Lean methane combustion over zeolite-supported Pd catalysts: Structure-performance relationship and deactivation mechanism.

Zeolites are a promising support for Pd catalysts in lean methane (CH4) combustion. Herein, three types of zeolites (H-MOR, H-ZSM-5 and H-Y) were selected to estimate their structural effects and deactivation mechanisms in CH4 combustion. We show that variations in zeolite structure and surface acidity led to distinct changes in Pd states. Pd/H-MOR with external high-dispersing Pd nanoparticles exhibited the best apparent activity, with activation energy (Ea) at 73 kJ/mol, while Pd/H-ZSM-5 displayed the highest turnover frequency (TOF) at 19.6 × 10-3 sec-1, presumably owing to its large particles with more step sites providing active sites in one particle for CH4 activation. Pd/H-Y with dispersed PdO within pore channels and/or Pd2+ ions on ion-exchange sites yielded the lowest apparent activity and TOF. Furthermore, Pd/H-MOR and Pd/H-ZSM-5 were both stable under a dry condition, but introducing 3 vol.% H2O caused the CH4 conversion rate on Pd/H-MOR drop from 100% to 63% and that on Pd/H-ZSM-5 decreased remarkably from 82% to 36%. The former was shown to originate from zeolite structural dealumination, and the latter principally owed to Pd aggregation and the loss of active PdO.

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

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

Synergistic Elimination of NOx and Chlorinated Organics over VOx/TiO2 Catalysts: A Combined Experimental and DFT Study for Exploring Vanadate Domain Effect.

Vanadium-based catalysts have been extensively applied for the synergistic control of NOx and chlorinated organics. However, how the vanadia species affect the reaction activity and products distribution, and what are the dominant reaction sites of these vanadia species are still unknown. Herein, we investigated the reaction characteristics of monomeric and polymeric vanadate domains for the catalytically synergistic elimination of NOx and chlorobenzene (CB). Density functional theory (DFT) calculations and experimental investigations have been combined to clarify the effects of different vanadyl species on the synergistic reaction. It was noted that the main adsorption site of CB on the monomeric domain was V-OH bond, and that on the polymeric one was V═O bond. The monomeric vanadyl was favorable for converting the Lewis V═O into Brønsted V-OH, which provided sufficient H protons for HCl formation, whereas the polymeric species could effectively retain the V4+/V5+ redox cycle, and yielded superior activity in CB catalytic oxidation (CBCO) reaction. However, the abundant oxygen vacancies and the inclined accumulation of Cl by forming the V-Cl bands led to significant polychlorinated byproducts on the polymeric vanadyl catalysts. Our work gives the first insight into different vanadate domain effects on the synergistic reaction, and is expected to provide theoretical basis for efficient design of the vanadium-based catalysts toward multipollutants elimination.

Preparation of MnO2 decorated Co3Fe1Ox powder/monolithic catalyst with improved catalytic activity for toluene oxidation.

In this paper, KMnO4 was used to pre-treat Co3Fe-layered double hydroxides (LDH) precursor to prepare MnO2 decorated Co3Fe1Ox catalyst. The toluene oxidation performance of the catalyst was investigated systematically. The optimized 0.1MnCF-LDO catalyst exhibited the best catalytic performance, and the temperatures of 50% and 90% toluene conversion (T50 and T90) were 218 and 243°C, respectively. The apparent activation energy (Ea) was 31.6 kJ/mol. The characterization results showed that the pre-redox reaction by KMnO4 could increase the specific surface area, Co3+ species amount and oxygen defect concentration of the catalyst, which are the main reason of the improved toluene catalytic activity. Besides, this method was also applied to enhance toluene oxidation of iron mesh based monolithic catalyst. The 0.1MnCF-LDO/Iron mesh (IM) catalyst showed a 90% toluene conversion at around 316°C which was much lower than that of without MnO2 addition (359°C). In addition, the water resistant of all the catalysts was studied as well, all the samples showed relatively good water resistance. The toluene conversion still remained to be over >80% even in the presence of 10 vol.% water vapor.

Dissolved black carbon enhanced the aquatic photo-transformation of chlortetracycline via triplet excited-state species: The role of chemical composition.

Dissolved black carbon (DBC), widely distributed in the aquatic environments, can accelerate sunlight-driven photo-transformation of micropollutants, however the photosensitization mechanisms are not clear. Herein, the DBC was extracted from bamboo biochar and fractionated by molecular weight (i.e. <10 k, <3 k, and <1 k Da). The effects of DBC on chlortetracycline (CTC) photolysis behaviors, and the role of chemical composition (i.e., molecular weight and chemical structure) in DBC-mediated photo-transformation were investigated. The results showed that DBC could accelerate CTC photodegradation significantly. At low DBC concentrations (<6.0 mg C/L), the photodegradation rate constant of CTC increased from 0.0299 to 0.0416 min-1 with the increasing DBC concentration. Via quenching experiment, the triplet excited-state of DBC was identified as the dominant reactive intermediate with >90% contribution to total CTC photodegradation. In addition, it was found that the photosensitive efficiency of DBC increased as the molecular weight decreased, and the stronger photosensitization ability exhibited in DBC with low-molecular weight was potentially attributed to its higher content of carbonyl compounds. The observed photosensitive efficiency of DBC sharply decreased after reduction by NaBH4, further confirming the key role of carbonyl compounds in the photosensitization process. Moreover, based on the result of photoproducts, the amidogen in CTC was verified to be susceptible to react with 3DBC*.

Preparation and Characterization of Highly Efficient CuFe Mixed Oxides for Total Oxidation of Toluene.

In this study, Cu/Fe type mixed oxides catalysts with different ratios of metal irons are successfully synthesized via fixed hydrothermal treatment. The prepared samples were then characterized by a combination of several techniques, such as XRD, BET, SEM, H2-TPR and FT-IR. The catalytic activity enhanced with the increasing amount of Cu in the HT-precursors, but it decreases when the ratio of Cu/Fe is above 4. The influence of calcination temperature was also studied in the search of highly dispersed active catalysts. The catalytic test indicated that the Cu/Fe mixed oxides possessed outstanding highly activity towards toluene oxidation. The highest catalytic activity was exhibited by Cu4Fe-400 of which the T50 and T90 reaches at about 258 °C and 294 °C respectively.

Photoaging processes of polyvinyl chloride microplastics enhance the adsorption of tetracycline and facilitate the formation of antibiotic resistance.

Microplastics (MPs), antibiotics and microorganism ubiquitously coexist in aquatic environments. MPs inevitably undergo photoaging processes in aquatic environments, affecting the interactions between MPs and antibiotics and the antibiotic resistance of microorganism. In this study, the impact of photoaging processes of MPs on their adsorption behavior of tetracycline (TC) and related formation of antibiotic resistance were investigated. It was found that the photoaging processes significantly increased the adsorption capacity of TC onto MPs, with the Qe increasing from 0.387 to 0.507 mg/g at 288 K and from 0.507 to 0.688 mg/g at 308 K. The site energy distribution (SED) analysis further confirmed that the enhanced adsorption capacity was attributed to more high-energy adsorption sites acquired from MPs photoaging processes. Moreover, the enhanced adsorption of TC further facilitated the formation of seven antibiotic resistance genes (i.e., tetA, tetB, tetC, tetD, tetE, tetG, tetK) when MPs adsorbed with TC was covered by biofilm. This study helps comprehensively understand the environmental behaviors of co-existing MPs, antibiotics and microorganisms, providing a theoretical basis for evaluating and mitigating their coexistence risks.

Inhibitory effects of antioxidant moieties in humic substances on phototransformation of chlortetracycline mediated by the algae extracellular organic matter.

In algae rich waters, sunlight-driven transformation of antibiotics could be accelerated via sensitization by algae extracellular organic matter (EOM), and this photosensitization process will be affected by coexisting humic substances. In this study, we explored the effect and mechanism of humic substances on photodegradation of chlortetracycline (CTC) mediated by EOM. We found that humic substances exhibited a marked inhibitory effect on the EOM-mediated photodegradation of CTC. Given that humic substances exhibited little effects on the EOM-mediated formation of triplet state species, the quenching effect of humic substances on reactive species was excluded. The inhibitory effect of humic substances was mainly attributed to the back reduction of CTC oxidation intermediates by the antioxidant moieties in humic substances. The ozone oxidation treatment for humic substances was applied to destroy antioxidant moieties. After ozonation, the inhibitory effects of humic substances were greatly decreased, confirming the dominant role of antioxidant moieties in humic substances, which inhibited CTC photodegradation mediated by EOM via reducing oxidation intermediates of CTC. This back reduction was further verified to be exergonic via reactive Gibbs free energy, indicating the back reduction by humic substances of CTC oxidation intermediates could occur spontaneously. The present study will be helpful for predicting the fate and risk of CTC in algae rich water environments, and is of great significance for the study of phototransformation of other antibiotics.

The complete chloroplast genome sequence of Potentilla tanacetifolia Willd. ex Schltdl.

Potentilla tanacetifolia Willd. ex Schltdl. is a perennial herb in China, which has high ecological and economic values. Its complete chloroplast genome was reported in this study for the first time. The whole chloroplast genome was 157, 051 base pairs in length with 129 genes, including 84 protein-coding genes, 37 tRNAs, and 8 rRNAs. In addition, phylogenetic analysis showed a sister relationship between P. tanacetifolia and P. chinensis.

Synthesis of ZSM-5/Siliceous Zeolite Composites for Improvement of Hydrophobic Adsorption of Volatile Organic Compounds.

In this research, we investigated the hydrophobicity and dynamic adsorption-desorption behaviors of volatile organic compounds (VOCs) by applying different optimized coating dosage (25, 50, and 75%) on designed novel ZSM-5/MCM-41 and ZSM-5/Silicalite-1 hierarchical composites. The relatively large specific surface area and pore volume of adsorbents ZSM-5/MCM-41 and ZSM-5/Silicalite-1 composites with excellent stability were affirmed by ex-situ XRD, FTIR, BET, SEM, and water contact angle analyses. Regarding, toluene adsorption-desorption investigation, ZSM-5/MCM-41 composite lead a longer stable toluene breakthrough time no matter under dry or 50% humid conditions. However, under different loading dosage condition, the breakthrough time of 75% coating ratio was the longest, which was 1.6 times as long as that of pure ZSM-5 under wet adsorption. Meanwhile, the complete elimination of toluene for ZSM-5/MCM-41-75% was done by largest desorption peak area and the lowest desorption temperature of 101.9°C, while, the largest contact angle of ZSM-5/MCM-41-75% was 17.0° higher than pure ZSM-5 zeolite. Therefore, we believe that the present hydrophobic sorbent will provide new insight with great research potential for removing low concentration of VOCs at industrial scale.

Microporous Zeolite@Vertically Aligned Mg-Al Layered Double Hydroxide Core@Shell Structures with Improved Hydrophobicity and Toluene Adsorption Capacity under Wet Conditions.

Zeolites have been recognized as one type of the most promising adsorbents for capturing volatile organic compounds (VOCs, e.g., toluene), but their performance suffers severely from water vapor under wet conditions. In this contribution, we demonstrated that the hydrophobicity of microporous zeolites can be significantly improved by coating vertically aligned LDH nanoplatelets when the contact angle is increased from 16.5-20.1° to 44.4-64.2°. The toluene adsorption capacity of such synthesized zeolite@LDH core@shell composites in wet conditions can thus be largely enhanced when the breakthrough time is increased from 6.4-10.8 to 20.1-27.5 min.

Analysis of organic and elemental carbon in heating and non-heating periods in four locations of Beijing.

The concentrations of elemental carbon (EC) and organic carbon (OC) in PM2.5 atmospheric aerosol were measured at four different sites in Beijing: Beijing Olympic Forest Park (OF), Jiufeng National Forest Park (JF), Beijing Forestry University campus lawn (G), and roads near the Beijing Forestry University (S). The winter heating period concentrations were 30-45% higher than the spring non-heating period. Possible reasons for this could be the severe convective weather in spring due to the temperate monsoon, deposition of PM2.5 to plants in spring, stable atmospheric conditions in winter, and/or a greater number of sources of carbonaceous aerosols in winter. The proportion of total carbon (i.e. EC + OC) in PM2.5 in Beijing is high. The OC/EC value was 2.45 (OF) and 2.39 (JF) in winter and 1.6 (OF) and 1.43 (JF) in spring. These ratios and the high correlation of OC with EC in the winter samples indicate a strong primary source of OC. Eight carbon fractions from the four different sampling locations were analysed, and the OC1-4 values were found to vary considerably. In winter, the OC1 values from all four sites were higher than the spring values. Although there were differences at each site, the percentages of OC2, OC3, EC1-OP, and EC2 were the largest. Secondary organic carbon (SOC) formed during long-range transport from the emission sources to the monitoring sites, and the increase of OC2 and OC3 concentrations could be associated with SOC.

Deposition velocity of PM2.5 in the winter and spring above deciduous and coniferous forests in Beijing, China.

To estimate the deposition effect of PM2.5 (particle matter with aerodynamic diameter <2.5 µm) in forests in northern China, we used the gradient method to measure the deposition velocity of PM2.5 during the winter and spring above a deciduous forest in Olympic Forest Park and above a coniferous forest in Jiufeng National Forest Park. Six aerosol samplers were placed on two towers at each site at heights of 9, 12 and 15 m above the ground surface. The sample filters were exchanged every four hours at 6∶00 AM, 10∶00 AM, 2∶00 PM, 6∶00 PM, 10∶00 PM, and 2∶00 AM. The daytime and nighttime deposition velocities in Jiufeng Park and Olympic Park were compared in this study. The February deposition velocities in Jiufeng Park were 1.2±1.3 and 0.7±0.7 cm s-1 during the day and night, respectively. The May deposition velocities in Olympic Park were 0.9±0.8 and 0.4±0.5 cm s-1 during the day and night, respectively. The May deposition velocities in Jiufeng Park were 1.1±1.2 and 0.6±0.5 cm s-1 during the day and night, respectively. The deposition velocities above Jiufeng National Forest Park were higher than those above Olympic Forest Park. The measured values were smaller than the simulated values obtained by the Ruijgrok et al. (1997) and Wesely et al. (1985) models. However, the reproducibility of the Ruijgrok et al. (1997) model was better than that of the Wesely et al. (1985) model. The Hicks et al. (1977) model was used to analyze additional forest parameters to calculate the PM2.5 deposition, which could better reflect the role of the forest in PM2.5 deposition.