Polyoxometalate Clusters Confined in Reduced Graphene Oxide Membranes for Effective Ion Sieving and Desalination.

Efficient 2D membranes play a critical role in water purification and desalination. However, most 2D membranes, such as graphene oxide (GO) membranes, tend to swell or disintegrate in liquid, making precise ionic sieving a tough challenge. Herein, the fabrication of the polyoxometalate clusters (PW12) intercalated reduced graphene oxide (rGO) membrane (rGO-PW12) is reported through a polyoxometalate-assisted in situ photoreduction strategy. The intercalated PW12 result in the interlayer spacing in the sub-nanometer scale and induce a nanoconfinement effect to repel the ions in various salt solutions. The permeation rate of rGO-PW12 membranes are about two orders of magnitude lower than those through the GO membrane. The confinement of nanochannels also generate the excellent non-swelling stability of rGO-PW12 membranes in aqueous solutions up to 400 h. Moreover, when applied in forward osmosis, the rGO-PW12 membranes with a thickness of 90 nm not only exhibit a high-water permeance of up to 0.11790 L m-2 h-1 bar-1 and high NaCl rejection (98.3%), but also reveal an ultrahigh water/salt selectivity of 4740. Such significantly improved ion-exclusion ability and high-water flux benefit from the multi-interactions and nanoconfinement effect between PW12 and rGO nanosheets, which afford a well-interlinked lamellar structure via hydrogen bonding and van der Waals interactions.

Revealing the synergistic effect of Ni single atoms and adjacent 3d metal doped Ni nanoparticles in electrocatalytic CO2 reduction.

Herein, we report the successful fabrication of a series of transition metal doped Ni nanoparticles (NPs) coordinated with Ni single atoms in nitrogen-doped carbon nanotubes (denoted as Ni1+NPsM-NCNTs, M = Mn, Fe, Co, Cu and Zn; Ni1 = Ni single atom). X-ray absorption fine structure reveals the coexistence of Ni single atoms with Ni-N4 coordination and NiM NPs. When applied for electrocatalytic CO2RR, the Ni1+NPsM-NCNT compounds show the Faradaic efficiency of CO (FECO) with a volcano-like tendency of Mn < Fe ≈ Co < Zn < Cu, in which the Ni1+NPsCu-NCNT exhibits the highest FECO of 96.92%, a current density of 171.25 mA cm-2 and a sustainable stability over 24 hours at a current density of 100 mA cm-2, outperforming most reported examples in the literature. Detailed experiments and theoretical calculations reveal that for Ni1+NPsCu-NCNTs, the electron transfer from NiCu NPs to Ni single atoms strengthens the adsorption of *COOH intermediates. Moreover, the d-band center of Ni-N in Ni1+NPsCu-NCNT is upshifted, providing stronger binding with the reaction intermediates of *COOH, whereas the NiCu NPs increase the Gibbs free energy change of the Volmer step, suppressing the competitive HER.

Spatiotemporal change characteristics of vegetation coverage in Shangwan Mine of China's Shendong Mining Area.

The coal mining might cause the disturbance to the vegetation and the disturbance impacts might exist the differences for different areas, and few literatures compared and analyzed different disturbed areas based on the location of the mining face, and paid attention to the post mining self-healing effects of vegetation. Here, this paper selected the GaoFen multispectral images during 2017-2021 to study different areas of Shangwan Mine which includes the old mining area more than 5 years after mining, the new working face underground mined in 2018 and 2019, the natural growth control area and the open-pit mining affected area. The spatiotemporal changes of the surface fraction vegetation coverage (FVC) were analyzed in each area and the correlation between vegetation coverage and climatic factors was studied. The results showed that: (1) The overall vegetation coverage showed a moderate decrease trend in fluctuation from 2017 to 2021. The Open-pit mining affected areas showed the largest decline, reaching 68.3%. The FVC in the underground mining areas had a downward trend, but self-healing effect after mining was also observed. (2) The overall FVC in the study area was positively correlated with the number of precipitation days. (3) There were differences in the sensitivity to mining disturbance for different landform in the underground mining areas. (4) Although the FVC in the Old mining areas had recovered to the level of Natural growth control area, but the annual fluctuation was larger, which might mean lower ecological stability.

Directional Activation of Oxygen by the Au-Loaded ZnAl-LDH with Defect Structure for Highly Efficient Photocatalytic Oxidative Coupling of Methane.

Photocatalytic oxidative coupling of CH4 (OCM) is a promising CH4 conversion process that can achieve efficient methane conversion with the assistance of O2 . It remains to be highly challenging to improve the photocatalytic OCM activity from catalyst design and to deepen the understanding of the reactant activation in the OCM process. In this work, the Au-loaded ZnAl-layered double hydroxides (LDHs) with and without oxygen vacancy are constructed (denoted as Au/ZnAl and Au/ZnAl-v), respectively. When applied for photocatalytic OCM, the Au/ZnAl-v shows a CH4 conversion rate of 8.5 mmol g-1 h-1 with 92% selectivity of C2 H6 at 40 °C, outperforming most reported photocatalytic OCM systems at low temperature reported in the literature. Furthermore, the catalytic performance of Au/ZnAl-v can be stable for 100 h. In contrast, the An/ZnAl exhibits a CH4 conversion rate of 0.8 mmol g-1 h-1 with 46% selectivity of C2 H6 . Detailed characterizations and DFT calculation studies reveal that the introduced Ov sites on Au/ZnAl-v are able to activate O2 , and the resulting superoxide radical O2 ·- greatly promotes the activation of CH4 . The coupling of CH3 · groups with the assistance of Au cocatalyst leads to the formation of C2 H6 with high photocatalytic activity.

Ultrathin NiV Layered Double Hydroxide for Methanol Electrooxidation: Understanding the Proton Detachment Kinetics and Methanol Dehydrogenation Oxidation.

Electrochemical methanol oxidation reaction (MOR) is regarded as a promising pathway to obtain value-added chemicals and drive cathodic H2 production, while the rational design of catalyst and in-depth understanding of the structure-activity relationship remains challenging. Herein, the ultrathin NiV-LDH (u-NiV-LDH) with abundant defects is successfully synthesized, and the defect-enriched structure is finely determined by X-ray adsorption fine structure etc. When applied for MOR, the as-prepared u-NiV-LDH presents a low potential of 1.41 V versus RHE at 100 mA cm-2, which is much lower than that of bulk NiV-LDH (1.75 V vs RHE) at the same current density. The yield of H2 and formate is 98.2% and 88.1% as its initial over five cycles and the ultrathin structure of u-NiV-LDH can be well maintained. Various operando experiments and theoretical calculations prove that the few-layer stacking structure makes u-NiV-LDH free from the interlayer hydrogen diffusion process and the hydrogen can be directly detached from LDH laminate. Moreover, the abundant surface defects upshift the d-band center of u-NiV-LDH and endow a higher local methanol concentration, resulting in an accelerated dehydrogenation kinetics on u-NiV-LDH. The synergy of the proton detachment from the laminate and the methanol dehydrogenation oxidation contributes to the excellent MOR performance of u-NiV-LDH.

Pd Loaded NiCo Hydroxides for Biomass Electrooxidation: Understanding the Synergistic Effect of Proton Deintercalation and Adsorption Kinetics.

The key issue in the 5-hydroxymethylfurfural oxidation reaction (HMFOR) is to understand the synergistic mechanism involving the protons deintercalation of catalyst and the adsorption of the substrate. In this study, a Pd/NiCo catalyst was fabricated by modifying Pd clusters onto a Co-doped Ni(OH)2 support, in which the introduction of Co induced lattice distortion and optimized the energy band structure of Ni sites, while the Pd clusters with an average size of 1.96 nm exhibited electronic interactions with NiCo support, resulting in electron transfer from Pd to Ni sites. The resulting Pd/NiCo exhibited low onset potential of 1.32 V and achieved a current density of 50 mA/cm2 at only 1.38 V. Compared to unmodified Ni(OH)2 , the Pd/NiCo achieved an 8.3-fold increase in peak current density. DFT calculations and in situ XAFS revealed that the Co sites affected the conformation and band structure of neighboring Ni sites through CoO6 octahedral distortion, reducing the proton deintercalation potential of Pd/NiCo and promoting the production of Ni3+ -O active species accordingly. The involvement of Pd decreased the electronic transfer impedance, and thereby accelerated Ni3+ -O formation. Moreover, the Pd clusters enhanced the adsorption of HMF through orbital hybridization, kinetically promoting the contact and reaction of HMF with Ni3+ -O.

Photocatalytic Oxidative Coupling of Ethane to n-Butane Using CO2 as a Soft Oxidant over NiTi-Layered Double Hydroxide.

Selective conversion of ethane (C2 H6 ) to high-value-added chemicals is a very important chemical process, yet it remains challenging owing to the difficulty of ethane activation. Here, a NiTi-layered double hydroxide (NiTi-LDH) photocatalyst is reported for oxidative coupling of ethane to n-butane (n-C4 H10 ) by using CO2 as an oxidant. Remarkably, the as-prepared NiTi-LDH exhibits a high selectivity for n-C4 H10 (92.35%) with a production rate of 62.06 µmol g-1 h-1 when the feed gas (CO2 /C2 H6 ) ratio is 2:8. The X-ray absorption fine structure (XAFS) and photoelectron characterizations demonstrate that NiTi-LDH possesses rich vacancies and high electron-hole separation efficiency, which can promote the coupling of C2 H6 to n-C4 H10 . More importantly, density functional theory (DFT) calculations reveal that ethane is first activated on the oxygen vacancies of the catalyst surface, and the C─C coupling pathway is more favorable than the C─H cleavage to C2 H4 or CH4 , resulting in the high production rate and selectivity for n-C4 H10 .

Coexistence of Au single atoms and Au nanoparticles on NiAl-LDH for selective electrooxidation of benzyl alcohol to benzaldehyde.

Introducing different active sites into heterogeneous catalysts provides new prospects to address the challenges in single-atom catalysis. Herein, the Au single atoms together and the Au nanoparticles were loaded onto NiAl-LDH by a facile impregnation-reduction method for the first time, resulting in the formation of Au1+n-NiAl-LDH, in which abundant Au single atoms are located around the Au nanoparticles with ∼5 nm size. When applied in the electrocatalytic benzyl alcohol oxidation reaction (BAOR), the as-prepared Au1+n-NiAl-LDH exhibits a remarkable selectivity of 91% and 177.63 µmol for benzaldehyde in 5 hours, while in contrast examples using solely Au single atom loaded NiAl-LDH (Au1-NiAl-LDH) and solely Au nanoparticle loaded NiAl-LDH (Aun-NiAl-LDH) can only realize 87.36 µmol production (75% selectivity) and 48.90 µmol production (28% selectivity) of benzaldehyde, respectively. Such a dramatic difference can be attributed to the synergistic effects of Au single atoms and Au nanoparticles. DFT calculation results reveal that for Au1+n-NiAl-LDH, Au single atoms promote the dehydrogenation capacity of LDH laminates, while Au nanoparticles offer adsorption sites for the electrophilic attachment of benzyl alcohol.

Enabling Specific Benzene Oxidation by Tuning the Adsorption Behavior on Au Loaded MgAl Layered Double Hydroxides.

Direct and selective oxidation of benzene to phenol is a long-term goal in industry. Although great efforts have been made in homogenous catalysis, it still remains a huge challenge to drive this reaction via heterogeneous catalysts under mild conditions. Herein, a single-atom Au loaded MgAl-layered double hydroxide (Au1 -MgAl-LDH) with a well-defined structure, in which the Au single atoms are located on the top of Al3+ with Au-O4 coordination as revealed by extended x-ray-absorption fine-structure (EXAFS)and density-functional theory (DFT)calculation is reported. The photocatalytic results prove the Au1 -MgAl-LDH is capable of driving benzene oxidation reaction with O2 in water, and exhibits a high selectivity of 99% for phenol. While contrast experiment shows a ≈99% selectivity for aliphatic acid with Au nanoparticle loaded MgAl-LDH (Au-NP-MgAl-LDH). Detailed characterizations confirm that the origin of the selectivity difference can be attributed to the profound adsorption behavior of substrate benzene with Au single atoms and nanoparticles. For Au1 -MgAl-LDH, single Au-C bond is formed in benzene activation and result in the production of phenol. While for Au-NP-MgAl-LDH, multiple AuC bonds are generated in benzene activation, leading to the crack of CC bond.

Dual Engineering of Lattice Strain and Valence State of NiAl-LDHs for Photoreduction of CO2 to Highly Selective CH4.

Converting CO2 to clean-burning fuel such as natural gas (CH4 ) with high activity and selectivity remains to be a grand challenge due to slow kinetics of multiple electron transfer processes and competitive hydrogen evolution reaction (HER). Herein, the fabrication of surfactants (C11 H23 COONa, C12 H25 SO4 Na, C16 H33 SO4 Na) intercalated NiAl-layered double hydroxides (NiAl-LDH) is reported, resulting in the formation of LDH-S1 (S1 = C11 H23 COO- ), LDH-S2 (S2 = C12 H25 SO4 - ) and LDH-S3 (S3 = C16 H33 SO4 - ) with curved morphology. Compared with NiAl-LDH with a 1.53% selectivity of CH4 , LDH-S2 shows higher selectivity of CH4 (83.07%) and lower activity of HER (3.84%) in CO2 photoreduction reaction (CO2 PR). Detailed characterizations and DFT calculation indicates that the inherent lattice strain in LDH-S2 leads to the structural distortion with the presence of VNi/Al defects and compressed MOM bonds, and thereby reduces the overall energy barrier of CO2 to CH4 . Moreover, the lower oxidation states of Ni in LDH-S2 enhances the adsorption of intermediates such as OCOH* and *CO, promoting the hydrogenation of CO to CH4 . Therefore, the coupling effect of both lattice strain and electronic structure of the LDH-S2 significantly improves the activity and selectivity for CO2 PR.

Fabrication of Epitaxially Grown Mg2Al-LDH-Modified Nanofiber Membranes for Efficient and Sustainable Separation of Water-in-Oil Emulsion.

Efficient separation of water-in-oil emulsion is of great importance but remains highly challenging since such emulsion contains stable tiny droplets with a diameter less than 20 µm. Herein, we reported the fabrication of a modular fibrous functional membrane using an "in situ growth and covalent functionalization" strategy. The as-prepared PAN@LDH@OTS (PAN = polyacrylonitrile; LDH = layered double hydroxides; and OTS = octadecyltrichlorosilane) membrane possessed an interlaced rough nanostructured surface with intriguing superhydrophobic/superlipophilic properties. When applied for the separation of surfactant-stabilized water-in-oil emulsion (SSE), the PAN@LDH@OTS membrane exhibited an ultrahigh permeation flux of up to 4.63 × 104 L m-2 h-1 with an outstanding separation efficiency of >99.92%, outperforming most of the state-of-the-art membranes. In addition, the membrane can maintain a stable permeation flux and superhydrophobic/superlipophilic properties after 20 times of use. Detailed characterization demonstrated that the demulsification of the SSE process was as follows: first, the droplets can be easily adsorbed to the PAN@LDH@OTS membrane due to the improved intermolecular interactions between OTS and the surfactants (Span 80); second, the droplets can be deformed by the electropositive LDH laminate; and third, the deformed tiny emulsion droplets coalesced into large droplets and floated up, and as a result, efficient separation of SSE can be achieved.

Fabrication of Porous Aluminum Coating by Cored Wire Arc Spray for Anchoring Antifouling Hydrogel Layer.

Biofouling has been persisting as a worldwide problem due to the difficulties in finding efficient environment-friendly antifouling coatings for long-term applications. Developing novel coatings with desired antifouling properties has been one of the research goals for surface coating community. Recently hydrogel coating was proposed to serve as antifouling layer, for it offers the advantages of the ease of incorporating green biocides, and resisting attachment of microorganisms by its soft surface. Yet poor adhesion of the hydrogel on steel surfaces is a big concern. In this study, porous matrix aluminum coatings were fabricated by cored wire arc spray, and the sizes of the pores in the aluminum (Al) coatings were controlled by altering the size of the cored powder of sodium chloride. Silicone hydrogel was further deposited on the porous coating. The hydrogel penetrated into the open pores of the porous Al coatings, and the porous Al structure significantly enhanced the adhesion of the hydrogel. In addition, hydrogel coating exhibited very encouraging antifouling properties.

Author Correction: Arbuscular mycorrhizal fungi promote the growth of plants in the mining associated clay.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Arbuscular mycorrhizal fungi promote the growth of plants in the mining associated clay.

It is urgent to restore the ecological function in open-pit mining areas on grassland in Eastern China. The open-pit mines have abundant of mining associated clay, which is desirable for using as a soil source for ecological restoration. The mining associated clay in Hulunbuir district, Inner Mongolia was selected and mixed with a sandy soil at a ratio of 1:1 (S_C soil). Also, effects of arbuscular mycorrhizal fungi (AMF) inoculation on soil functions were studied. The aboveground and underground biomass of maize in S_C soil was 1.49 and 2.41 times higher than that of clay soil, respectively. In the topsoil and S_C soil, the growth hormone (IAA) and cytokinin (CTK) levels of maize were higher than that of clay, while abscission acid (ABA) levels were lower. The inoculation with AMF could significantly improve the biomass of maize and enhance the stress resistance of plants. Through structural equation model (SEM) analyses, it was found that the soil type and AMF inoculation had the most direct impact on maize growth and biomass content. These finds extend our knowledge regarding a low-cost method for physical and biological improvement of mining associated clay, and to provide theoretical support for large-scale application in the future.

Arbuscular mycorrhizal fungi alleviate root damage stress induced by simulated coal mining subsidence ground fissures.

Coal mining results in surface subsidence and induces the development of ground fissures that damage surrounding plant roots. Very few studies have explored the stress of root damage caused by ground fissures and whether arbuscular mycorrhizal fungi (AMF) can relieve root damage stress induced by ground fissures. In the present study we simulated ground fissure induced root damage, examined the resultant changes in endogenous hormones, root system morphology, leaf area, leaf chlorophyll content, nutrient content and biomass of maize, and examined the ameliorative effects of AMF on maize with root damage. Ground fissures led to significantly higher levels of endogenous abscisic acid (ABA) but significantly reduced levels of indole-3-acetic acid (IAA), gibberellins (GA) and cytokinin (CTK). In addition, ground fissures led to significantly reduced root biomass, total root length, root tip number, total root volume, plant nutrient content, leaf chlorophyll content and leaf area. The shoot biomass of root damaged maize decreased significantly by 46%. By contrast, AMF increased IAA and CTK levels in maize roots, reduced ABA levels, improved the hormone balance of damaged plants, increased total root length, root tip number, total root volume, leaf area and leaf chlorophyll content, increased nutrient content and increased shoot biomass by 34%. Overall, by simulating coal mining subsidence ground fissures, the study investigated the effects of root damage stress on plant biomass, found that AMF can alleviate the mechanical damages to the root system, and provided a theoretical basis for microbial remediation in areas subject to subsidence due to coal mining.

Wheat straw biochar amendments on the removal of polycyclic aromatic hydrocarbons (PAHs) in contaminated soil.

Soil amendments of wheat straw biochar (BC), lignocellulosic substrate (LS), BC+LS, and BC+LS+BR (surfactant Brij30) were investigated for the first time in order to remedy polycyclic aromatic hydrocarbons (PAHs)-polluted soil using pilot scale microcosm incubation. We hypothesized that the removal of PAHs could be inhibited due to the adsorption and immobilization of biochar and the inhibition depends on the molecular-weight of PAHs. The removal rates of phenanthrene (PHE) and Benzo[a]pyrene (BaP) ranked as C=BC>LS=LS+BC=LS+BC+BR and C=BC=LS+BC+BR>LS=LS+BC. Wheat straw biochar inhibited the removal of PHE and accelerated BaP removal. The activity of Dehydrogenase (DH) was depressed by the addition of the biochar while the activity of polyphenol oxidase (PPO) was stimulated. Lignocellulose and surfactant are favourable to sustain soil microbiological activity and the removal of PAHs although the diversity of bacterial community was not significantly changed. The findings implied that the components of PAHs are necessary to consider when the amendments are implemented by associated biochar in PAH-polluted soil.

Responses of soil ammonia-oxidizing microorganisms to repeated exposure of single-walled and multi-walled carbon nanotubes.

The impacts of carbon nanotubes (CNTs) including single-walled carbon nanotubes (SWNTs) and multi-walled carbon nanotubes (MWNTs) on soil microbial biomass and microbial community composition (especially on ammonium oxidizing microorganisms) have been evaluated. The first exposure of CNTs lowered the microbial biomass immediately, but the values recovered to the level of the control at the end of the experiment despite the repeated addition of CNTs. The abundance and diversity of ammonium-oxidizing archaea (AOA) were higher than that of ammonium-oxidizing bacteria (AOB) under the exposure of CNTs. The addition of CNTs decreased Shannon-Wiener diversity index of AOB and AOA. Two-way ANOVA analysis showed that CNTs had significant effects on the abundance and diversity of AOB and AOA. Dominant terminal restriction fragments (TRFs) of AOB exhibited a positive relationship with NH4(+), while AOA was on the contrary. It implied that AOB prefer for high-NH4(+) soils whereas AOA is favored in low NH4(+) soils in the CNT-contaminated soil.