Effects of Zr substitution on soot combustion over cubic fluorite-structured nanoceria: Soot-ceria contact and interfacial oxygen evolution

Ceria is widely used as a catalyst for soot combustion, but effects of Zr substitution on the reaction mechanism is ambiguous. The present work elucidates effects of Zr substitution on soot combustion over cubic fluorite-structured nanoceria. The nanostructured CeO₂, Ce_0.92Zr_0.08O₂, and Ce_0.84Zr_0.16O₂ composed of 5–6 nm crystallites display T_m-CO2 (the temperature at maximum CO₂ yield) at 383, 355, and 375°C under 10 vol.% O₂/N₂, respectively. The size of agglomerate decreases from 165.5 to 51.9–57.3 nm, which is beneficial for the soot-ceria contact. Moreover, Zr increases the amount of surface oxygen vacancies, generating more active oxygen (O₂^? and O^?) for soot oxidation. Thus, the activities of Ce_0.92Zr_0.08O₂ and Ce_0.84Zr_0.16O₂ in soot combustion are better than that of CeO₂. Although oxygen vacancies promote the migration of lattice O^2?, the enriched surface Zr also inhibits the mobility of lattice O^2?. Therefore, the T_m-CO2 of Ce_0.84Zr_0.16O₂ is higher than that of Ce_0.92Zr_0.08O₂. Based on reaction kinetic study, soot in direct contact with ceria preferentially decomposes with low activation energy, while the oxidation of isolated soot occurs through diffusion with high activation energy. The obtained findings provide new understanding on the soot combustion over nanoceria.     

Remediation of 2,4-dichlorophenol-contaminated groundwater using nano-sized CaO2 in a two-dimensional scale tank

• Nano CaO₂ is evaluated as a remediation agent for 2,4-DCP contaminated groundwater. • 2,4-DCP degradation mechanism by different Fe²⁺ concentration was proposed. • 2,4-DCP was not degraded in the system for solution pH>10. • The 2,4-DCP degradation area is inconsistent with the nano CaO₂ distribution area. This study evaluates the applicability of nano-sized calcium peroxide (CaO₂) as a source of H₂O₂ to remediate 2,4-dichlorophenol (2,4-DCP) contaminated groundwater via the advanced oxidation process (AOP). First, the effect and mechanism of 2,4-DCP degradation by CaO₂ at different Fe concentrations were studied (Fenton reaction). We found that at high Fe concentrations, 2,4-DCP almost completely degrades via primarily the oxidation of •OH within 5 h. At low Fe concentrations, the degradation rate of 2,4-DCP decreased rapidly. The main mechanism was the combined action of •OH and O₂^•−. Without Fe, the 2,4-DCP degradation reached 13.6% in 213 h, primarily via the heterogeneous reaction on the surface of CaO₂. Besides, 2,4-DCP degradation was significantly affected by solution pH. When the solution pH was>10, the degradation was almost completely inhibited. Thus, we adopted a two-dimensional water tank experiment to study the remediation efficiency CaO₂ on the water sample. We noticed that the degradation took place mainly in regions of pH<10 (i.e., CaO₂ distribution area), both upstream and downstream of the tank. After 28 days of treatment, the average 2,4-DCP degradation level was ≈36.5%. Given the inadequacy of the results, we recommend that groundwater remediation using nano CaO₂: (1) a buffer solution should be added to retard the rapid increase in pH, and (2) the nano CaO₂ should be injected copiously in batches to reduce CaO₂ deposition.     

Parsing organizational culture: How the norm for adaptability influences the relationship between culture consensus and financial performance in high‐technology firms

The relationship between organizational culture and financial performance remains elusive even though researchers have studied it for some time. Early research suggested that a strong culture that aligns members' behavior with organizational objectives boosts financial performance. A more recent view is that, because strong cultures promote adherence to routines and behavioral uniformity, they are less effective in dynamic environments. We suggest that the relationship between culture and performance can be reconciled by recognizing that culture encompasses three components: (1) the content of norms (norm content); (2) how widely members agree about norms (culture consensus); and (3) how intensely organizational members hold particular norms (norm intensity). We hypothesize that “strong cultures”—where a high consensus exists among members across a broad set of culture norms—can contribute to better financial performance even in dynamic environments if norm content intensely emphasizes adaptability. We test this hypothesis in a sample of large firms in the high‐technology industry. Firms characterized by higher culture consensus and intensity about adaptability performed better three years later than did those characterized by lower consensus, lower intensity about adaptability, or both. We discuss how parsing culture into content, consensus, and intensity advances theoretical and empirical understanding of the culture–performance relationship. Copyright © 2014 John Wiley & Sons, Ltd.     

Natural attenuation characteristics and comprehensive toxicity changes of C9 aromatics under simulated marine conditions

Microcosmic experiments were performed under a simulated marine environment to investigate the natural attenuation of C9 aromatics using nine components (propylbenzene, isopropylbenzene, 2-ethyltoluene, 3-ethyltoluene, 4-ethyltoluene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, and indene). This research aims to assess the contribution of biodegradation and abiotic activity to total attenuation of C9 aromatics and ascertain the changes in the comprehensive toxicity of seawater in the natural environment. The process of natural attenuation indicates the agreement with pseudo-first-order kinetics for all nine components in microcosmic experiments. The half-lives of the nine main compounds in C9 aromatics ranged between 0.34 day and 0.44 day under optimal conditions. The experiments showed that the natural attenuation of nine aromatic hydrocarbons mainly occurred via abiotic processes. Seawater samples significantly inhibited the luminescence of P. phosphoreum (the luminescence inhibition ratio reached 100%) at the beginning of the experiment. In addition, the toxicity declined slowly and continued for 25 days. The attenuation kinetics and changes in toxicity could be applied to explore the natural attenuation of C9 aromatics in the marine environment.     

Product identification and toxicity change during oxidation of methotrexate by ferrate and permanganate in water

• Oxidation of methotrexate by high-valent metal-oxo species was first explored. • Fe(VI) presented a higher reactivity to MTX than Mn(VII) at pH 8.0. • Ketonization and cleavage of peptide bond were two initial reaction pathways. • Products of MTX were not genotoxic, neurotoxic, or endocrine-disrupting chemicals. • The less biodegradable products exhibited developmental and acute/chronic toxicity. Accompanying an annual increase in cancer incidence, the global use of anticancer drugs has remarkably increased with their worldwide environmental prevalence and ecological risks. In this study, the oxidation of methotrexate (MTX), a typical anticancer drug with ubiquitous occurrence and multi-endpoint toxicity, by ferrate(VI) (Fe(VI)) and permanganate (Mn(VII))) was investigated in water. Fe(VI) exhibited a higher reactivity with MTX (93.34 M⁻¹ s⁻¹) than Mn(VII) (3.01 M⁻¹ s⁻¹) at pH 8.0. The introduction of Cu(II) and Fe(III) at 1.0 mM improved the removal efficiency of 5.0 μM MTX by 100.0 μM Fe(VI) from 80% to 95% and 100% after 4 min, respectively. Seven oxidized products (OPs) were identified during oxidative treatments, while OP-191 and OP-205 were characterized as specific products for Fe(VI) oxidation. Initial ketonization of the L-glutamic acid moiety and cleavage of the peptide bond of MTX were proposed. Additionally, a multi-endpoint toxicity evaluation indicated no genotoxicity, neurotoxicity, or endocrine-disrupting effects of MTX and its OPs. Particularly, serious developmental toxicity in zebrafish larvae was observed in the treated MTX solutions. Based on the acute and chronic aquatic toxicity prediction, OP-190, OP-192, OP-206, and OP-208 were deemed toxic or very toxic compared to harmful MTX. Furthermore, the reduced biodegradability index from 0.15 (MTX) to −0.5 to −0.2 (OP-192, OP-206, and OP-468) indicated the formation of lower biodegradable OPs. Overall, this study suggests that Fe(VI) and Mn(VII) oxidation are promising treatments for remediating anticancer drug-contaminated water. However, the environmental risks associated with these treatments should be considered in the evaluation of water safety.     

Ethanol washing of PAH-contaminated soil and Fenton oxidation of washing solution

As a means to remediate soil contaminated by polycyclic aromatic hydrocarbons, we investigated a combined process involving ethanol washing followed by a Fenton oxidation reaction. Artificial loamy soil was contaminated with various representative polycyclic aromatic hydrocarbons (i.e., fluorene, anthracene, pyrene, benzo(b)fluoranthene, or benzo(a)pyrene) at concentrations ten times higher than regulatory soil standards of The Netherlands or Canada, and then washed four times in ethanol, which reduced the concentration of polycyclic aromatic hydrocarbon contamination to below the regulatory standard. Fenton oxidation of ethanol solutions containing anthracene, benzo(a)pyrene, pyrene, acenaphthylene, acenaphthene, benz(a)anthracene, benzo(j)fluoranthene, or indeno(1,2,3-cd)pyrene showed a removal efficiency of 73.3%–99.0%; by contrast, solutions containing naphthalene, fluorene, fluoranthene, phenanthrene, or benzo(b)fluoranthene showed a removal efficiency of 9.6%–27.6%. Since each of the nonremediated polycyclic aromatic hydrocarbons, excluding benzo(b)fluoranthene, are easily biodegradable, these results indicate that the proposed treatment can be successfully applied to polycyclic aromatic hydrocarbon-contaminated soil that does not contain high concentrations of benzo(b)fluoranthene. The main reaction products resulting from Fenton oxidation of ethanol solutions containing anthracene or benz(a)anthracene were anthraquinon or benz(a)anthracene-7,12-dione, respectively; while 1,8-naphthalic anhydride was produced by solutions of acenaphthylene and acenaphthene, and 9-fluorenone by a fluorene solution. Received: June 9, 1998 / Accepted: March 24, 1999     

催化湿式氧化处理H—酸溶液的反应动力学

两阶段一级反应动力学模型和广义动力学模型被用来描述湿式氧化（ＷＡＯ）及催化湿式氧化（ＣＷＡＯ）反应过程，并确定了动力学参数。２个模型的计算值均与实验值相符，而广义动力学模型相对现准确些。２个确定均表明反尖分２个步骤：首先是Ｈ－酸被迅速氧化成小分子有机酸，后者再缓慢氧化，这２个步骤由模型参数加以表征，因而模型可被用来对ＣＷＡＯ催化剂进行评价。     

Effect of substituents in hydroxyl radical-mediated degradation of azo pyridone dyes: Theoretical approaches on the reaction mechanism

Understanding the degradation behavior of azo dyes in photocatalytic wastewater treatment is of fundamental and practical importance for their application in textile-processing and other coloration industries. In this study, quantum chemistry, as density functional theory, was used to elucidate different degradation pathways of azo pyridone dyes in a hydroxyl radical (HO^?)-initiated photocatalytic system. A series of substituted azo pyridone dyes were synthesized by changing the substituent group in the para position of the benzene moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The effect of dye molecular structure on the photocatalytic degradation reaction mechanism was analyzed and quantification of substituent effects on the thermodynamic and kinetics parameters was performed. Potential energy surface analysis revealed the most susceptible reaction site for the HO^? attack. The calculated reaction barriers are found to be strongly affected by the nature of substituent group with a good correlation using Hammett σ_p constants and experimentally determined reaction rates. The stability of pre-reaction complexes and transition state complexes were analyzed applying the distortion-interaction model. The increased stability of the transition state complexes with the distancing from the substituent group has been established.     

Five lessons to guide more effective biodiversity conservation message framing

Communication and advocacy approaches that influence attitudes and behaviors are key to addressing conservation problems, and the way an issue is framed can affect how people view, judge, and respond to an issue. Responses to conservation interventions can also be influenced by subtle wording changes in statements that may appeal to different values, activate social norms, influence a person's affect or mood, or trigger certain biases, each of which can differently influence the resulting engagement, attitudes, and behavior. We contend that by strategically considering how conservation communications are framed, they can be made more effective with little or no additional cost. Key framing considerations include, emphasizing things that matter to the audience, evoking helpful social norms, reducing psychological distance, leveraging useful biases, and, where practicable, testing messages. These lessons will help communicators think strategically about how to frame messages for greater effect.     

Essential hazard and process safety assessment of para-toluene sulfonic acid through calorimetry and advanced thermokinetics

Para-toluene sulfonic acid is a typical intermediary for the synthesis of pharmaceuticals, pesticides, and dyes and is a catalyst for organic synthesis. The consumption of para-toluene sulfonic acid used in organic synthesis has increased substantially. The toluene sulfonation process is the central path for synthesizing para-toluene sulfonic acid in China. However, the process has risks and has resulted in numerous disasters. This study utilized a reaction calorimeter 1 to reproduce the commercial toluene sulfonation process in a laboratory. The para-toluene sulfonic acid product was examined with an accelerating rate calorimeter and through differential scanning calorimetry. Both differential and integral isoconversional methods were used to determine the thermal stability of and appropriate thermokinetic models for para-toluene sulfonic acid. The safety parameters of para-toluene sulfonic acid were estimated. The research findings can be used for optimization of the toluene sulfonation process and for safe handling of para-toluene sulfonic acid.