Hydrolytic degradation of methoxychlor by immobilized cellulase on LDHs@Fe3O4 nanocomposites.

In this study, we synthesized Fe3O4 using the co-precipitation method and then prepared magnetic carrier LDHs@Fe3O4 by immobilizing layered double hydroxide on Fe3O4 by in situ growth method. Cellulase was immobilized on this magnetic carrier by using glutaraldehyde as a coupling agent, which can be used for degrading Methoxychlor (MXC). The results demonstrated the maximum MXC removal efficiency of 73.4% at 45 °C and pH = 6.0 with excellent reusability. Through kinetic analysis, it was found that the degradation reaction conforms to the Langmuir-Hinshelwood model and is a first-order reaction. Finally, according to the EPR analysis, the active radicals in the system were found to be OH· and the degradation mechanism was proposed in combination with LC-MS. This study provides a feasible method for degrading organochlorine pesticides, which can be used for groundwater purification.

Strain-modulated Ru-O Covalency in Ru-Sn Oxide Enabling Efficient and Stable Water Oxidation in Acidic Solution.

RuO2 is one of the benchmark electrocatalysts used as the anode material in proton exchange membrane water electrolyser. However, its long-term stability is compromised due to the participation of lattice oxygen and metal dissolution during oxygen evolution reaction (OER). In this work, weakened covalency of Ru-O bond was tailored by introducing tensile strain to RuO6 octahedrons in a binary Ru-Sn oxide matrix, prohibiting the participation of lattice oxygen and the dissolution of Ru, thereby significantly improving the long-term stability. Moreover, the tensile strain also optimized the adsorption energy of intermediates and boosted the OER activity. Remarkably, the RuSnOx electrocatalyst exhibited excellent OER activity in 0.1 M HClO4 and required merely 184 mV overpotential at a current density of 10 mA cm-2 . Moreover, it delivered a current density of 10 mA cm-2 for at least 150 h with negligible potential increase. This work exemplifies an effective strategy for engineering Ru-based catalysts with extraordinary performance toward water splitting.

Polymorphism-Dependent Organic Room Temperature Phosphorescent Scintillation for X-Ray Imaging.

Organic phosphorescent scintillating materials have shown great potential for applications in radiography and radiation detection due to their efficient utilization of excitons. However, revealing the relationship between molecule stacking and the phosphorescent radioluminescence of scintillators is still challenging. This study reports on two phenothiazine derivatives with polymorphism-dependent phosphorescence radioluminescence. The experiments reveal that molecule stacking significantly affects the non-radiation decay of the triplet excitons of scintillators, which further determines the phosphorescence scintillation performance under X-ray irradiation. These phosphorescent scintillators exhibit high radio stability and have a low detection limit of 278 nGys-1 . Additionally, the potential application of these scintillators in X-ray radiography, based on their X-ray excited radioluminescence properties, is demonstrated. These findings provide a guideline for obtaining high-performance phosphorescent scintillating materials by shedding light on the effect of crystal packing on the radioluminescence of organic molecules.

Narrowband Organic Afterglow via Phosphorescence Förster Resonance Energy Transfer for Multifunctional Applications.

Achieving multicolor organic afterglow materials with narrowband emission and high color purity is important in various optoelectronic fields but remains a great challenge. Here, an efficient strategy is presented to obtain narrowband organic afterglow materials via Förster resonance energy transfer from long-lived phosphorescence donors to narrowband fluorescence acceptors in a polyvinyl alcohol matrix. The resulting materials exhibit narrowband emission with a full width at half maximum (FWHM) as small as 23 nm and the longest lifetime of 721.22 ms. Meanwhile, by pairing the appropriate donors and acceptors, multicolor and high color purity afterglow ranging from green to red with the maximum photoluminescence quantum yield of 67.1% are achieved. Moreover, given their long luminescence lifetime, high color purity, and flexibility, the potential applications are demonstrated in high-resolution afterglow displays and dynamic and quick information identification in low-light conditions. This work provides a facile approach for developing multicolor and narrowband afterglow materials as well as expands the features of organic afterglow.

Load and release of gambogic acid via dual-target ellipsoidal-Fe3O4@SiO2@mSiO2-C18@dopamine hydrochloride -graphene quantum dots-folic acid and its inhibition to VX2 tumor cells.

Ellipsoidal-Fe3O4@SiO2@mSiO2-C18@dopamine hydrochloride-graphene quantum dots-folic acid (ellipsoidal-HMNPs@PDA-GQDs-FA), a dual-functional drug carrier, was stepwise constructed. Theα-Fe2O3ellipsoidal nanoparticles were prepared by a hydrothermal method, and then coated with SiO2by Stöber method. The resulting core-shell structure, Fe3O4@SiO2@mSiO2-C18magnetic nano hollow spheres, abbreviated as HMNPs, was finally grafted with graphene quantum dots (GQDs), dopamine hydrochloride (PDA) and folic acid (FA) by amide reaction to obtain HMNPs@PDA-GQDs-FA. Transmission electron microscopy, Fourier transform infrared spectroscopy, fluorescence spectroscopy and element analysis proved the successful construction of the HMNPs@PDA-GQDs-FA nanoscale carrier-cargo composite. The carrier HMNPs@PDA-GQDs-FA has higher load (51.63 ± 1.53%) and release (38.56 ± 1.95%) capacity for gambogic acid (GA). Cytotoxicity test showed that the cell survival rate was above 95%, suggesting the cytotoxicity of the carrier-cargo was very low. The cell lethality (74.91 ± 1.2%) is greatly improved after loading GA because of the magnetic targeting of HMNPs, the targeting performance of FA to tumor cells, and the pH response to the surrounding environment of tumor cells of PDA. All results showed that HMNPs@PDA-GQDs-FA had good biocompatibility and could be used in the treatment of VX2 tumor cells after loading GA.

Organic phosphorescent scintillation from copolymers by X-ray irradiation.

Scintillators that exhibit X-ray-excited luminescence have great potential in radiation detection, X-ray imaging, radiotherapy, and non-destructive testing. However, most reported scintillators are limited to inorganic or organic crystal materials, which have some obstacles in repeatability and processability. Here we present a facile strategy to achieve the X-ray-excited organic phosphorescent scintillation from amorphous copolymers through the copolymerization of the bromine-substituted chromophores and acrylic acid. These polymeric scintillators exhibit efficient X-ray responsibility and decent phosphorescent quantum yield up to 51.4% under ambient conditions. The universality of the design principle was further confirmed by a series of copolymers with multi-color radioluminescence ranging from green to orange-red. Moreover, we demonstrated their potential application in X-ray radiography. This finding not only outlines a feasible principle to develop X-ray responsive phosphorescent polymers, but also expands the potential applications of polymer materials with phosphorescence features.

Synergistic Cr2 O3 @Ag Heterostructure Enhanced Electrocatalytic CO2 Reduction to CO.

The electrocatalytic CO2 RR to produce value-added chemicals and fuels has been recognized as a promising means to reduce the reliance on fossil resources; it is, however, hindered due to the lack of high-performance electrocatalysts. The effectiveness of sculpturing metal/metal oxides (MMO) heterostructures to enhance electrocatalytic performance toward CO2 RR has been well documented, nonetheless, the precise synergistic mechanism of MMO remains elusive. Herein, an in operando electrochemically synthesized Cr2 O3 -Ag heterostructure electrocatalyst (Cr2 O3 @Ag) is reported for efficient electrocatalytic reduction of CO2 to CO. The obtained Cr2 O3 @Ag can readily achieve a superb FECO of 99.6% at -0.8 V (vs RHE) with a high JCO of 19.0 mA cm-2 . These studies also confirm that the operando synthesized Cr2 O3 @Ag possesses high operational stability. Notably, operando Raman spectroscopy studies reveal that the markedly enhanced performance is attributable to the synergistic Cr2 O3 -Ag heterostructure induced stabilization of CO2 •- /*COOH intermediates. DFT calculations unveil that the metallic-Ag-catalyzed CO2 reduction to CO requires a 1.45 eV energy input to proceed, which is 0.93 eV higher than that of the MMO-structured Cr2 O3 @Ag. The exemplified approaches in this work would be adoptable for design and development of high-performance electrocatalysts for other important reactions.

Stable Two-dimensional Nanoconfined Ionic Liquids with Highly Efficient Ionic Conductivity.

Amid the burgeoning environmental concerns, electrochemical energy storage is of great demand, inspiring the rapid development of electrolytes. Quasi-liquid solid electrolytes (QLSEs) demonstrate exciting properties that combine high ionic conductivity and safety. Herein, a QLSE system is constructed by confining ionic liquids (ILs) into 2D materials-based membranes, which creates a subtle platform for the investigation of the nanoconfined ion transport process. The highest ionic conductivity increment of 506% can be observed when ILs are under nanoconfinement. Correlation of experimental results and simulation evidently prove the diffusion behaviors of ILs are remarkably accelerated when confined in nanochannels, ascribing from the promoted dissociation of ILs. Concurrently, nanoconfined ILs demonstrate a highly ordered distribution, lower interplay, and higher free volume compared against bulk systems. This work reveals and analyzes the phenomenon of ionic conductivity elevation in nanoconfined ILs, and offers inspiring opportunities to fabricate the highly stable and efficient QLSEs based on layered nanomaterials for energy storage applications.

Recovery of microbial community in strongly alkaline bauxite residues after amending biomass residue.

The aim of this study was to characterize the effects of cornstalk biomass amendments on microbial communities in bauxite residues (BRs) by phylogenetic analysis. Improvements in soil geochemical, physical, and biological properties were assessed to identify the major factors controlling microbial community development in BRs. After one year of incubation, the salinity and structure of the amended BRs had gradually improved, with pH dropping from 11.39 to 9.89, the exchangeable sodium percentage (ESP) dropping from 86.3% to 35.2%, and the mean weight diameter (MWD) rising from 0.12 mm to 0.38 mm. Further analysis of community level physiological profiles (CLPP) showed that the microbial utilization of different carbohydrates had shifted significantly, in addition to increases in the diversity index H' (0.7-7.34), U (2.16-3.14), and the average well color development (0.059-1.08). Over the one-year outside incubation, the dominant fungal phyla in the BRs had shifted gradually from Ascomycota (85.64%) to Ascomycota (52.07%) and Basidiomycota (35.53%), while the dominant bacterial phyla had shifted from Actinobacteria (38.47%), Proteobacteria (21.39%), and Gemmatimonadetes (12.72%) to Actinobacteria (14.87%), Proteobacteria (23.53%), and Acidobacteria (14.37%). Despite these shifts, microbial diversity remained lower in the amended BRs than in the natural soil. Further redundancy analysis indicated that pH was the major factor driving shifts in the bacterial community, while aggregates were the major factor driving shifts in the fungal community. This study demonstrated that amendment with cornstalk biomass shifted the microbial community in the BRs from halophilic groups to acidogenic groups by improving the soil environmental conditions.

Rational design of metal oxide catalysts for electrocatalytic water splitting.

Electrocatalytic energy conversion between electricity and chemical bonding energy is realized through redox reactions with multiple charge transfer steps at the electrode-electrolyte interface. The surface atomic structure of the electrode materials, if appropriately designed, will provide an energetically affordable pathway with individual reaction intermediates that not only reduce the thermodynamic energy barrier but also allow an acceptably fast kinetic rate of the overall redox reaction. As one of the most abundant and stable forms, oxides of transitional metals demonstrated promising electrocatalytic activities towards multiple important chemical reactions. In this topical review, we attempt to discuss the possible avenues to construct the electrocatalytic active surface for this important class of materials for two essential chemical reactions for water splitting. A general introduction of the electrochemical water splitting process on the electrocatalyst surface with applied potential will be provided, followed by a discussion on the fundamental charge transfers and the mechanism. As the generally perceived active sites are chemical reaction dependent, we offer a general overview of the possible approaches to construct or create electrocatalytically active sites in the context of surface atomic structure engineering. The review concludes with perspectives that summarize challenges and opportunities in electrocatalysis and how these can be addressed to unlock the electrocatalytic potentials of the metal oxide materials.

Effect of Soil Solution Properties and Cu2+ Co-Existence on the Adsorption of Sulfadiazine onto Paddy Soil.

Paddy soils are globally distributed and saturated with water long term, which is different from most terrestrial ecosystems. To better understand the environmental risks of antibiotics in paddy soils, this study chose sulfadiazine (SDZ) as a typical antibiotic. We investigated its adsorption behavior and the influence of soil solution properties, such as pH conditions, dissolved organic carbon (DOC), ionic concentrations (IC), and the co-existence of Cu2+. The results indicated that (1) changes in soil solution pH and IC lower the adsorption of SDZ in paddy soils. (2) Increase of DOC facilitated the adsorption of SDZ in paddy soils. (3) Cu2+ co-existence increased the adsorption of SDZ on organic components, but decreased the adsorption capacity of clay soil for SDZ. (4) Further FTIR and SEM analyses indicated that complexation may not be the only form of Cu2+ and SDZ co-adsorption in paddy soils. Based on the above results, it can be concluded that soil solution properties and co-existent cations determine the sorption behavior of SDZ in paddy soils.

Wide-range lifetime-tunable and responsive ultralong organic phosphorescent multi-host/guest system.

The rational lifetime-tuning strategy of ultralong organic phosphorescence is extraordinarily important but seldom reported. Herein, a series of multi-host/guest ultralong organic phosphorescence materials with dynamic lifetime-tuning properties were reported. By doping a non-room-temperature phosphorescence emitter into various solid host matrices with continuously reduced triplet energy levels, a wide-range lifetime (from 3.9 ms gradually to 376.9 ms) phosphorescence with unchangeable afterglow colors were realized. Further studies revealed that the host matrices were employed to afford rigid environment and proper energy levels to generate and stabilize the long-live triplet excitons. Meanwhile, these multi-host/guest ultralong organic phosphorescence materials also exhibited excitation-dependent phosphorescence and temperature-controlled afterglow on/off switching properties, according to the virtue of various photophysical and thermal properties of the host matrices. This work provides a guiding strategy to realize lifetime-tuning ultralong organic phosphorescence with lifetime-order encoding characteristic towards widespread applications in time-resolved information displaying, higher-level security protection, and dynamic multi-dimensional anti-counterfeiting.

Resilience of fungal flora in bauxite residues amended with organic matter and vermiculite/fly ash.

The fungal community and soil geochemical, physical and biological parameters were analyzed, respectively, in bauxite residues (BRs) treated with organic matter and vermiculite/fly ash by phylogenetic analysis of ITS-18 S rRNA, community level physiological profiles (CLPP) and so on. The results indicated that after amendment of the BR, microbial utilization of carbohydrates and their enzyme activities were significantly increased, but fungal compositions at the phylum level were similar and dominated by the phylum of Ascomycota (82.05-98.96%, RA: relative abundance) after one year of incubation. The fungal taxa in the amended BR treatments, however, show significantly less alpha and beta diversity compared with the reference soils, although they still harbor a substantial novel taxon. The combined amendment of organic matter (OM) and vermiculite/fly ash significantly increases the fungal taxa at the genus and species level compared with solely OM amendment. The results of the following canonical correspondence analysis found that, over 90% variation of the fungal community could be explained by pH, OM and mean weight diameter (MWD) of aggregates; but the biological indicators, including urease (UR), dehydrogenase (DHA) and the value of average well color development (AWCD) could explain only 50% variation of the fungal flora in BRs. This paper indicated that resilience of fungal community in BRs was positively correlated with the BRs' improvement in fertility as well as biogeochemical properties, but alkalinity must be firstly decreased to the target level of BRs' rehabilitation.

Response of ammonia-oxidizing archaea and bacteria to sulfadiazine and copper and their interaction in black soils.

The large-scale development of animal husbandry and the wide agricultural application of livestock manure lead to more and more serious co-pollution of heavy metals and antibiotics in soil. In this study, two common feed additives, copper (Cu) and sulfadiazine (SDZ), were selected as target pollutants to evaluate the toxicity and interaction of antibiotics and heavy metals on ammonia oxidizers diversity, potential nitrification rate (PNR), and enzymatic activity in black soils. The results showed that soil enzyme activity was significantly inhibited by single Cu pollution, but the toxicity could be reduced by introducing low-concentration SDZ (5 mg · kg-1), which showed an antagonistic effect between Cu and SDZ (5 mg · kg-1), while the combined toxicity of high-concentration SDZ (10 mg · kg-1) and Cu were strengthened compared with the single Cu contamination on soil enzymes. In contrast, soil PNR was more sensitive to single Cu pollution and its combined pollution with SDZ than the enzyme activity. Real-time fluorescence quota PCR and Illumina Hiseq/Miseq sequencing results showed that ammonia-oxidizing archaea (AOA) was decreased in C2 (200 mg · kg-1 Cu treatment) and ammonia-oxidizing bacteria (AOB) was obviously stimulated in soil contaminated in C2, while in S5 (5 mg · kg-1 SDZ treatment), AOB was decreased; both AOA and AOB were significantly decreased at gene level in soils with combined pollutants (C2S5, 200 mg · kg-1 Cu combined with 5 mg · kg-1 SDZ). So, it can be concluded that combined pollution can cause more serious toxicity on the enzymatic activity, PNR, and ammonia-oxidizing microorganisms in soil through the synergistic effect between heavy metals and antibiotics pollutants.

Coexisting Single-Atomic Fe and Ni Sites on Hierarchically Ordered Porous Carbon as a Highly Efficient ORR Electrocatalyst.

The development of oxygen reduction reaction (ORR) electrocatalysts based on earth-abundant nonprecious materials is critically important for sustainable large-scale applications of fuel cells and metal-air batteries. Herein, a hetero-single-atom (h-SA) ORR electrocatalyst is presented, which has atomically dispersed Fe and Ni coanchored to a microsized nitrogen-doped graphitic carbon support with unique trimodal-porous structure configured by highly ordered macropores interconnected through mesopores. Extended X-ray absorption fine structure spectra confirm that Fe- and Ni-SAs are affixed to the carbon support via FeN4 and NiN4 coordination bonds. The resultant Fe/Ni h-SA electrocatalyst exhibits an outstanding ORR activity, outperforming SA electrocatalysts with only Fe- or Ni-SAs, and the benchmark Pt/C. The obtained experimental results indicate that the achieved outstanding ORR performance results from the synergetic enhancement induced by the coexisting FeN4 and NiN4 sites, and the superior mass-transfer capability promoted by the trimodal-porous-structured carbon support.

Engineering the Core-Shell-Structured NCNTs-Ni2Si@Porous Si Composite with Robust Ni-Si Interfacial Bonding for High-Performance Li-Ion Batteries.

A new strategy has been innovatively proposed for wrapping the Ni-incorporated and N-doped carbon nanotube arrays (Ni-NCNTs) on porous Si with robust Ni-Si interfacial bonding to form the core-shell-structured NCNTs-Ni2Si@Si. The hierarchical porous silicon core was first fabricated via a novel self-templating synthesis route based on two crucial strategies: in situ thermal evaporation of crystal water from the perlite for producing porous SiO2 and subsequent magnesiothermic reduction of porous SiO2 into porous Si. Ni-NCNTs were subsequently constructed based on the Ni-catalyzed tip-growth mechanism and were further engineered to fully wrap the porous Si microparticles by forming the Ni2Si alloy at the heterojunction interface. When the prepared NCNTs-Ni2Si@Si was evaluated as the anode material for Li-ion batteries, the hierarchical porous system in the Si core and the rich void spaces in carbon nanotube arrays contributed to the remarkable accommodation of volume expansion of Si as well as the significant increase of Li+ diffusion and Si utilization. Moreover, the Ni2Si alloy, which chemically linked the Ni-NCNTs and porous Si, not only provided good electronic contact between the Si core and carbon shell but also effectively prevented the CNTs' detachment from the Si core during cycling. The multifunctional structural design rendered the whole electrode highly stable and active in Li storage, and the electrochemically active NCNTs-Ni2Si@Si electrode delivered a high reversible capacity of 1547 mAh g-1 and excellent cycling stability (85% capacity retention after 600 discharge-charge cycles) at a current density of 358 mA g-1 (0.1 C) as well as good rate performance (778 mAh g-1 at 2 C), showing great potential as an efficient and stable anode for high energy density Li-ion batteries.

Vapor-phase polymerization of poly(3, 4-ethylenedioxythiophene) nanofibers on carbon cloth as electrodes for flexible supercapacitors.

In this study, an evaporative vapor-phase polymerization approach was employed to fabricate vertically aligned poly(3, 4-ethylenedioxythiophene) (PEDOT) nanofibers on the surface of carbon cloth (CC). Optimized reaction conditions can obtain well distributed and uniform layers of high-aspect-ratio PEDOT nanofibers on CC. The hierarchical PEDOT/CC structure as a freestanding electrode exhibits good electrochemical properties. As a flexible symmetric supercapacitor, the PEDOT/CC hybrid electrode displays a specific areal capacitance of 201.4 mF cm(-2) at 1 mA cm(-2), good flexibility with a higher value (204.6 mF cm(-2)) in the bending state, and a good cycling stability of 92.4% after 1000 cycles. Moreover, the device shows a maximum energy density of 4.0 Wh kg(-1) (with a power density of 3.2 kW kg(-1)) and a maximum power density of 4.2 kW kg(-1) (with an energy density of 3.1 Wh kg(-1)). The results demonstrate that PEDOT may be a promising material for storage devices through a simple and efficient vapor-phase polymerization process with precisely controlled reaction conditions.