Targeted improvement of narrow micropores in porous carbon for enhancing trace benzene vapor removal: Revealing the adsorption mechanism via experimental and molecular simulation.

Porous carbon materials are highly desirable for removing benzene due to their low energy for capture and regeneration. Research has demonstrated that narrow microporous volume is crucial for effective adsorption of benzene at ultra-low concentration. Unfortunately, achieving directional increase in the narrow microporous volume in porous carbon remains a challenge. Here, nitrogen-doped hydrothermal carbon was prepared using urea-assisted hydrothermal method, and then porous carbon (PUC800) was prepared by KOH activation. The resulting material had 180 % higher pore volume and 179 % higher surface area compared to non-nitrogen activation methods. Then, using mechanochemical (mechanical compaction and KOH activation) approach to produce PUC800-3T, which had a 30 % increase in pore volume and a 33 % increase in surface area compared to PUC800. PUC800-3T showed benzene adsorption capacity of 4.2 mmol g-1 at 1 Pa and 5.8 mmol g-1 at 5 Pa. Experimental and molecular simulation indicate that the benzene adsorption at 1 and 5 Pa is determined by pore volume of less than 0.8 and 0.9 nm, respectively. Density functional theory calculations provided insight into the CH⋯X (X = N/O) interactions drive benzene adsorption on the carbon framework. This work provides valuable theoretical and experimental support for designing, preparing, and applying adsorbents for trace removal of benzene vapor.

Phytostabilization of Heavy Metals and Fungal Community Response in Manganese Slag under the Mediation of Soil Amendments and Plants.

The addition of soil amendments and plants in heavy metal-contaminated soil can result in a significant impact on physicochemical properties, microbial communities and heavy metal distribution, but the specific mechanisms remain to be explored. In this study, Koelreuteria paniculata was used as a test plant, spent mushroom compost (SMC) and attapulgite (ATP) were used as amendments, and manganese slag was used as a substrate. CK (100% slag), M0 (90% slag + 5% SMC + 5% ATP) and M1 (90% slag + 5% SMC + 5% ATP, planting K. paniculata) groups were assessed in a pilot-scale experiment to explore their different impacts on phytoremediation. The results indicated that adding the amendments significantly improved the pH of the manganese slag, enhancing and maintaining its fertility and water retention. Adding the amendments and planting K. paniculata (M1) significantly reduced the bioavailability and migration of heavy metals (HMs). The loss of Mn, Pb and Zn via runoff decreased by 15.7%, 8.4% and 10.2%, respectively, compared to CK. K. paniculata recruited and enriched beneficial fungi, inhibited pathogenic fungi, and a more stable fungal community was built. This significantly improved the soil quality, promoted plant growth and mitigated heavy metal toxicity. In conclusion, this study demonstrated that the addition of SMC-ATP and planting K. paniculata showed a good phytostabilization effect in the manganese slag and further revealed the response process of the fungal community in phytoremediation.

Revealing the Adsorption Mechanisms of Methanol on Lithium-Doped Porous Carbon through Experimental and Theoretical Calculations.

Previous reports have shown that it is difficult to improve the methanol adsorption performance of nitrogen and oxygen groups due to their low polarity. Here, we first prepared porous carbon with a high specific surface area and large pore volume using benzimidazole as a carbon precursor and KOH as an activating agent. Then, we improved the surface polarity of the porous carbon by doping with Lithium (Li) to enhance the methanol adsorption performance. The results showed that the methanol adsorption capacity of Li-doped porous carbon reached 35.4 mmol g-1, which increased by 57% compared to undoped porous carbon. Molecular simulation results showed that Li doping not only improved the methanol adsorption performance at low pressure, but also at relatively high pressure. This is mainly because Li-modified porous carbon has higher surface polarity than nitrogen and oxygen-modified surfaces, which can generate stronger electrostatic interactions. Furthermore, through density functional theory (DFT) calculations, we determined the adsorption energy, adsorption distance, and charge transfer between Li atom and methanol. Our results demonstrate that Li doping enhances the adsorption energy, reduces the adsorption distance, and increases the charge transfer in porous carbon. The mechanism of methanol adsorption by Li groups was revealed through experimental and theoretical calculations, providing a theoretical basis for the design and preparation of methanol adsorbents.

Experimental and theoretical calculations insight into acetone adsorption by porous carbon at different pressures: Effects of pore structure and oxygen groups.

The influence of different pore size and oxygen groups for porous carbons on acetone adsorption at different pressure was studied by using experimental data and theoretical calculation, and the results were applied to prepare carbon-based adsorbents with superior adsorption capacity. First, we successfully prepared five types of porous carbons with different gradient pore structure but similar oxygen contents (4.9 ± 0.25 at.%). We found that the acetone uptake at different pressure depends on the different pore sizes. Besides, we demonstrate how to accurately decompose the acetone adsorption isotherm into multiple sub-isotherms based on different pore sizes. Based on the isotherm decomposition method, the acetone adsorption at 18 kPa is mainly in the form of pore-filling adsorption in the pore size range of 0.6-2.0 nm. When the pore size is greater than 2 nm, the acetone uptake mainly depends on the surface area. Second, porous carbons with different oxygen content, similar surface area and pore structure were prepared to study the influence of oxygen groups on acetone adsorption. The results show that the acetone adsorption capacity is determined by the pore structure at relatively high pressure, and the oxygen groups only slightly increase the adsorption capacity. However, the oxygen groups can provide more active sites, thereby enhancing acetone adsorption at low pressure.

Organic-inorganic composite modifiers enhance restoration potential of Nerium oleander L. to lead-zinc tailing: application of phytoremediation.

Lead-zinc tailings are complex heavy metal solid wastes produced in the mining process. In this study, two kinds of organic-inorganic mixed improvers mushroom residue + calcium carbonate (M + C) and peat soil + calcium carbonate (N + C) were selected. Then, the effect of two improvers and a woody plant, Nerium oleander L., on the combined remediation of lead-zinc tailings was compared, respectively. The results showed that two combined improvers can slightly improve the pH of tailing, significantly increase the activity of phosphatase and catalase, effectively reduce the contents of DTPA-extractable Pb and Zn, and significantly improve the structure of tailing. However, the improvement effect of M + C was better than that of N + C on tailings' physical and chemical properties. Two improvers can reduce the enrichment and the stress degree of Pb and Zn on the N. oleander and increase the accumulation of Pb and Zn while promoting the growth of the N. oleander. The content of Pb and Zn showed the trend of root > stem > leaf under the two improvers, and the content of Zn was basically higher than that of Pb. To sum up, the combination of two modifiers and N. oleander has a good effect on the remediation of lead-zinc tailings, and the remediation effect of M + C was better than N + C.

Lead Responses and Tolerance Mechanisms of Koelreuteria paniculata: A Newly Potential Plant for Sustainable Phytoremediation of Pb-Contaminated Soil.

Phytoremediation could be an alternative strategy for lead (Pb) contamination. K. paniculata has been reported as a newly potential plant for sustainable phytoremediation of Pb-contaminated soil. Physiological indexes, enrichment accumulation characteristics, Pb subcellular distribution and microstructure of K. paniculata were carefully studied at different levels of Pb stress (0-1200 mg/L). The results showed that plant growth increased up to 123.8% and 112.7%, relative to the control group when Pb stress was 200 mg/L and 400 mg/L, respectively. However, the average height and biomass of K. paniculata decrease when the Pb stress continues to increase. In all treatment groups, the accumulation of Pb in plant organs showed a trend of root > stem > leaf, and Pb accumulation reached 81.31%~86.69% in the root. Chlorophyll content and chlorophyll a/b showed a rising trend and then fell with increasing Pb stress. Catalase (CAT) and peroxidase (POD) activity showed a positive trend followed by a negative decline, while superoxide dismutase (SOD) activity significantly increased with increasing levels of Pb exposure stress. Transmission electron microscopy (TEM) showed that Pb accumulates in the inactive metabolic regions (cell walls and vesicles) in roots and stems, which may be the main mechanism for plants to reduce Pb biotoxicity. Fourier transform infrared spectroscopy (FTIR) showed that Pb stress increased the content of intracellular -OH and -COOH functional groups. Through organic acids, polysaccharides, proteins and other compounds bound to Pb, the adaptation and tolerance of K. paniculata to Pb were enhanced. K. paniculata showed good phytoremediation potential and has broad application prospects for heavy metal-contaminated soil.

Current Progress, Challenges and Perspectives in the Microalgal-Bacterial Aerobic Granular Sludge Process: A Review.

Traditional wastewater treatment technologies have become increasingly inefficient to meet the needs of low-consumption and sustainable wastewater treatment. Researchers are committed to seeking new wastewater treatment technologies, to reduce the pressure on the environment caused by resource shortages. Recently, a microalgal-bacterial granular sludge (MBGS) technology has attracted widespread attention due to its high efficiency wastewater treatment capacity, low energy consumption, low CO2 emissions, potentially high added values, and resource recovery capabilities. This review focused primarily on the following aspects of microalgal-bacterial granular sludge technology: (1) MBGS culture and maintenance operating parameters, (2) MBGS application in different wastewaters, (3) MBGS additional products: biofuels and bioproducts, (4) MBGS energy saving and consumption reduction: greenhouse gas emission reduction, and (5) challenges and prospects. The information in this review will help us better understand the current progress and future direction of the MBGS technology development. It is expected that this review will provide a sound theoretical basis for the practical applications of a MBGS technology in environmentally sustainable wastewater treatment, resource recovery, and system optimization.

Metronidazole Degradation by UV and UV/H2O2 Advanced Oxidation Processes: Kinetics, Mechanisms, and Effects of Natural Water Matrices.

Advanced oxidation technology represented by hydroxyl radicals has great potential to remove residual antibiotics. In this study, we systematically compared the metronidazole (MTZ) degradation behavior and mechanism in the UV and UV/H2O2 systems at pH 3.00 condition. The results show that the initial reaction rates were 0.147 and 1.47 µM min-1 in the UV and UV/H2O2 systems, respectively. The main reason for the slow direct photolysis of MTZ is the relatively low molar absorption coefficient (2645.44 M-1 cm-1) and quantum yield (5.9 × 10-3 mol Einstein-1). Then, we measured kMTZ,OH â€¢ as 2.79 (±0.12) × 109 M-1 s-1 by competitive kinetics, and calculated kMTZ,OH â€¢ and [OH â€¢]SS as 2.43 (±0.11) × 109 M-1 s-1 and 2.36 × 10-13 M by establishing a kinetic model based on the steady-state hypothesis in our UV/H2O2 system. The contribution of direct photolysis and •OH to the MTZ degradation was 9.9% and 90.1%. •OH plays a major role in the MTZ degradation, and •OH was the main active material in the UV/H2O2 system. This result was also confirmed by MTZ degradation and radicals' identification experiments. MTZ degradation increases with H2O2 dosage, but excessive H2O2 had the opposite effect. A complex matrix has influence on MTZ degradation. Organic matter could inhibit the degradation of MTZ, and the quenching of the radical was the main reason. NO3- promoted the MTZ degradation, while SO42- and Cl- had no effect. These results are of fundamental and practical importance in understanding the MTZ degradation, and to help select preferred processes for the optimal removal of antibiotics in natural water bodies, such as rivers, lakes, and groundwater.

[Mechanism of Lead-zinc Enrichment and Resistance of Spent Mushroom Compost to Lead-Zinc Slag in Koelreuteria paniculata].

Phytoremediation is an ecological technique for tailing area restoration; adding substrate modifiers can reduce the stress of heavy metals on plants and enhance the restoration efficiency. The woody plant Koelreuteria paniculata was used as a test plant and potted in 100% tailings (S), 90% tailings+5% mushroom residue (SMC)+5% CaCO3 (MS), and natural red soil (RS). The effects of physiological responses and tolerance enrichment effects on Pb and Zn tolerance in K. paniculata under different treatments were investigated to compare the growth morphology, microscopic morphological changes, and microbial diversity changes in each substrate of K. paniculata seedlings. The results showed that compared with the control group S, the MS treatment group could significantly improve the structure and fertility of the tailing substrates; significantly enhance the relevant physiological indicators such as biomass, plant height, and chlorophyll content of K. paniculate; and increase the accumulated heavy metal content in K. paniculata. In the treatment group, the overall physiological indexes of MS compared to RS biomass and plant height were promoted, and the total root length increased up to 69.3%, whereas the average root diameter of RS in the treatment group decreased 118.7% compared to that in the control group S. The MS treatment group showed a 266.67% increase in Pb and Zn residue state, a significant decrease in the weak acid extractable state and oxide-bound state compared to that in the control group S. The heavy metals were less active for plant migration. Furthermore, most of the heavy metals were trapped in the roots of K. paniculata, and the changes in its root conformation indicated its strong adaptability in the face of high Pb stress. Transmission electron microscopy (TEM) analysis showed that the higher concentration of heavy metals in the S control damaged the cell wall structure and caused toxic effects on plant cells. The addition of the modifier effectively alleviated the effects of heavy metal stress on various tissues of K. paniculata, affected the structure of microbial communities, significantly increased microbial richness and diversity, and enhanced the adaptability of K. paniculata to heavy metals and phytoremediation ability.

Application for Ecological Restoration of Contaminated Soil: Phytoremediation.

Nowadays, with the rapid development of industry and agriculture, heavy metal pollution is becoming more and more serious, mainly deriving from natural and man-made sources [...].

Applications of Single Atom Catalysts for Environmental Management.

With the rapid development of industrialization, human beings have caused many negative effects on the environment that have endangered the survival and development of human beings, such as the greenhouse effect, water pollution, energy depletion, etc [...].

Neutralization and Improvement of Bauxite Residue by Saline-Alkali Tolerant Bacteria.

The high salt-alkalinity of bauxite residue (BR) hinders plant growth and revegetation of bauxite residue disposal areas (BRDA), which cause serious potential environmental and ecological risks. Bioneutralization is a promising method for improving the properties of BR and plant colonization. In the present study, a strong saline-alkali tolerant bacteria (ZH-1) was isolated from aged BR and identified as Bacillus sp. The medium of ZH-1 was optimized by orthogonal tests, and ZH-1 could decrease the medium pH from 11.8 to 6.01 (agitated culture) and 6.48 (static culture) by secretion of citric acid, oxalic acid and tartaric acid. With the inoculation of ZH-1, the pH of BR decreased from 11.6 to 8.76, and the water-soluble salt in BR increased by 68.11%. ZH-1 also changed the aggregate size distribution of BR, the mechanical-stable aggregates and water-stable aggregates increased by 18.76% and 10.83%, respectively. At the same time, the stability of the aggregates obviously increased and the destruction rate decreased from 94.37% to 73.46%. In addition, the microbial biomass carbon increased from 425 to 2794 mg/kg with the inoculation of ZH-1. Bacterial community analysis revealed that Clostridia, Bacilli, Gammaproteobacteria, Betaproteobacteria and Alphaproteobacteria were the main classes in the naturalized BR, and the inoculation of ZH-1 increased the diversity of bacteria in the BR. Overall, ZH-1 has great potential for neutralization and improvement the properties of BR and may be greatly beneficial for the revegetation of BRDA.

Comparison of Phytoremediation Potential of Nerium indicum with Inorganic Modifier Calcium Carbonate and Organic Modifier Mushroom Residue to Lead-Zinc Tailings.

At present, the application of phytoremediation technology in the ecological remediation of heavy metal tailings is receiving more and more attention. In this study, the physiological and biochemical response and tolerance mechanism of woody plant Nerium indicum to Pb and Zn under different proportions of inorganic modifier calcium carbonate (C1: 5%, C2: 10%, C3: 15%) and organic modifier mushroom residue (M1: 10%, M2: 20%, M3: 30%) was compared. The results showed that the pH value has a trend of C group > M group > CK group and organic matter has a trend of M group > CK group > C group. Phosphatase activity and catalase activity has a trend of M group > C group > CK group, but catalase was more vulnerable to the calcium carbonate concentration. Both modifiers can promote the transformation of Pb, Zn, Cu, and Cd in tailings to more stable organic bound and residual states. However, the stabilization effect of mushroom residue is better, and its stability is Pb, Zn > Cd, Cu. Both modifiers can increase the biomass of Nerium indicum and the modification effect of mushroom residue is better than calcium carbonate. Pb/Zn content and accumulation in Nerium indicum organs showed root > stem > leaf in all groups. Compared with the CK group, the enrichment coefficient of Pb/Zn in C1 and M1 groups decreased, while the translocation factor of Pb/Zn in C1 and M1 groups increased. With the increase in modifier concentration, the enrichment coefficient increases about 1.75~52.94%, but the translocation factor decreases rapidly (20.01~64.46%). Clearly, both the calcium carbonate and mushroom residue amendment could promote the growth ability of Nerium indicum in lead−zinc tailings and strengthen the phytoremediation potential.

Integration of manganese accumulation, subcellular distribution, chemical forms, and physiological responses to understand manganese tolerance in Macleaya cordata.

Macleaya cordata (Willd.) R. Br. are proposed for the application in phytoremediation of heavy metal-contaminated soil. In this paper, the physiological response, subcellular distribution, chemical form, ultrastructure, and manganese (Mn) absorption characteristics of M. cordata under the stress of 0, 3, 6, 9, 12, and 15 mmol/L manganese concentration were studied by sand culture experiment. The results showed that M. cordata seedlings show high tolerance to Mn stress with a concentration of less than 6 mmol/L, while higher Mn concentration showed a significant toxic effect. A low concentration of Mn (≤ 6 mmol/L) can promote the synthesis of chlorophyll and soluble protein; furthermore, superoxide dismutase and peroxidase activities responded positively. The accumulation of Mn in the inactive metabolic part (cell wall and vacuole) of M. cordata leaves might be one of the main Mn detoxification mechanism. According to the ultrastructure of M. cordata, high-concentration Mn2+ (≥ 12 mmol/L) stress can cause M. cordata cells to be distorted and deformed, black precipitates appeared in the intercellular space, mitochondria decrease, chloroplasts shrink, hungry particles increased, and starch granules decrease. The uptake ability of different tissues for Mn is leaf > root > stem, and transport coefficient decreases with the increase of Mn concentration. Clearly, M. cordata has a certain tolerance to manganese, which has the ecological application potential in Mn-polluted areas.

Degradation of trimethoprim by sulfate radical-based advanced oxidation processes: kinetics, mechanisms, and effects of natural water matrices.

In this study, we investigated the removal efficiency of a broad-spectrum antimicrobial agent trimethoprim (TMP) in a UV-activated persulfate system (UV/PS). The pseudo-first-order reaction kinetic model based on the steady-state hypothesis was used to explain TMP degradation behavior in UV-activated persulfate system. Due to the low quantum yield and molar absorptivity of TMP at 254 nm, the direct photolysis of TMP was slower. Since the free radicals generated by adding H2O2 or PS to the system can react with TMP, the degradation rate was significantly accelerated, and[Formula: see text] played a dominant role in the UV/PS system. [Formula: see text] and [Formula: see text] were determined by the pseudo-first-order reaction kinetic model to be 6.02×109 and 3.88×109 M-1s-1, respectively. The values were consistent with competitive kinetic measurements. The pseudo-first-order reaction kinetics model can predict and explain the effect of PS concentration, natural organic matter, and chloride ion on the TMP degradation in the UV/PS system. The observed pseudo first-order rate constants for TMP degradation (kobs) increased with the persulfate concentration, but it significantly decreased in the presence of NOM and chloride. [Formula: see text] has no effect on the degradation of TMP, while [Formula: see text] promotes the degradation and [Formula: see text] inhibits the degradation. The common transition metal ion (such as Cu2+, Zn2+, and Co2+) in industrial wastewater has a synergistic effect on the TMP degradation in the UV/PS system, but excessive metal ions will lead to a decrease of the degradation rate.

Enhanced removal of Co(II) and Ni(II) from high-salinity aqueous solution using reductive self-assembly of three-dimensional magnetic fungal hyphal/graphene oxide nanofibers.

Layer-structured graphene oxide excellent carrier for modifications; however, its poor recoverability and stability preclude its application in wastewater treatment fields. Herein, three-dimensional magnetic fungal hyphal/graphene oxide nanofibers (MFHGs) were assembled by a reductive self-assembly (RSA) strategy for the efficient capture of Co(II) and Ni(II) from high-salinity aqueous solution. The RSA strategy is inexpensive, eco-friendly and easy to scale up. The obtained MFHGs enhanced the dispersity and stability of graphene oxide and exhibited excellent magnetization and large coercivity, leading to satisfactory solid-liquid separation performance and denser sediment. The results of batch removal experiments showed that the maximum removal capacity of MFHGs for Ni(II) and Co(II) was 97.44 and 104.34 mg/g, respectively, in 2 g/L Na2SO4 aqueous solution with a pH of 6.0 at 323 K, and the effects of initial pH and ionic strength on Co(II) and Ni(II) removal were explored. Yield residue analysis indicated that the high porosity and oxygen-containing functional groups of MFHGs remarkably improved their Co(II)- and Ni(II)-removal capacities. According to the analysis, hydroxyl groups and amine groups participated in the chemical reaction of Co(II) and Ni(II) removal, and cation-exchange chemical adsorption was dominant during the Co(II)- and Ni(II)-removal process. Based on the attributes of MFHGs, a continuous-flow recycle reactor (CFRR) was proposed for emergency aqueous solution treatment and exhibited satisfactory removal efficiency and regeneration performance. The combination of MFHGs and the proposed CFRR is a promising water treatment strategy for rapid treatment applications.

Oxygen Reduction Reaction in the Field of Water Environment for Application of Nanomaterials.

Water pollution has caused the ecosystem to be in a state of imbalance for a long time. It has become a major global ecological and environmental problem today. Solving the potential hidden dangers of pollutants and avoiding unauthorized access to resources has become the necessary condition and important task to ensure the sustainable development of human society. To solve such problems, this review summarizes the research progress of nanomaterials in the field of water aimed at the treatment of water pollution and the development and utilization of new energy. The paper also tries to seek scientific solutions to environmental degradation and to create better living environmental conditions from previously published cutting edge research. The main content in this review article includes four parts: advanced oxidation, catalytic adsorption, hydrogen, and oxygen production. Among a host of other things, this paper also summarizes the various ways by which composite nanomaterials have been combined for enhancing catalytic efficiency, reducing energy consumption, recycling, and ability to expand their scope of application. Hence, this paper provides a clear roadmap on the status, success, problems, and the way forward for future studies.

Efficient copper(i)-catalyzed oxidative intermolecular 1,2-estersulfenylation of styrenes with peroxyesters and disulfides.

A simple and practical method for the synthesis of thio-substituted esters through copper(i)-catalyzed intermolecular 1,2-estersulfenylation of styrenes with peroxyesters and disulfides was developed. In this transformation, two new C-S bond and C-O bond were constructed simultaneously under a copper catalyst system, and the transformation exhibits a broad substrate scope and good functional group compatibility. In addition, this method can also be applied to arylthiols. It should be noted that peroxyesters not only acted as nucleophilic reagents but also as oxidants.

Mushroom residue modification enhances phytoremediation potential of Paulownia fortunei to lead-zinc slag.

Phytoremediation is an effective strategy for the remediation of lead-zinc slag, while the response of plant on lead and zinc was less concerned. In this study, mushroom residue was adding in lead-zinc slag to enhance the phytoremediation potential of P. fortunei, the effects of three treatments (lead-zinc slag, red soil, lead-zinc slag + 10% (m/m) mushroom residue) on the growth, physiology and microstructure of P. fortunei were determined. The results showed that the addition of mushroom residue increased the biomass, plant height and chlorophyll concentration of P. fortunei, indicating that the addition of mushroom residue can facilitate the growth of P. fortunei. Moreover, the proportions of oxalate-Pb forms and phosphate-Zn were dominant in leaves and stems of P. fortunei. With the addition of mushroom residue, Pb and Zn were transformed to the extraction state with weak migration activity, which can reduce the damage level of Pb and Zn to P. fortunei. The results from scanning transmission electron microscopy (STEM) showed that, the mushroom residue amendment could maintain the integrity of the cell structural of P. fortunei. The results from fourier transform infrared spectrometer (FTIR) analysis showed that the mushroom residue amendment could increase the contents of proteins and polysaccharides in P. fortunei, which can combine with the metals. Clearly, the mushroom residue amendment could promote the growth ability of P. fortunei in lead and zinc slag and strengthen the phytoremediation potential.

Annulation Cascades of N-Allyl- N-((2-bromoaryl)ethynyl)amides Involving C-H Functionalization.

An annulation cascades of N-allyl- N-((2-bromoaryl)ethynyl)amides with terminal alkynes or 1,3-dicarbonyls involving C-H functionalization for producing 2,3-functionalized indoles has been first developed by means of Cu catalysis. The method is enabled by the formation of the ketenimine intermediates to deliver 2,3-disubstituted indoles through a sequence of aza-Claisen rearrangement, C-H functionalization, Ullmann C-N coupling, and cyclization.