Double-walled Al-based MOF with large microporous specific surface area for trace benzene adsorption.

Double-walled metal-organic frameworks (MOFs), synthesized using Zn and Co, are potential porous materials for trace benzene adsorption. Aluminum is with low-toxicity and abundance in nature, in comparison with Zn and Co. Therefore, a double-walled Al-based MOF, named as ZJU-520(Al), with large microporous specific surface area of 2235 m2 g-1, pore size distribution in the range of 9.26-12.99 Å and excellent chemical stability, was synthesized. ZJU-520(Al) is consisted by helical chain of AlO6 clusters and 4,6-Di(4-carboxyphenyl)pyrimidine ligands. Trace benzene adsorption of ZJU-520(Al) is up to 5.98 mmol g-1 at 298 K and P/P0 = 0.01. Adsorbed benzene molecules are trapped on two types of sites. One (site I) is near the AlO6 clusters, another (site II) is near the N atom of ligands, using Grand Canonical Monte Carlo simulations. ZJU-520(Al) can effectively separate trace benzene from mixed vapor flow of benzene and cyclohexane, due to the adsorption affinity of benzene higher than that of cyclohexane. Therefore, ZJU-520(Al) is a potential adsorbent for trace benzene adsorption and benzene/cyclohexane separation.

Nematode Uptake Preference toward Different Nanoplastics through Avoidance Behavior Regulation.

Expounding bioaccumulation pathways of nanoplastics in organisms is a prerequisite for assessing their ecological risks in the context of global plastic pollution. Invertebrate uptake preference toward nanoplastics is a key initial step of nanoplastic food chain transport that controls their global biosafety, while the biological regulatory mechanism remains unclear. Here, we reveal a preferential uptake mechanism involving active avoidance of nanoplastics by Caenorhabditis elegans and demonstrate the relationship between the uptake preference and nanoplastic characteristics. Nanoplastics with 100 nm in size or positive surface charges induce stronger avoidance due to higher toxicity, causing lower accumulation in nematodes, compared to the 500 nm-sized or negatively charged nanoplastics, respectively. Further evidence showed that nematodes did not actively ingest any types of nanoplastics, while different nanoplastics induced defense responses in a toxicity-dependent manner and distinctly stimulated the avoidance behavior of nematodes (ranged from 15.8 to 68.7%). Transcriptomics and validations using mutants confirmed that the insulin/IGF signaling (IIS) pathway is essential for the selective avoidance of nanoplastics. Specifically, the activation of DAF-16 promoted the IIS pathway-mediated defense against nanoplastics and stimulated the avoidance behavior, increasing the survival chances of nematodes. Considering the genetical universality of this defense response among invertebrates, such an uptake preference toward certain nanoplastics could lead to cascaded risks in the ecosystem.

Pollution characteristics and source apportionment of heavy metal(loid)s in soil and groundwater of a retired industrial park.

Heavy metal(loid)s (HMs) pollution has become a common and complex problem in industrial parks due to rapid industrialization and urbanization. Here, soil and groundwater were sampled from a retired industrial park to investigate the pollution characteristics of HMs. Results show that Ni, Pb, Cr, Zn, Cd, and Cu were the typical HMs in the soil. Source analysis with the positive matrix factorization model indicates that HMs in the topsoil stemmed from industrial activities, traffic emission, and natural source, and the groundwater HMs originated from industrial activities, groundwater-soil interaction, groundwater-rock interaction, and atmosphere deposition. The sequential extraction of soil HMs reveals that As and Hg were mainly distributed in the residue fraction, while Ni, Pb, Cr, Zn, Cd, and Cu mainly existed in the mobile fraction. Most HMs either in the total concentration or in the bioavailable fraction preferred to retain in soil as indicated by their high soil-water partitioning coefficients (Kd), and the Kd values were correlated with soil pH, groundwater redox potential, and dissolved oxygen. The relative stable soil-groundwater circumstance and the low active fraction contents limited the vertical migration of soil HMs and their release to groundwater. These findings increase our knowledge about HMs pollution characteristics of traditional industrial parks and provide a protocol for HMs pollution scrutinizing in large zones.

Nanoplastics increase algal absorption and toxicity of Cd through alterations in cell wall structure and composition.

Nanoplastics (NPs) may act as carriers of heavy metals and cause complex toxicity to aquatic organisms, while the exact role of NPs in the joint toxicity remains unclear. Here, we investigated the joint toxicity of polystyrene NPs (PS-NPs) and Cd to freshwater algae (Chlorella vulgaris). It was found that PS-NPs (1 mg L-1) could hardly enter algal cells and slightly inhibit algal growth (p < 0.01). The effect of PS-NPs as carriers on the joint toxicity of PS-NPs and heavy metals could be neglected because of the limited adsorption of Cd by PS-NPs, while the PS-NPs altered the cell wall structure and composition, which resulted in the increased algal absorption and toxicity of Cd. Compared to the low dose Cd (0.4 mg L-1) treatment alone, the extracellular and intracellular Cd contents in the cotreatment were significantly increased by 27.3 % and 18.0 %, respectively, due to the increased contents of cell wall polysaccharides (pectin and hemicellulose in particular) by the PS-NPs. Furthermore, after the high dose Cd (2 mg L-1) exposure, the inhibited polysaccharide biosynthesis and the loosen cell wall structure weakened the tolerance of cell wall to abiotic stress, facilitating the entry of PS-NPs into the algal cells and inducing the higher toxicity. These results elucidate the mechanism by which NPs enhance heavy metal toxicity to algae, providing a novel insight into environmental risks of NPs.

Simultaneous adsorption of fulvic acid and organic contaminants by KOH activated mesoporous biochar with large surface area.

Returning carbon materials from biomass to soil is a potential technology to retard organic contaminants or dissolved organic matter (DOM) in soil by adsorption, as well as to store carbon in soil for carbon sequestration. However, DOM was widely reported to inhibit adsorption of organic contaminants on carbon materials by competition and by enhancing contaminants' solubility. In this study, a KOH activated carbon material (KAC), pyrolyzed from bamboo chips, with high surface area (3108 m2/g), micropores volumes (0.964 cm3/g), mesopores volumes (1.284 cm3/g), was observed that it can adsorb fulvic acid (FA) and organic contaminants (e.g., nitrobenzene, phenols, and anilines) simultaneously with weak competition and high adsorption capacity. With 50 mg TOC/L FA, for example, the average competition suppressing rate (ΔKf/Kf-m) of organic contaminants on KAC was lower than 5%, the adsorption for organic contaminants and FA were higher than 1100 mg/g and 90 mg TOC/g, respectively. The weak competition on KAC could be attributed to the low micropore blockage (<35%) and the weak adsorption sites competition on mesopores of KAC, as well as the minimal solubility enhancement of organic contaminants by FA because most FA is adsorbed on KAC but is not dissolved in the solution. In addition, adsorption of organic contaminants with high hydrogen-bonding donor ability (αm) and adsorption affinity was less suppressed by FA because of the heterogeneous nature of hydrophilic sites on KAC's surface. Therefore, KAC could be a potential carbon material to be produced to implement to soil for carbon storage and simultaneous retarding organic contaminants and DOM.

Role of biochar pyrolysis temperature on intracellular and extracellular biodegradation of biochar-adsorbed organic compounds.

Immobilizing organic pollutants by adsorption of biochar in farmland soil is a cost-effective remediation method for contaminated soil. As the adsorption capacity of biochar is limited, biodegradation of biochar-adsorbed organic pollutants was a potential way to regenerate biochars and maintain the adsorption performance of biochars to lower the cost. It could be affected by the biochar pyrolysis temperature, but was not evaluated yet. In this study, biodegradation of adsorbed phenanthrene on a series of biochars with pyrolysis temperatures from 150 to 700 °C by Sphingobium yanoikuyae B1 was investigated using batch experiments of biodegradation kinetics at 30 °C, to explore the role of biochar pyrolysis temperature on biodegradation of biochar-adsorbed organic compounds. It was observed that 37.5-47.9% of adsorbed phenanthrene on moderate temperature-pyrolyzed biochars produced at 400 and 500 °C were biodegraded, less than that on high temperature-pyrolyzed biochars produced at ≥600 °C (48.8-60.8%) and low temperature-pyrolyzed biochars produced at ≤300 °C (63.4-92.5%). Phenanthrene adsorbed largely on the low temperature-pyrolyzed biochars by partition mechanism and thus is easily desorbed to water for a dominated intracellular biodegradation. On the high temperature-pyrolyzed biochars, phenanthrene is adsorbed largely by pore-filling mechanism and thus less desorbed to water for intracellular biodegradation. However, high temperature-pyrolyzed biochars can promote microbes to produce siderophore, H2O2 and thus release extracellular •OH for a dominated degradation of adsorbed phenanthrene by Fenton-like reaction. With the increase of biochar pyrolysis temperature, desorption and consequently the intracellular biodegradation of adsorbed phenanthrene on biochars decreased, while the secretion of siderophore and H2O2 by microbes on biochars increased to produce more extracellular •OH for degradation by Fenton-like reaction. The results could provide deep insights into the role of biochar pyrolysis temperature on biodegradation of biochar-adsorbed organic compounds, and optimize the selection of biochar with higher adsorption performance and easier regeneration for soil remediation.

Drivers distinguishing of PAHs heterogeneity in surface soil of China using deep learning coupled with geo-statistical approach.

Although numerous studies have reported the influencing factors of polycyclic aromatic hydrocarbons (PAHs) in surface soil from source, process or soil perspectives, the mechanism of PAHs heterogeneity in surface soil are still not well understood. In this study, the effects of 16 PAHs in surface soil of China sampled between 2003 and 2020 with their 17 "source-process-sink" factors at 1 km resolution (N = 660)) were explored using deep learning (eXtreme Gradient Boosting) to mine key information from complex dataset under the optimized parameters (i.e., learning rate = 0.05, maximum depth = 5, sub-sample = 0.8). It was observed that top five factors of 16 PAH had the largest cumulative contribution (i.e., from 84.8% to 98.1%) on their soil concentrations. PAH emission was the predominant driver, and its effect on soil PAH increases with increasing logKow. Soil was the second driver, in which clay can promote the partition of PAHs with low or middle logKow. However, sand can accumulate those congeners with high logKow. Moreover, the deep learning plus geo-statistical models (with low deviation for testing dataset (N = 283)) were capable of predicting soil PAH concentrations using their drivers with high accuracy. This study improved the understanding of the environmental fate and spatial variability of soil PAHs, as well as provided a novel technique (i.e., deep learning coupled with geo-statistics) for accurate prediction of soil pollutants.

Linear adsorption of organic compounds on mesoporous activated carbon in bi-solute system.

Knowledge of organic compounds adsorption by adsorbents is essential for evaluating the environmental fates of organic compounds and removing them from the environment. Linear adsorption, as a supplement to the traditionally nonlinear adsorption, was previously proposed for the linear sorption of organic compounds on the mesoporous surface of carbon nanotubes (CNTs) in multi-solute system. However, CNTs are not the ideal adsorbent to verify the linear adsorption mechanism, because of their partition-like phase components such as mobile graphene layers that could be responsible for the linear sorption through linear partition mechanism instead, and thus the linear adsorption theory was argued. In this study, therefore, mesoporous activated carbon (MAC), widely accepted as the model free of partition phase components, was selected as an adsorbent to investigate the adsorption of typical organic compounds in the bi-solute system for verifying whether the linear adsorption phenomenon existed or not. The isotherm of nitrobenzene on MAC was changed from nonlinear to linear with 4-nitrophenol up to 1400 mg/L, and the linear isotherm slope decreased more as 4-nitrophenol concentration increased until 4000 mg/L. It agreed with the characteristics of adsorption (i.e., competition) but not partition (i.e., noncompetition), confirming the existence of linear adsorption. The isotherm linearity was attributed to the reduction of adsorption interactions by displacement and multilayer adsorption. Moreover, linear adsorption of apolar compounds on MAC could occur with apolar or polar competitors, while for polar compounds, linear adsorption could occur with only polar competitors. The observed linear sorption and the competition of organic compounds in the bi-solute system on MAC free of partition phase components verified that the linear adsorption existed, which gives a new insight into the adsorption theory for organic compounds. The results could provide better fundamental theory of adsorption for improving the accuracy of environmental risk assessment of organic pollution and enhancing the efficiency of organic pollution control in the environment.

Epidermal microorganisms contributed to the toxic mechanism of nZVI and TCEP in earthworms by robbing metal elements and nutrients.

Disrupting effects of pollutants on symbiotic microbiota have been regarded as an important mechanism of host toxicity, with most current research focusing on the intestinal microbiota. In fact, the epidermal microbiota, which participates in the nutrient exchange between hosts and environments, could play a crucial role in host toxicity via community changes. To compare the contributions of intestinal and epidermal symbiotic microorganisms to host toxicity, this study designed single and combined scenarios of soil contamination [nano zero-valent iron (nZVI) and tris (2-chloroethyl) phosphate (TCEP)], and revealed the coupling mechanisms between intestinal/epidermal symbiotic bacterial communities and earthworm toxicological endpoints. Microbiome analysis showed that 15% of intestinal microbes were highly correlated with host endpoints, compared to 45% of epidermal microbes showing a similar correlation. Functional comparisons revealed that key species on the epidermis were mainly heterotrophic microbes with genetic abilities to utilize metal elements and carbohydrate nutrients. Further verifications demonstrated that when facing the co-contamination of nZVI and TCEP, certain symbiotic microorganisms became dominant and consumed zinc, copper, and manganese along with saccharides and amino acids, which may be responsible for the nutritional deficiencies in the host earthworms. The findings can enrich the understanding of the coupling relationship between symbiotic microorganisms and host toxicity, highlighting the importance of epidermal microorganisms in host resistance to environmental pollution.

Differential photodegradation processes of adsorbed polychlorinated biphenyls on biochar colloids with various pyrolysis temperatures.

Despite the crucial role of photodegradation in the environmental transformation of organic pollutants, the photodegradation process of organic pollutants irreversibly absorbed on biochar colloids (BCCs) remains poorly understood. This study investigated the photodegradation processes and mechanisms of 2,4,4'-trichlorobiphenyl (PCB28) adsorbed on BCCs released from bulk biochars derived from bamboo chips at pyrolysis temperatures of 300, 500, and 700 °C. Results show that BCCs-adsorbed PCB28 could be degraded under simulated solar illumination (95-105 mW·cm-2) but at decreased photodegradation rates compared to the dissolved PCB28. The inhibition effect of BCCs on the PCB28 photodegradation increased with increasing pyrolysis temperature. After adsorptive binding to BCCs, the half-life of PCB28 (0.1 mg/L) was prolonged from 2.65 h for the dissolved PCB28 alone in deionized water to 7.48, 40.67, and 81.82 h in the presence of BCC300, BCC500, and BCC700 (5.0 mg/L), respectively. Mechanistically, the photodegradation of adsorbed pollutants was regulated by the photogenerated free radicals and surface functional groups of the low-temperature BCCs, as well as the defects and direct electron transfer capabilities of the high-temperature BCCs; PCB28 adsorbed on the low-temperature BCCs accepted electrons from persistent free radicals under light illumination, which led to PCB28 dechlorination, followed by ring-opening oxidation through hydroxyl radical attack, ultimately resulting in progressive mineralization; singlet oxygen caused preferential ring opening of adsorbed PCB28 on the high-temperature BCCs, preceding dechlorination. The photodegradation of BCCs-adsorbed PCB28 remained significant though more or less being inhibited under the effects of water pH, ionic strength, dissolved organic matters (humic acid and fulvic acid), and in natural water samples. These findings contribute to a better understanding of the structural properties of BCCs that impact phototransformation processes of adsorbed pollutants and facilitate an accurate assessment of the environmental risk associated with biochar application.

Toxic effects of nanoplastics and microcystin-LR coexposure on the liver-gut axis of Hypophthalmichthys molitrix.

Plastic products and nutrients are widely used in aquaculture facilities, resulting in copresence of nanoplastics (NPs) released from plastics and microcystins (MCs) from toxic cyanobacteria. The potential effects of NPs-MCs coexposure on aquatic products require investigation. This study investigated the toxic effects of polystyrene (PS) NPs and MC-LR on the gut-liver axis of silver carp Hypophthalmichthys molitrix, a representative commercial fish, and explored the effects of the coexposure on intestinal microorganism structure and liver metabolic function using traditional toxicology and multi-omics association analysis. The results showed that the PS-NPs and MC-LR coexposure significantly shortened villi length, and the higher the concentration of PS-NPs, the more obvious the villi shortening. The coexposure of high concentrations of PS-NPs and MC-LR increased the hepatocyte space in fish, and caused obvious loss of gill filaments. The diversity and richness of the fish gut microbes significantly increased after the PS-NPs exposure, and this trend was amplified in the copresence of MC-LR. In the coexposure, MC-LR contributed more to the alteration of fish liver metabolism, which affected the enrichment pathway in glycerophospholipid metabolism and folic acid biosynthesis, and there was a correlation between the differential glycerophospholipid metabolites and affected bacteria. These results suggested that the toxic mechanism of PS-NPs and MC-LR coexposure may be pathological changes of the liver, gut, and gill tissues, intestinal microbiota disturbance, and glycerophospholipid metabolism imbalance. The findings not only improve the understanding of environmental risks of NPs combined with other pollutants, but also provide potential microbiota and glycerophospholipid biomarkers in silver carp.

Precise coordination of high-loading Fe single atoms with sulfur boosts selective generation of nonradicals.

Nonradicals are effective in selectively degrading electron-rich organic contaminants, which unfortunately suffer from unsatisfactory yield and uncontrollable composition due to the competitive generation of radicals. Herein, we precisely construct a local microenvironment of the carbon nitride-supported high-loading (~9 wt.%) Fe single-atom catalyst (Fe SAC) with sulfur via a facile supermolecular self-assembly strategy. Short-distance S coordination boosts the peroxymonosulfate (PMS) activation and selectively generates high-valent iron-oxo species (FeIV=O) along with singlet oxygen (1O2), significantly increasing the 1O2 yield, PMS utilization, and p-chlorophenol reactivity by 6.0, 3.0, and 8.4 times, respectively. The composition of nonradicals is controllable by simply changing the S content. In contrast, long-distance S coordination generates both radicals and nonradicals, and could not promote reactivity. Experimental and theoretical analyses suggest that the short-distance S upshifts the d-band center of the Fe atom, i.e., being close to the Fermi level, which changes the binding mode between the Fe atom and O site of PMS to selectively generate 1O2 and FeIV=O with a high yield. The short-distance S-coordinated Fe SAC exhibits excellent application potential in various water matrices. These findings can guide the rational design of robust SACs toward a selective and controllable generation of nonradicals with high yield and PMS utilization.

Elucidating the impacts of microplastics on soil greenhouse gas emissions through automatic machine learning frameworks.

With the rise in global plastic production and agricultural demand, the released microplastics (MPs) have increasingly influenced the elemental cycles of soils, leading to notable effects on greenhouse gas emissions. Despite initial research, there remains a gap in establishing a detailed modeling approach that comprehensively explores the impacts of MPs on GHG emissions. Herein, we utilized literature mining to assemble a comprehensive dataset examining the interplays between MPs and emissions of CO2, CH4, and N2O. Five automated machine learning frameworks were employed for predictive modeling. The GAMA framework was particularly effective in predicting CO2 (Q2 = 0.946) and CH4 (Q2 = 0.991) emissions. The Autogluon framework provided the most accurate prediction for N2O emission, though it exhibited signs of overfitting. Interpretability analysis indicated that the type of MPs significantly influenced CO2 emission. Degradable MPs (i.e., polyamide) inherently led to elevated CO2 emission, and the environmental aging further exacerbated this effect. Although both linear and nonlinear correlations between MPs and CH4 emission were not identified, the incorporation of specific MPs that elevate soil pH, augment soil water retention, and cultivate anaerobic conditions may potentially elevate soil CH4 emission. This research underscores the profound influence of MPs on soil GHG emissions, providing vital insights for shaping agricultural policies and soil management practices in the context of escalating plastic use.

Regulating electronic structure of Fe single-atom site by S/N dual-coordination for efficient Fenton-like catalysis.

The activity of single-atom catalysts in peroxymonosulfate activation process is bound up with the local electronic state of metal center. However, the large electronegativity of N atoms in Metal-N4 restricts the electron transfer between center metal atom and peroxymonosulfate. Herein, we constructed Fe-SN-C catalyst by incorporating S atom in the first coordination sphere of Fe single-atom site (Fe-S1N3) for Fenton-like catalysis. The Fe-SN-C with a low valent Fe is found to exhibit excellent catalytic activity for bisphenol A degradation, and the corresponding rate constant reaches 0.405 min-1, 11.9-fold higher than the original Fe-N-C. Besides, the Fe-SN-C/PMS system exhibits ideal catalytic stability under the effect of wide pH range and background substrates by the fast generation of high-valent Fe species. Experimental results and theoretical calculations reveal that the dual coordination of S and N atoms notably increases the local electron density of Fe atoms and electron filling in eg orbital, causing a d band center shifting close to the fermi level and thereby optimizes the activation energy for peroxymonosulfate decomposition via Fe 3d-O 2p orbital interaction. This work provides further development of promising SACs for the efficient activation of peroxymonosulfate based on direct regulation of the coordination environment of active center metal atoms.

Effects and mechanisms of nZVI on CO2 and CH4 emissions in uncontaminated and pentachlorophenol-contaminated soils.

With the increasing application of nanoscale zero-valent iron (nZVI) for in situ soil remediation, its effects on soil functionality and ecosystem need to be thoroughly evaluated. Herein, we investigated the effects of nZVI on CO2 and CH4 emissions from uncontaminated and pentachlorophenol (PCP)-contaminated soils and the underlying microbial mechanisms by designing a 68-day anaerobic soil culture experiment; thereafter, the effects of above aged nZVI on soil CO2 and CH4 emissions in the following 20 days were further studied. In the uncontaminated soil, 1-10 g/kg nZVI treatments reduced soil CO2 emission by 17.4-82.6% and increased soil CH4 emission by 10.8%-119.7%, but these effects disappeared after the nZVI was aged. The emissions of soil CO2 and CH4 were significantly inhibited by the PCP contamination (100 mg/kg) mainly due to the toxicity to related soil microorganisms. The applications of 1-10 g/kg nZVI significantly reduced CO2 emissions from the PCP-contaminated soil by 24.0-86.7%, while 10 g/kg nZVI markedly increased soil CH4 emission by 1875.4% and restored the methanogenic activity to the control level after the nZVI was aged. The 10 g/kg nZVI treatment enriched hydrogenotrophic methanogen (Methanobacterium) and organics-degrading bacteria by releasing H2, increasing soil pH, and decreasing soil Eh; the abundance of genes encoding key enzymes (Mcr, Mtr, Hdr, Mta, and Mtb) in all methanogenic pathways significantly increased after the nZVI treatment, indicating that nZVI could have a broad promoting effects on soil methanogenic processes. The findings demonstrate that the addition of nZVI for in situ remediation of organochlorines-contaminated soils will affect soil greenhouse gas emissions and provide basic data for safe nZVI applications.

Particle-Scale Understanding of Arsenic Interactions with Sulfidized Nanoscale Zerovalent Iron and Their Impacts on Dehalogenation Reactivity.

Co-occurrence of organic contaminants and arsenic oxoanions occurs often at polluted groundwater sites, but the effect of arsenite on the reactivity of sulfidized nanoscale zerovalent iron (SNZVI) used to remediate groundwater has not been evaluated. Here, we study the interaction of arsenite [As(III)] with SNZVI at the individual-particle scale to better understand the impacts on the SNZVI properties and reactivity. Surface and intraparticle accumulation of As was observed on hydrophilic FeS-Fe0 and hydrophobic FeS2-Fe0 particles, respectively. X-ray absorption spectroscopy indicated the presence of realgar-like As-S and elemental As0 species at low and high As/Fe concentration ratios, respectively. Single-particle inductively coupled plasma time-of-flight mass spectrometry analysis identified As-containing particles both with and without Fe. The probability of finding As-containing particles without Fe increased with the S-induced hydrophobicity of SNZVI. The interactions of SNZVI materials with coexisting arsenite inhibited their reactivity with water (∼5.8-230.7-fold), trichloroethylene (∼3.6-67.5-fold), and florfenicol (∼1.1-5.9-fold). However, the overall selectivity toward trichloroethylene and florfenicol relative to water was improved (up to 9.0-fold) because the surface-associated As increased the SNZVI hydrophobicity. These results indicate that reactions of SNZVI with arsenite can remove As from groundwater and improve the properties of SNZVI for dehalogenation selectivity.

Few-Atomic Zero-Valent Palladium Ensembles for Efficient Reductive Dehydrogenation and Dehalogenation Catalysis.

Single-atom catalysts (SACs) offer immense potential in heterogeneous catalysis due to their maximized atomic utilization and high selectivity but suffer the problem of low reactivity in catalytic reductive reactions due to their high-valent state. Here, we demonstrate that supported palladium (Pd) ensembles consisting of a few zero-valent Pd atoms (Pd1+c-red/CN) exhibit exceptional reactivity in formic acid (FA) dehydrogenation and 4-chlorophenol (4-CP) dechlorination. The initial FA dehydrogenation and 4-CP dechlorination rates of Pd1+c-red/CN are 42-104 and 16-210 times higher than that of supported Pd SACs (Pd1-ox/CN), respectively. Experimental results and density functional theory (DFT) calculations reveal that optimal adsorption sites of Pd1+c-red/CN stimulate the formation of H*, which is indispensable for 4-CP dechlorination. Moreover, direct electron transfer from Pd atoms to FA with a high electron density on Pd1+c-red/CN also contributes to the rapid 4-CP dechlorination. The superior dehalogenation capability of Pd1+c-red/CN for organohalides of great environmental and health concerns suggested its immense application potential in environmental remediation. This work highlights the pivotal roles of the structure and valence state of Pd ensembles in catalytic reductive reactions and provides a strategy to broaden the application of Pd-based catalysts for dehydrogenation and dehalogenation.

Tailoring Fe0 Nanoparticles via Lattice Engineering for Environmental Remediation.

Lattice engineering of nanomaterials holds promise in simultaneously regulating their geometric and electronic effects to promote their performance. However, local microenvironment engineering of Fe0 nanoparticles (nFe0) for efficient and selective environmental remediation is still in its infancy and lacks deep understanding. Here, we present the design principles and characterization techniques of lattice-doped nFe0 from the point of view of microenvironment chemistry at both atomic and elemental levels, revealing their crystalline structure, electronic effects, and physicochemical properties. We summarize the current knowledge about the impacts of doping nonmetal p-block elements, transition-metal d-block elements, and hybrid elements into nFe0 crystals on their local coordination environment, which largely determines their structure-property-activity relationships. The materials' reactivity-selectivity trade-off can be altered via facile and feasible approaches, e.g., controlling doping elements' amounts, types, and speciation. We also discuss the remaining challenges and future outlooks of using lattice-doped nFe0 materials in real applications. This perspective provides an intuitive interpretation for the rational design of lattice-doped nFe0, which is conducive to real practice for efficient and selective environmental remediation.

Methyl-Functionalized Al-Based MOF ZJU-620(Al): A Potential Physisorbent for Carbon Dioxide Capture.

Developing Al-based metal-organic frameworks (MOFs) with moisture-resistance ability is a challenge for carbon dioxide (CO2) capture. Methyl-functionalized Al-based MOF ZJU-620(Al), with excellent chemical-thermal stability and specific surface area of 1347 m2/g, observed here, is a potential adsorbent for CO2 capture with good recyclability and large capacity up to 4.25 mmol/g at 298 K and 1 atm. CO2 molecules are largely trapped on two types of sites. One (site I) is near the AlO6 clusters, and another (site II) is between two parallel benzene rings with a distance of 6.64 Å. ZJU-620(Al) can be used for CO2/N2 (15/85) separation with the excellent selectivity up to 107.20 at 273 K and 31.93 at 298 K, and the separation factor of 13.68. It is also with excellent moisture-resistance ability due to 5% breakthrough time (outlet concentration reached the 5% of inlet concentration) without reduction at 80% relative humidity than under dry conditions. Water molecules occupy a small amount of CO2 adsorption site I, but they almost do not occupy the CO2 adsorption site II due to hydrophobic methyl-functional ligands. Moreover, CO2 can be adsorbed on the ZJU-620(Al) surface through C═O···H binding of water molecules with high affinity. Thus, ZJU-620(Al) is a candidate adsorbent for CO2 capture and separation especially under humidity conditions.

Activation of peroxymonosulfate by Cu-Ni-Fe layered double oxides for degradation of butyl 4-hydroxybenzoate: Synergistic effect of oxygen vacancy and Cu(I).

In this study, Cu hybridization coupling oxygen defect engineering was adopted to synthesis of CuNiFe layered double oxides (CuNiFe-LDOs) in peroxymonosulfate (PMS) activation for degradation of methyl 4-hydroxybenzoate. The morphology and crystal structure of CuNiFe-LDOs was characterized in detail, which exhibited regular layered-structure at a Cu:Ni doping ratio of 1:1 and annealing temperature of 400 °C, and presented the crystal of CuxO@Fe3O4-NiO. Besides, the X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) results demonstrated that abundant oxygen vacancies (OVs) and low oxidation state Cu species were composed in CuNiFe-LDOs400. The Cu1·5Ni1·5Fe1-LDOs400/PMS system showed excellent catalytic performance toward the degradation of butyl 4-hydroxybenzoate (BuP), and resistant to the effect of pH value and background inorganic anions. Based on quenching experiments and EPR measurements, singlet oxygen (1O2) was identified as the dominant active species during the heterogeneous catalytic process, which was generated by the synergistic interaction between OVs-Cu(I) site and PMS. In this process, the electron-drawing property of OVs promoted the adsorption of PMS molecule on Cu(I) site, followed by the accumulation of electron and cleavage of O-O bond to generate intermediate oxygen radical species, which donated one electron to eventually generate singlet oxygen.