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.

Excellent Mercury Removal in High Sulfur Atmosphere Using a Novel CuS-BDC-2D Derived by Metal-Organic Frame.

To effectively remove high concentrations of mercury in a high sulfur atmosphere of nonferrous smelting flue gas, a novel two-dimensional CuS-MOF (CuS-BDC-2D) material is synthesized by anchoring S to Cu sites in the Cu-BDC MOF. The highly dispersed CuS active sites and MOF framework structural properties in CuS-BDC-2D enable efficiently collaborate in capturing mercury. CuS-BDC-2D exhibits a layered floral structure with high specific surface area and thermal stability, with poor crystallinity. Compared to CuS and the three-dimensional CuS-MOF (CuS-BDC-3D) structure, CuS-BDC-2D demonstrates significantly higher mercury capture capacity due to the high exposure of active sites and defects sites in the two-dimensional material. Moreover, CuS-BDC-2D exhibits excellent resistance to sulfur, maintaining its high efficiency in removing Hg0 even at high levels of sulfur dioxide (SO2), such as 5000-20,000 ppm. The superior performance of CuS-BDC-2D makes it suitable for controlling mercury emissions in actual nonferrous smelting flue gas. This discovery also paves the way for the development of new mercury adsorbents, which can guide future advancements in this field.

Pilot-Scale Experimental Investigation on Dry Capture of Mercury and SO3 in Smelting Gas of Acid Making.

In this study, a novel dry capture process utilizing a mixed adsorbent of ZnO and CuS was proposed for the simultaneous removal of Hg0 and SO3 in flue gas from zinc smelting, addressing severe mercury pollution and high SO3 concentrations. The experimental results showed that flue gas cooling caused the SO3 to transform into sulfuric acid mist, which changed the reaction mechanism from a gas-solid to a liquid-solid reaction and helped to improve the SO3 removal efficiency. Additionally, properly increasing the absorbent/SO3 molar ratio significantly improved the SO3 removal performance. However, excessive absorbent injection could cause aggregation and uneven dispersion of the absorbent particles in the flue gas, therefore impairing the effectiveness of SO3 capture. Under typical operating conditions (flue gas flow rate of 3500 m3/h, flue gas temperature of 180 °C, ZnO/SO3 molar ratio of 0.74, and residence time of 0.5 s), using a mixed absorbent of ZnO and CuS achieved an SO3 removal efficiency of up to 32.6%, and a total mercury capture at 43.2%, of which the Hg0 removal attained a remarkable 76.3%. These results preliminarily confirm the feasibility of the dry capture technology for simultaneous removal of SO3 and mercury, laying the foundation for further application and promotion.

Efficient removal of Hg0 in flue gas using a novel Sn-based porphyrin polymer.

A Sn-based porphyrin polymer (TAPP(Sn)-FAC) synthesized in a mild condition was introduced for the Hg0 removal in flue gas. The properties characterization of materials revealed the two-dimensional sheet structure, an amorphous structure and high stability of TAPP(Sn)-FAC, and Sn was successfully incorporated into TAPP-FAC in the form of SnN. The removal performance of Hg0 under different conditions was investigated using a lab-scale fixed-bed reactor. TAPP(Sn)-FAC presented an excellent Hg0 removal efficiency from 100 °C to 250 °C, which can reach 8 mg/g of Hg0 capture capacity at 100 °C for 300 min. Besides, TAPP(Sn)-FAC had a strong sulfur and water resistance, and the presence of NO and O2 had a facilitating effect for Hg0 removal. Moreover, the existence of Sn can enhance the Hg0 adsorption and oxidation capacity of TAPP(Sn)-FAC by promoting the electron transfer process. Furthermore, TAPP(Sn)-FAC presented an excellent chemical stability, which was a promising material in the Hg0 removal in flue gas.

Efficient mercury removal in chlorine-free flue gas by doping Cl into Cu2O nanocrystals.

The low content of hydrogen chloride (HCl) in flue gas is difficult to meet the request of Hg0 removal. Here, a small amount of Cl was doped into the crystal lattice of Cu2O nanocrystals (Cl-Cu2O), presenting excellent Hg0 removal efficiency in chlorine-free coal combustion flue gas. SEM, XRD, BET, and XPS characterizations revealed well crystal morphology and structure of Cl-Cu2O catalyst. Besides, Cl-Cu2O had smaller sizes and higher BET surface area compared with Cu2O. Hg0 removal behaviors were studied using a lab-scale fixed-bed reactor. After doping Cl, Hg0 removal efficiency was improved obviously and could reach nearly 100% above 150 â„ƒ, indicating chlorine incorporated into the catalyst lattice had a better role for Hg0 removal. Besides, gas composition effect on Hg0 removal was analyzed. Cl-Cu2O had high sulfur resistance capacity, and Hg0 removal efficiency can still reach above 90% even at 2000 ppm SO2. O2 played a critical role in the Hg0 removal reaction. Furthermore, a plausible mechanism for Hg0 removal was analyzed. Doping Cl into the lattice of Cu2O nanocrystals was beneficial for the activation of molecular oxygen, and generated reactive oxygen species can further activate Cl to participate in the Hg0 removal reaction.

Functional groups influence and mechanism research of UiO-66-type metal-organic frameworks for ketoprofen delivery.

UiO-66 metal-organic framework (MOF) was introduced as ketoprofen delivery system for treating osteoarthritis (OA), and two different kinds of NH2 and NO2 functional groups were grafted into the UiO-66 framework to investigate the effect of functional groups on the drug loading level and release rate. Structural characterization of the samples showed that grafting functional groups had no significant effect on the morphological characteristic and crystal structure of UiO-66. All synthesized MOFs carriers had excellent BET, chemical and thermal stability, though the introduction of NH2 and NO2 functional groups were detrimental for these characteristics. Ketoprofen was successfully loaded on the MOFs carriers, and the results of high performance liquid chromatography (HPLC) indicated UiO-66-NH2 had the highest loading amount (38%). The ketoprofen release experiment manifested that UiO-66-NH2 exhibited lowest release rate and partial release of ketoprofen (about 65%) even after 72 h due to the high hydrogen bonds capacity and alkaline characteristic of -NH2. Furthermore, chondrocyte cytotoxicity experiment manifested that the synthesized MOFs carriers were rather bio-safe, which ensured them to be used as the drug delivery vehicles.

Research of mercury removal from sintering flue gas of iron and steel by the open metal site of Mil-101(Cr).

Metal-organic frameworks (MOFs) adsorbent Mil-101(Cr) was introduced for the removal of elemental mercury from sintering flue gas. Physical and chemical characterization of the adsorbents showed that MIL-101(Cr) had the largest BET surface area, high thermal stability and oxidation capacity. Hg0 removal performance analysis indicated that the Hg0 removal efficiency of MIL-101(Cr) increased with the increasing temperature and oxygen content. Besides, MIL-101(Cr) had the highest Hg0 removal performance compared with Cu-BTC, UiO-66 and activated carbon, which can reach about 88% at 250 °C. The XPS and Hg-TPD methods were used to analyze the Hg0 removal mechanism; the results show that Hg0 was first adsorbed on the surface of Mil-101(Cr), and then oxidized by the open metal site Cr3+. The generated Hg2+ was then combined surface adsorbed oxygen of adsorbent to form HgO, and the open metal site Cr2+ was oxidized to Cr3+ by surface active oxygen again. Furthermore, MIL-101(Cr) had good chemical and thermal stability.

Combined effects of Ag and UiO-66 for removal of elemental mercury from flue gas.

The zirconium metal-organic framework material UiO-66 was doped with Ag nanoparticles and investigated for the removal of elemental mercury (Hg0) in flue gas. Physical and chemical characterization of the adsorbents showed that adding Ag did not change the crystal structure and morphology of the UiO-66. Ag doping can improve the redox activity of UiO-66, and the adsorbent exhibited high thermal stability and surface area. Hg0 removal experiments indicated that UiO-66 exhibited the higher performance compared with P25 and activated carbon, and the addition of Ag exhibited a significant synergistic effect with the UiO-66, which had highest Hg0 adsorption capacity (3.7 mg/g) at 50 °C. Furthermore, the Hg0 removal mechanism was investigated, revealing that Hg0 is removed by the formation of an Ag amalgam and channel adsorption at low temperature, and through Ag-activated oxygen oxidation and channel capture at high temperature.

Comprehensive analysis of differential co-expression patterns reveal transcriptional dysregulation mechanism and identify novel prognostic lncRNAs in esophageal squamous cell carcinoma.

Esophageal squamous cell carcinoma (ESCC) is one of the most common malignancies worldwide and occurs at a relatively high frequency in People's Republic of China. However, the molecular mechanism underlying ESCC is still unclear. In this study, the mRNA and long non-coding RNA (lncRNA) expression profiles of ESCC were downloaded from the Gene Expression Omnibus database, and then differential co-expression analysis was used to reveal the altered co-expression relationship of gene pairs in ESCC tumors. A total of 3,709 mRNAs and 923 lncRNAs were differentially co-expressed between normal and tumor tissues, and we found that most of the gene pairs lost associations in the tumor tissues. The differential regulatory networking approach deciphered that transcriptional dysregulation was ubiquitous in ESCC, and most of the differentially regulated links were modulated by 37 TFs. Our study also found that two novel lncRNAs (ADAMTS9-AS1 and AP000696.2) might be essential in the development of ectoderm and epithelial cells, which could significantly stratify ESCC patients into high-risk and low-risk groups, and were much better than traditional clinical tumor markers. Further inspection of two risk groups showed that the changes in TF-target regulation in the high-risk patients were significantly higher than those in the low-risk patients. In addition, four signal transduction-related DCmRNAs (ERBB3, ENSA, KCNK7, MFSD5), which were differentially co-expressed with the two lncRNAs, might also have the predictive capacity. Our findings will enhance the understanding of ESCC transcriptional dysregulation from a view of cross-link of lncRNA and mRNA, and the two-lncRNA combination may serve as a novel prognostic biomarker for clinical applications of ESCC.

Gaseous Heterogeneous Catalytic Reactions over Mn-Based Oxides for Environmental Applications: A Critical Review.

Manganese oxide has been recognized as one of the most promising gaseous heterogeneous catalysts due to its low cost, environmental friendliness, and high catalytic oxidation performance. Mn-based oxides can be classified into four types: (1) single manganese oxide (MnOx), (2) supported manganese oxide (MnOx/support), (3) composite manganese oxides (MnOx-X), and (4) special crystalline manganese oxides (S-MnOx). These Mn-based oxides have been widely used as catalysts for the elimination of gaseous pollutants. This review aims to describe the environmental applications of these manganese oxides and provide perspectives. It gives detailed descriptions of environmental applications of the selective catalytic reduction of NOx with NH3, the catalytic combustion of volatile organic compounds, Hg0 oxidation and adsorption, and soot oxidation, in addition to some other environmental applications. Furthermore, this review mainly focuses on the effects of structure, morphology, and modified elements and on the role of catalyst supports in gaseous heterogeneous catalytic reactions. Finally, future research directions for developing manganese oxide catalysts are proposed.

Protein coding gene CRNKL1 as a potential prognostic biomarker in esophageal adenocarcinoma.

BACKGROUND: Esophageal adenocarcinoma (EAC) is one of the most aggressive gastroesophageal cancers. PTGS2, EGFR, ERBB2 and TP53 are the traditional EAC prognostic biomarkers, but they are still limited in their ability to effectively predict the overall survival. OBJECTIVES: To identify an improved biomarker for predicting the prognosis of EAC by using the expression profile. MATERIALS AND METHODS: Differential co-expression analysis and differential expression analysis were performed to identify the related genes of EAC. The 5-fold cross-validation was used to select a prognostic biomarker from the 532 EAC related genes. RESULTS: CRNKL1 was identified as a prognostic biomarker to predict the survival of EAC patients. It could significantly stratify EAC patients into high-risk and low-risk groups and was much better than the traditional biomarkers. Furthermore, ROC curve also verified that CRNKL1 with the highest area under the curve (AUC), reaching a sensitivity of 83.33% and a specificity of 78.57%. CONCLUSIONS: Our research proposed that CRNKL1 might be a novel prognostic biomarker with better predictive ability by comparing with the traditional biomarkers, which provided a preferable opportunity in the clinical applications of EAC.

Stabilization of mercury over Mn-based oxides: Speciation and reactivity by temperature programmed desorption analysis.

Mercury temperature-programmed desorption (Hg-TPD) method was employed to clarify mercury species over Mn-based oxides. The elemental mercury (Hg0) removal mechanism over MnOx was ascribed to chemical-adsorption. HgO was the primary mercury chemical compound adsorbed on the surface of MnOx. Rare earth element (Ce), main group element (Sn) and transition metal elements (Zr and Fe) were chosen for the modification of MnOx. Hg-TPD results indicated that the binding strength of mercury on these binary oxides followed the order of Sn-MnOx

Mn-Promoted Co3O4/TiO2 as an efficient catalyst for catalytic oxidation of dibromomethane (CH2Br2).

Brominated hydrocarbon is the typical pollutant in the exhaust gas from the synthesis process of Purified Terephthalic Acid (PTA), which may cause various environmental problems once emitted into atmosphere. Dibromomethane (DBM) was employed as the model compound in this study, and a series of TiO2-supported manganese and cobalt oxide catalysts with different Mn/Co molar ratio were prepared by the impregnation method and used for catalytic oxidation of DBM. It was found that the addition of Mn significantly enhanced the catalytic performance of Co/TiO2 catalyst. Among all the prepared catalysts, Mn(1)-Co/TiO2 (Mn/Co molar ratio was 1) catalyst exhibited the highest activity with T90 at about 325°C and good stability maintained for at least 30h at 500ppm DBM and 10% O2 at GHSV=60,000h(-1), and the final products in the reaction were COx, HBr and Br2, without the formation of Br-containing organics. The high activity and high stability might be attributed to the redox cycle (Co(2+)+Mn(4+)↔Co(3+)+Mn(3+)) over Mn-promoted Co3O4/TiO2 catalyst. Based on the results of in situ DRIFT studies and analysis of products, a plausible reaction mechanism for catalytic oxidation of DBM over Mn-Co/TiO2 catalysts was also proposed.

Different crystal-forms of one-dimensional MnO2 nanomaterials for the catalytic oxidation and adsorption of elemental mercury.

MnO2 has been found to be a promising material to capture elemental mercury (Hg(0)) from waste gases. To investigate the structure effect on Hg(0) uptake, three types of one-dimensional (1D) MnO2 nano-particles, α-, ß- and γ-MnO2, were successfully prepared and tested. The structures of α-, ß- and γ-MnO2 were characterized by XRD, BET, TEM and SEM. The results indicate that α-, ß- and γ-MnO2 were present in the morphologies of belt-, rod- and spindle-like 1D materials, respectively. These findings demonstrated noticeably different activities in capturing Hg(0), depending on the surface area and crystalline structure. The performance enhancement is in the order of: ß-MnO2<γ-MnO2<α-MnO2 at 150°C. The mechanism for Hg(0) removal using MnO2 was discussed with the help of results from H2-TPR, XPS and Hg(0) removal experiments in the absence of O2. It was determined that the oxidizability of three forms of MnO2 increased as follows: ß-MnO2<γ-MnO2<α-MnO2. The mechanism for Hg(0) capture was ascribed to the Hg(0) catalytic oxidation with the reduction of Mn(4+)→Mn(3+)→Mn(2+). Furthermore, the interaction forces between mercury and manganese oxide sites are demonstrated to increase in the following order: ß-MnO2<γ-MnO2<α-MnO2 based on the desorption tests.

Sn-Mn binary metal oxides as non-carbon sorbent for mercury removal in a wide-temperature window.

A series of Sn-Mn binary metal oxides were prepared through co-precipitation method. The sorbents were characterized by powder X-ray diffraction (powder XRD), transmission electronic microscopy (TEM), H2-temperature-programmed reduction (H2-TPR) and NH3-temperature-programmed desorption (NH3-TPD) methods. The capability of the prepared sorbents for mercury adsorption from simulated flue gas was investigated by fixed-bed experiments. Results showed that mercury adsorption on pure SnO2 particles was negligible in the test temperature range, comparatively, mercury capacity on MnOx at low temperature was relative high, but the capacity would decrease significantly when the temperature was elevated. Interestingly, for Sn-Mn binary metal oxide, mercury capacity increased not only at low temperature but also at high temperature. Furthermore, the impact of SO2 on mercury adsorption capability of Sn-Mn binary metal oxides was also investigated and it was noted that the effect at low temperature was different comparing with that of high temperature. The mechanism was investigated by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTs). Moreover, a mathematic model was built to calculate mercury desorption activation energy from Sn to Mn binary metal oxides.