dispersive spectrometer (SEM-EDS) (mapping), N2 adsorption-desorption test and X-ray diffraction (XRD). H2 temperature programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS) results indicated that Ag-modification enhanced the mobility and activation of oxygen-species leading to a promotion on CeO2 reducibility and synergistic Ag0/Ag+ and Ce4+/Ce3+ redox cycles. Besides, Ag+/Ag2O clusters could facilitate the formation of surface oxygen vacancies that was beneficial to the adsorption and activation of ammonia. NH3-temperature programmed desorption (NH3-TPD) showed more adsorption-desorption capacity to ammonia were provided by physical, weak- and medium-strong acid sites. Diffused reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments revealed the activation of ammonia might be the control step of NH3-SCO procedure, during which NH3 dehydrogenation derived from NHx-species and also internal selective catalytic reduction (i-SCR) reactions were proposed.
Subject(s)
Ammonia , Silver , Ammonia/chemistry , Catalysis , Cetrimonium , Oxidation-Reduction , Oxides , OxygenABSTRACT
Energy-saving and efficient monolithic catalysts are hotspots of catalytic purification of industrial gaseous pollutants. Here, we have developed an electrothermal catalytic mode, in which the ignition temperature required for the reaction is provided by Joule heat generated when the current flows through the catalyst. In this paper, Mn/NiAl/NF, Mn/NiFe/NF and Mn/NF metal-based monolithic catalysts were prepared using nickel foam (NF) as the carrier for thermal and electrothermal catalysis of n-heptane. The results indicated that Mn-based monolithic catalysts exhibit high activity in thermal and electrothermal catalysis. Mn/NiFe/NF achieve conversion of n-heptane more than 99% in electrothermal catalysis under a direct-current (DC) power of 6 W, and energy-saving is 54% compared with thermal catalysis. In addition, the results indicated that the introduction of NiAl (or NiFe) greatly enhanced the catalytic activity of Mn/NF, which attributed to the higher specific surface area, Mn3+/Mn4+, Ni3+/Ni2+, adsorbed oxygen species (Oads)/lattice oxygen species (Olatt), redox performance of the catalyst. Electrothermal catalytic activity was significantly higher than thermal catalytic activity before complete conversion, which may be related to electronic effects. Besides, Mn/NiFe/NF has good cyclic and long-term stability in electrothermal catalysis. This paper provided a theoretical basis for applying electrothermal catalysis in the field of VOCs elimination.
Subject(s)
Nickel , Oxides , Manganese Compounds , OxygenABSTRACT
BACKGROUND: Perivascular epithelioid cell tumor (PEComa) represents a group of rare mesenchymal tumors. PEComa can occur in many organs but is rare in the colorectum, especially in children. Furthermore, PEComa is a rare cause of intussusception, the telescoping of a segment of the gastrointestinal tract into an adjacent one. We describe a rare case of pediatric PEComa complicated with intussusception and anal incarceration, and conduct a review of the current literature. CASE SUMMARY: A 12-year-old girl presented with abdominal pain and abdominal ultrasound suggested intussusception. Endoscopic direct-vision intussusception treatment and colonoscopy was performed. A spherical tumor was discovered in the transverse colon and removed by surgery. Postoperative pathologic analyses revealed that the tumor volume was 5.0 cm × 4.5 cm × 3.0 cm and the tumor tissue was located in the submucosa of the colon, arranged in an alveolar pattern. The cell morphology was regular, no neoplastic necrosis was observed, and nuclear fission was rare. The immunohistochemical staining results were as follows: Human melanoma black 45 (HMB 45) (+), cluster of differentiation 31 (CD31) (+), cytokeratin (-), melanoma-associated antigen recognized by T cells (-), smooth muscle actin (-), molleya (-), desmin (-), S-100 (-), CD117 (-), and Ki67 (positive rate in hot spot < 5%). Combined with the results of pathology and immunohistochemistry, we diagnosed the tumor as PEComa. Postoperative recovery was good at the 4 mo follow-up. CONCLUSION: The diagnosis of PEComa mainly depends on pathology and immunohistochemistry. Radical resection is the preferred treatment method.
ABSTRACT
The iron and steel industry (ISI) is one of the most energy-intensive industries in China, which makes a substantial contribution to the emissions of air pollutants. Among the various manufacturing processes, sintering is the major emitting process, which shares over half of the emissions of sulfur dioxide (SO2), nitrogen oxide (NOx) and particulate matter (PM) for the entire industry. In this study we made a comprehensive evaluation of the air pollutant emissions from the sintering process of China's ISI in 2017 based on the Continuous Emission Monitoring System (CEMS) database and estimated the future reduction potentials. We found that there was a general decreasing trend of emission concentrations in the sintering flue gas in response to the strengthened emission control policies, but the mild increase of the oxygen content in the second half of the year flattened the decreasing trend, indicating the necessity for simultaneous control of the oxygen content in the flue gas. Despite the relative high standard-reaching rates of 90% to the emission concentration limits in GB 28662-2012, the standard-reaching rates to the ultra-low emission standards were only 12%, 40% and 27% for NOx, SO2 and PM respectively, with the lowest value mostly occurred in the western provinces. In 2017, the NOx, SO2 and PM emissions from the sintering process were 378.6 kt, 169.0 kt and 51.9 kt, respectively. If the ultra-low emission standards were met, the corresponding NOx, SO2 and PM emissions would decrease by 69.9%, 52.9%, and 56.4% respectively, illustrating large emission reducing potentials by achieving the ultra-low emission standards.
Subject(s)
Air Pollutants , Air Pollution , Air Pollutants/analysis , Air Pollution/analysis , Air Pollution/prevention & control , China , Environmental Monitoring , Iron , Oxygen , Particulate Matter/analysis , SteelABSTRACT
China is the largest iron and steel producer and consumer in the world. The iron and steel manufacture, especially the sintering process, is energy-intensive, and contributes substantially to air pollutant emissions in China. Compared with other regions, the Fenwei Plain, a coal base, has a heavy industry concentration, and high pollutant emission total amount. In addition, urban air pollution has rebounded, and the pollutants concentrations in many cities have increased rather than decreased. In this study, we investigated the inter-annual trends of particulate matter (PM), sulfur dioxide (SO2) and nitrogen oxide (NOx) from the sintering process of iron and steel industry (ISI) in the Fenwei Plain and the surrounding regions in China from 2014 to 2017 based on the Continuous Emission Monitoring System (CEMS). We found that the oxygen content of the flue gas is the key to judge whether the sintering flue gas air pollutant emission concentration can meet the standard. Therefore, we adopted the converted concentration by the reference oxygen content in the final analysis. Overall, the SO2 and PM emission concentrations exhibit a downward trend from 2014 to 2017, in response to the strengthening of the emission control policies and standards in the ISI, whereas the NOx emission concentration did not change significantly during the same period The emission factors (EFs) of PM, NOx and SO2 obtained in this study are lower than previous estimates. In 2017, the SO2 and PM emissions were 27% and 32% lower than the levels in 2014.While NOx was 22% higher than the level in 2014. Our study confirmed the effectiveness of current emission control policies and standards in the iron and steel sector. However, the levels of NOx emissions were still high until 2017, illustrating the urgent need for more advanced emission control technologies to further reduce NOx emissions from the sintering flue gas in China.
Subject(s)
Air Pollutants , Air Pollution , Air Pollutants/analysis , Air Pollution/analysis , China , Environmental Monitoring , Iron , Metallurgy , Particulate Matter/analysis , SteelABSTRACT
NH3-SCR performances were explored to the relationship between structure morphology and physio-chemical properties over low-dimensional ternary Mn-based catalysts prepared by one-step synthesis method. Due to its strong oxidation performance, Sn-MnOx was prone to side reactions between NO, NH3 and O2, resulting in the generation of more NO2 and N2O, here most of N2O was driven from the non-selective oxidation of NH3, while a small part generated from the side reaction between NH3 and NO2. Co or Ni doping into Sn-MnOx as solid solution components obviously stronged the electronic interaction for actively mobilization and weakened the oxidation performance for signally reducing the selective tendency of side reactions to N2O. The optimal modification resulted in improving the surface area and enhancing the strong interaction between polyvalent cations in Co/Ni-Mn-SnO2 to provide more surface adsorbed oxygen, active sites of Mn3+ and Mn4+, high-content Sn4+ and plentiful Lewis-acidity for more active intermediates, which significantly broadened the activity window of Sn-MnOx, improved the N2 selectivity by inhibiting N2O formation, and also contributed to an acceptable resistances to water and sulfur. At low reaction temperatures, the SCR reactions over three catalysts mainly obeyed the typical Elye-rideal (E-R) routs via the reactions of adsorbed l-NHx (x = 3, 2, 1) and B-NH4+ with the gaseous NO to generate N2 but also N2O by-products. Except for the above basic E-R reactions, as increasing the reaction temperature, the main adsorbed NOx-species were bidentate nitrates that were also active in the Langmuir-Hinshelwood reactions with adsorbed l-NHx species over Co/Ni modified Mn-SnO2 catalyst.
Subject(s)
Ammonia , Oxides , Catalysis , Nitrogen Oxides , Oxidation-ReductionABSTRACT
In this research, one-step synthesis of redox co-precipitation method (using sodium lauryl sulfate, KMnO4, and metal precursor) was well applicable in universally preparing low-dimensional Me-MnOx nanosheet catalysts with different metal doping (Me=Co, Ni, or Sn). NH3-SCR activity was explored to the relationship with structure morphology and physio-chemical properties via the characterization techniques of SEM, XRD, XPS, H2-TPR, and NH3-TPD. It was found that Ni-MnOx has a relatively poor activity at low-down temperature but was improved as the reaction temperature rising. Co-MnOx presented a relatively stable catalytic activity of which the NOx conversion rate can be maintained 80~90% in a wide temperature window of 100-250 °C with relatively better N2 selectivity. Compared with Co- or Ni-modified MnOx, Sn-MnOx catalyst has an excellent low-temperature catalytic activity (93% NOx conversion at 100 °C) that was maintained > 80% before 200 °C but with poor selectivity to N2. Due to its nanosheet-structured solid solution structure, Sn-MnOx promoted the interaction between MnOx and SnO2 with the increased contents of adsorbed oxygen and also the numbers of surface Lewis acid sites, which integrally promoted the NH3-SCR reaction at low temperature and also contributed to an acceptable resistances to water and sulfur. High content of adsorbed oxygen was beneficial to improve the catalytic activity at lower temperatures, while the electron cycle interaction of different metal valence ions will play a more important role with the increase of reaction temperature.
Subject(s)
Ammonia , Oxides , Ammonia/chemistry , Catalysis , Oxidation-Reduction , Oxides/chemistry , TemperatureABSTRACT
Improving the SO2 resistance of catalysts is crucial to driving commercial applications of Mn-based catalysts. In this work, the phosphotungstic acid (HPW) modification strategy was applied to improve the N2 selectivity, SO2 and H2O resistance of the Mn-Ce-Co catalyst, and further, the mechanism of HWP modification on enhanced catalytic performance was explored. The results showed that HPW-Mn-Ce-Co catalyst exhibits higher NOx conversion (~100% at 100-250 °C) and N2 selectivity (exceed 80% at 50-350 °C) due to more oxygen vacancies, greater surface acidity, and lower redox capacity. In situ diffused reflectance infrared Fourier transform spectroscopy (in situ DRIFTS) reveal that HPW changed the reaction path of Mn-Ce-Co catalysts, promoted the adsorption and activation of NH3, and reduced the effect of SO2 on the active bidentate nitrate species, and thereby exhibiting good SO2 resistance. X-ray photoelectron spectrometer (XPS) and NH3 temperature-programmed desorption of (NH3-TPD) results show that HPW can inhibit the formation of metal sulfate, and SO2 can be combined with Ce species more easily. The generated Ce2(SO3)3 can not only protect Mn species but also increase the acid sites and weaken the poisoning effect of metal sulfate. This study provides a simple design strategy for the catalyst to improve the low-temperature catalytic performance and toxicity resistance.
Subject(s)
Cerium , Sulfur Dioxide , Ammonia , Catalysis , Cobalt , Manganese , Oxidation-Reduction , Phosphotungstic AcidABSTRACT
The unexpected phenomenon in which different transition metals (Co, Ni and Cu) presented significant variation of participation levels as the auxiliaries in Mn-based bimetallic oxide catalysts were reported here. It is found that the Co element more easily to form Mn enriched surface bimetallic oxides with Mn than Ni and Cu, resulting in Co-MnOx exhibited the best deNOx activity and SO2 tolerance, followed by Ni-MnOx and Cu-MnOx. The role of different transition metal and structure-activity relationships were systematically investigated by advanced techniques including Synchrotron XAFS and in situ DRIFTs analysis. The excellent activity of Co-MnOx was related to its unique Mn-enriched surface (Co2+)tet(Mn3+ Co3+)octO4 structure with Mn cations occupying the octahedral sites, which is superior to the Ni-MnOx and Cu-MnOx with Mn-lean surface. In addition, the reaction energy barrier of Co-MnOx is weakened due to the lower electron cloud density around the Mn atom as compared to Ni-MnOx and Cu-MnOx. Moreover, Co-MnOx benefiting from the rapid electron migration between Mn and Co, more active bidentate/bridged nitrates could react with adsorbed NH3 in faster reaction rates following the L-H mechanism.