Graphdiyne Enabled Nitrogen Vacancy Formation in Copper Nitride for Efficient Ammonia Synthesis.

The electrocatalytic reduction of nitrate is promising for sustainable ammonia synthesis but suffers from slow reduction kinetics and multiple competing reactions. Here, we report a catalyst featuring copper nitride (Cu3N) anchored on a novel graphdiyne support (termed Cu3N/GDY), which is used for electrocatalytic reduction of nitrate to produce ammonia. The GDY absorbed hydrogen and enabled nitrogen (N) vacancy formation in Cu3N for the fast nitrate reduction reaction (NO3RR). Further, the distinct absorption sites formed by GDY and N vacancy enabled the excellent selectivity and stability of NO3RR. Notably, the Cu3N/GDY catalyst achieved a high ammonia yield (YNH3) up to 35280 µg h-1 mgcat.-1 and a high Faradaic efficiency (FE) of 98.1% using 0.1 M NO3- at -0.9 V versus a reversible hydrogen electrode (RHE). Using electron paramagnetic resonance (EPR) technology and in situ X-ray absorption fine structure (XAFS) spectroscopy measurement, we visualized the N vacancy formation in Cu3N and electrocatalytic NO3RR enabled by GDY. These findings show the promise of GDY in sustainable ammonia synthesis and highlight the efficacy of Cu3N/GDY as a catalyst.

Kinetic Modulation of Carbon Nanotube Growth in Direct Spinning for High-Strength Carbon Nanotube Fibers.

With impressive individual properties, carbon nanotubes (CNTs) show great potential in constructing high-performance fibers. However, the tensile strength of as-prepared carbon nanotube fibers (CNTFs) by floating catalyst chemical vapor deposition (FCCVD) is plagued by the weak intertube interaction between the essential CNTs. Here, we developed a chlorine (Cl)/water (H2O)-assisted length furtherance FCCVD (CALF-FCCVD) method to modulate the intertube interaction of CNTs and enhance the mechanical strength of macroscopic fibers. The CNTs acquired by the CALF-FCCVD method show an improvement of 731% in length compared to that by the conventional iron-based FCCVD system. Moreover, CNTFs prepared by CALF-FCCVD spinning exhibit a high tensile strength of 5.27 ± 0.27 GPa (4.62 ± 0.24 N/tex) and reach up to 5.61 GPa (4.92 N/tex), which outperforms most previously reported results. Experimental measurements and density functional theory calculations show that Cl and H2O play a crucial role in the furtherance of CNT growth. Cl released from the decomposition of methylene dichloride greatly accelerates the growth of the CNTs; H2O can remove amorphous carbon on the floating catalysts to extend their lifetime, which further modulates the growth kinetics and improves the purity of the as-prepared fibers. Our design of the CALF-FCCVD platform offers a powerful way to tune CNT growth kinetics in direct spinning toward high-strength CNTFs.

Optimization of Bear Oil Extraction Process and Hair Growth Activity.

According to ancient Chinese books, bear grease has the effects of strengthening muscles and bones, which is beneficial for weakness, but there is relatively little research on it. Thus, the extraction of it is beneficial for compensating for research in this area. In this study, a uniform experimental design method was used to optimize the extraction process of bear grease by enzymatic hydrolysis extraction, and the extraction rate can reach 81.89% under optimized extraction conditions. Furthermore, the components of bear grease obtained by this study were analyzed by GC-MS, and the results showed that ursolic oil was rich in unsaturated fatty acids (67.51%), which was higher than that of the traditional method (66.92%). The composition of bear grease extracted by the enzymatic method was also better than that extracted by the traditional method. In addition, bear grease obtained in this study had the obvious activity of promoting hair growth. The length, weight, and number of hair follicles in the depilation area of mice in the high-dose group were significantly different from those in the blank group (p < 0.01). This study optimized the extraction process of bear grease and conducted a preliminary analysis of its fatty acid composition, which is expected to provide some reference for the development of the medicinal value of bear grease.

Engineering Electronic Structure of Nitrogen-Carbon Sites by sp3 -Hybridized Carbon and Incorporating Chlorine to Boost Oxygen Reduction Activity.

Development of efficient and easy-to-prepare low-cost oxygen reaction electrocatalysts is essential for widespread application of rechargeable Zn-air batteries (ZABs). Herein, we mixed NaCl and ZIF-8 by simple physical milling and pyrolysis to obtain a metal-free porous electrocatalyst doped with Cl (mf-pClNC). The mf-pClNC electrocatalyst exhibits a good oxygen reduction reaction (ORR) activity (E1/2 =0.91 V vs. RHE) and high stability in alkaline electrolyte, exceeding most of the reported transition metal carbon-based electrocatalysts and being comparable to commercial Pt/C electrocatalysts. Likewise, the mf-pClNC electrocatalyst also shows state-of-the-art ORR activity and stability in acidic electrolyte. From experimental and theoretical calculations, the better ORR activity is most likely originated from the fact that the introduced Cl promotes the increase of sp3 -hybridized carbon, while the sp3 -hybridized carbon and Cl together modify the electronic structure of the N-adjacent carbons, as the active sites, while NaCl molten-salt etching provides abundant paths for the transport of electrons/protons. Furthermore, the liquid rechargeable ZAB using the mf-pClNC electrocatalyst as the cathode shows a fulfilling performance with a peak power density of 276.88 mW cm-2 . Flexible quasi-solid-state rechargeable ZAB constructed with the mf-pClNC electrocatalyst as the cathode exhibits an exciting performance both at low, high and room temperatures.

Hydrogen Radical-Induced Electrocatalytic N2 Reduction at a Low Potential.

Realizing efficient hydrogenation of N2 molecules in the electrocatalytic nitrogen reduction reaction (NRR) is crucial in achieving high activity at a low potential because it theoretically requires a higher equilibrium potential than other steps. Analogous to metal hydride complexes for N2 reduction, achieving this step by chemical hydrogenation can weaken the potential dependence of the initial hydrogenation process. However, this strategy is rarely reported in the electrocatalytic NRR, and the catalytic mechanism remains ambiguous and lacks experimental evidence. Here, we show a highly efficient electrocatalyst (ruthenium single atoms anchored on graphdiyne/graphene sandwich structures) with a hydrogen radical-transferring mechanism, in which graphdiyne (GDY) generates hydrogen radicals (H•), which can effectively activate N2 to generate NNH radicals (•NNH). A dual-active site is constructed to suppress competing hydrogen evolution, where hydrogen preferentially adsorbs on GDY and Ru single atoms serve as the adsorption site of •NNH to promote further hydrogenation of NH3 synthesis. As a result, high activity and selectivity are obtained simultaneously at -0.1 V versus a reversible hydrogen electrode. Our findings illustrate a novel hydrogen transfer mechanism that can greatly reduce the potential and maintain the high activity and selectivity in NRR and provide powerful guidelines for the design concept of electrocatalysts.

Recent Advances on Single-Atom Catalysts for Photocatalytic CO2 Reduction.

The present energy crisis and environmental challenges may be efficiently resolved by converting carbon dioxide (CO2 ) into various useful carbon products. The development of more effective catalysts has been the main focus of current research on photocatalytic CO2 reduction. Due to their high atomic efficiency and superior catalytic activity, single-atom catalysts (SACs) have attracted considerable interest in catalytic CO2 conversion. This review discusses the current research developments, obstacles, and potential of SACs for photocatalytic CO2 reduction. And further, discusses the principle of photocatalytic carbon dioxide reduction. This work has compared and analyzed the effects of support materials and active site types in SACs on photocatalytic CO2 reduction performance. This work believes that by sharing these developments, some inspiration for the rational design and development of stable and effective photocatalytic CO2 reduction catalysts based on SACs can be provided.

Integrating Amorphous Molybdenum Sulfide Nanosheets with a Co9S8@Ni3S2 Array as an Efficient Electrocatalyst for Overall Water Splitting.

It is highly challenging to design low-cost, efficient electrocatalysts for both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Herein, a hierarchical heterostructure was constructed on three-dimensional (3D) Ni foam, which contains Ni3S2 nanorods decorated with both Co9S8 and amorphous MoSx nanosheets and Ni3S2 nanowires decorated with amorphous MoSx nanosheets, namely, MoSx@Co9S8@Ni3S2/NF. The synergistic effects from the strong interactions of the heterointerface and unique hierarchical heterostructure endow the MoSx@Co9S8@Ni3S2/NF with abundant active sites and effective mass and electron transport pathways, resulting in excellent activity toward both HER and OER in 1 M KOH. It only gives a low overpotential of 76.5 mV to achieve 10 mA cm-2 for HER and a low overpotential of 310 mV to achieve 100 mA cm-2 for OER. Based on the superior catalytic activity of MoSx@Co9S8@Ni3S2/NF for OER and HER, we demonstrated the activity of overall water splitting using MoSx@Co9S8@Ni3S2/NF as both the anode and cathode. It shows a higher catalytic activity for overall water splitting with a low cell voltage of 1.52 V at 10 mA cm-2 than commercial Pt/C/NF||IrO2/NF (1.61 V) and superior stability. This work provides a platform for the design and preparation of efficient electrocatalysts with various hierarchical heterostructures.

Systematic investigation for extraction and separation of polyphenols in tea leaves by magnetic ionic liquids.

BACKGROUND: Magnetic separation has become a mature industrial technique in many fields and its application in the food and agricultural fields is expected for further extension. Furthermore, there has been little application of magnetic ionic liquids in the preparation of bioactive products. In the present study, 0.8 mol L-1 C3 MIMFeCl4 in its aqueous solution was found to be ideal for the extraction of active constituents from tea leaves. After extraction, polyphenols, caffeine and ionic liquid were also satisfactorily separated from the crude extract by various easy operations. RESULTS: The average extraction efficiency of tea polyphenols could reach up to 185.38 g kg-1 and the recovery percent of the magnetic ionic liquid was 99.8% through an external magnetic field. The extraction process was more consistent with a pseudo-second order kinetic model. Moreover, C3 MIMFeCl4 had no effect on the stability of tea polyphenols, which was very different from ordinary ferric salt. The presence of magnetic ionic liquid had a positive effect on the antioxidant activity of the product. CONCLUSION: The developed method had a good performance for selective extraction together with separation of tea polyphenols and caffeine, which is expected in the preparation of more similar active components from food and agricultural resources as a useful multifunctional solvent. © 2018 Society of Chemical Industry.

Can environmental protection tax force enterprises to improve green technology innovation?

The introduction of an environmental protection tax enables a smooth shift from the sewerage charge system to the environmental protection tax scheme. This, in turn, promotes a more sustainable development of enterprise growth, emphasizing eco-friendliness. This is of immense importance in advancing environmentally aware practices and sustainability. Based on data collected from A-share listed companies in Shanghai and Shenzhen from 2014 to 2021, this paper investigates the influence of environmental protection taxes on the advancement of green technology and the underlying mechanisms. Taking the execution of the Environmental Protection Tax Law in 2018 as a quasi-natural experiment, a double-difference model is employed to examine the causal relationship between environmental protection taxes and the adoption of green technology by companies. The findings indicate that the introduction of an environmental tax could markedly enhance the extent of green technological innovation within corporations. The evidence arising from the testing mechanism implies that such a tax can encourage firms to boost their investments in research and development, upgrade their innovative human capital, and mitigate financing limitations. The study found that there is heterogeneity in the promotion effect of the environmental protection tax on the green technological innovation of businesses in different regions and provinces with varying tax burdens and types of equity capital. Further research shows that the environmental protection tax has a greater impact on the promotion of utility model patent applications for green technology innovation. This paper presents empirical evidence to support further enhancement of the environmental protection tax system. It recommends designing the environmental protection tax policy with consideration for enterprises and local conditions and bolstering the system's capacity for guiding and stimulating enterprises' green development.

Ru/Ir-Based Electrocatalysts for Oxygen Evolution Reaction in Acidic Conditions: From Mechanisms, Optimizations to Challenges.

The generation of green hydrogen by water splitting is identified as a key strategic energy technology, and proton exchange membrane water electrolysis (PEMWE) is one of the desirable technologies for converting renewable energy sources into hydrogen. However, the harsh anode environment of PEMWE and the oxygen evolution reaction (OER) involving four-electron transfer result in a large overpotential, which limits the overall efficiency of hydrogen production, and thus efficient electrocatalysts are needed to overcome the high overpotential and slow kinetic process. In recent years, noble metal-based electrocatalysts (e.g., Ru/Ir-based metal/oxide electrocatalysts) have received much attention due to their unique catalytic properties, and have already become the dominant electrocatalysts for the acidic OER process and are applied in commercial PEMWE devices. However, these noble metal-based electrocatalysts still face the thorny problem of conflicting performance and cost. In this review, first, noble metal Ru/Ir-based OER electrocatalysts are briefly classified according to their forms of existence, and the OER catalytic mechanisms are outlined. Then, the focus is on summarizing the improvement strategies of Ru/Ir-based OER electrocatalysts with respect to their activity and stability over recent years. Finally, the challenges and development prospects of noble metal-based OER electrocatalysts are discussed.

Degradation of fluoride in groundwater by electrochemical fixed bed system with bauxite: performance and synergistic catalytic mechanism.

Fluoride pollution in water has garnered significant attention worldwide. The issue of fluoride removal remains challenging in areas not covered by municipal water systems. The industrial aluminum electrode and natural bauxite coordinated defluorination system (IE-BA) have been employed for fluoride removal. The experiment investigated the effects of pH, current density, and inter-electrode mineral layer thickness on the defluorination process of IE-BA. Additionally, the study examined the treatment efficiency of IE-BA for simulated water with varying F- concentrations and assessed its long-term performance. The results demonstrate that the defluorination efficiency can reach 98.4% after optimization. Moreover, irrespective of different fluoride concentrations, the defluorination rate exceeds 95.2%. After 72 hours of continuous operation, the defluorination rate reached 91.9%. The effluent exhibited weak alkalinity with a pH of around 8.0, and the voltage increased by 2.0 V compared to the initial moment. By analyzing the characterization properties of minerals and flocs, this study puts forward the possible defluorination mechanism of the IE-BA system. The efficacy of the IE-BA system in fluoride removal from water was ultimately confirmed, demonstrating its advantages in terms of defluorination ability under different initial conditions and resistance to complex interference. This study demonstrates that the IE-BA technology is a promising approach for defluorination.

Cu/CuxO/Graphdiyne Tandem Catalyst for Efficient Electrocatalytic Nitrate Reduction to Ammonia.

The electrocatalytic reduction reaction of nitrate (NO3 -) to ammonia (NH3) is a feasible way to achieve artificial nitrogen cycle. However, the low yield rate and poor selectivity towards NH3 product is a technical challenge. Here we present a graphdiyne (GDY)-based tandem catalyst featuring Cu/CuxO nanoparticles anchored to GDY support (termed Cu/CuxO/GDY) for efficient electrocatalytic NO3 - reduction. We achieve a high NH3 yield rate of 25.4 mg h-1 mgcat. -1 (25.4 mg h-1 cm-2) with a Faradaic efficiency of 99.8% at an applied potential of -0.8 V versus RHE using the designed catalyst. These performance metrics outperform most reported NO3 - to NH3 catalysts in the alkaline media. Electrochemical measurements and density functional theory reveal that the NO3 - preferentially attacks Cu/CuxO, and the GDY can effectively catalyze the reduction of NO2 - to NH3. This work highlights the efficacy of GDY as a new class of tandem catalysts for the artificial nitrogen cycle and provides powerful guidelines for the design of tandem electrocatalysts. This article is protected by copyright. All rights reserved.

A brief review of polysialic acid-based drug delivery systems.

Polysialic acid (PSA) is a straight-chain homoglycan linked by N-acetylneuraminic acid monomers via α-2, 8- or α-2, 9-glycosidic bonds. As a negatively charged non-glycosaminoglycan, PSA has the remarkable characteristics of non-immunogenicity and biodegradation. Although different in class, PSA is similar to poly(ethylene glycol), and was originally used to increase the stability of the delivery system in circulation to prolong the half-life. As research continues, PSA's application potential in the pharmaceutical field becomes increasingly prominent. It can be used as a biomaterial for protein polysialylation and tissue engineering, and it can be used alone or with other materials to develop multifunctional drug delivery systems. In this article, the results of the bioproduction and biofunction of PSA are introduced, the common strategies for chemical modification of PSA are summarized, and the application progress of PSA-based drug delivery systems is reviewed.

Triphase dynamic extraction system involved with ionic liquid and deep eutectic solvent for various bioactive constituents from Tartary buckwheat simultaneously.

Friendly and highly efficient acquisition of multiple active components from foods is always of great interest. For synchronous extraction and separation flavonoids together with oil from Tartary buckwheat, a new triphase dynamic system was developed with magnetic nanofluid based on deep eutectic solvent (N888-Cl/lauric acid, 1:2) (liquid phase 1), ionic liquid ([C4mim]Br) aqueous solution (liquid phase 2) and raw material powders (solid phase). It was the first time that two types of green solvents were simultaneously applied and assisted by magnetic separation. Through the investigation on key properties and operational conditions of this system, the extraction efficiency of oil and flavonoids in liquid phase 1 and 2 was achieved as 35.29 and 41.17 mg/g respectively, which were higher than that of conventional ways. Then kinetic and thermodynamics mechanisms were discovered comprehensively. After targeted recovery, the spectral characterization and antioxidant activity of two products proved the effectiveness of the developed method.

Efficient removal of norfloxacin from water using batch airlift-electrocoagulation reactor: optimization and mechanisms analysis.

In this study, we developed an airlift-electrocoagulation (AL-EC) reactor to remove norfloxacin (NOR) from water. Six parameters influencing NOR removal were investigated, and the possible removal mechanism was proposed based on flocs characterization and intermediates analysis. The performances for treating different antibiotics and removing NOR from 3 types of water were also evaluated. The best NOR removal efficiency was obtained with the iron anode and aluminum cathode combination, a current density of 2 mA cm-2, an initial pH of 7, a treatment time of 32 minutes and an air flow rate of 200 mL min-1, the supporting electrolyte type was NaCl, and the initial NOR concentration was 10 mg L-1. Flocs adsorption and electrochemical oxidation were the main ways to remove NOR from water. The average removal efficiency of the AL-EC reactor exceeded 60% of the different antibiotic concentrations in artificial and real water. The highest NOR removal rate reached 93.48% with an operating cost of 0.153 USD m-3. The present work offers a strategy for NOR removal from water with high efficiency and low cost, showing a huge potential for the application of the AL-EC in antibiotic contaminated water treatment.

Structure of the branched-chain aminotransferase from Streptococcus mutans.

The branched-chain amino-acid aminotransferase from Streptococcus mutans (SmIlvE) was recombinantly expressed in Escherichia coli with high yield. An effective purification protocol was established. A bioactivity assay indicated that SmIlvE had aminotransferase activity. The specific activity of SmIlvE towards amino-acid substrates was found to be as follows (in descending order): Ile > Leu > Val > Trp > Gly. The protein was crystallized using the hanging-drop vapour-diffusion method with PEG 3350 as the primary precipitant. The structure of SmIlvE was solved at 1.97 Å resolution by the molecular-replacement method. Comparison with structures of homologous proteins enabled the identification of conserved structural elements that might play a role in substrate binding. Further work is needed to confirm the interaction between SmIlvE and its substrates by determining the structures of their complexes.

Rapid Synthesis of Graphdiyne Films on Hydrogel at the Superspreading Interface for Antibacteria.

Graphdiyne (GDY), a two-dimensional (2D) carbon material with diacetylenic linkages (-C≡C-C≡C-) structures, has attracted enormous attention in various fields. However, the controlled synthesis of GDY films is still challenging because of the low alkyne coupling efficiency and out-of-plane growth. Here, we employed a highly efficient Cu(II)-N,N,N',N'-tetramethylethylenediamine (Cu(II)-TMEDA) catalyst and constructed a superspreading liquid/liquid interface on a hydrogel for rapid and controllable synthesis of GDY thin films. GDY films with controllable thickness from 4 to 50 nm and large-scale uniform morphology can be prepared within 2 h at room temperature. The mechanism of growth was revealed to be a nucleation and in-plane extension process. Meanwhile, the as-grown GDY films showed excellent photothermal conversion efficiency, which induces the release of Cu(II) ions from the hydrogel and exhibits high efficiency in synergistic antibacteria.

Metal - organic frameworks derived Ni5P4/NC@CoFeP/NC composites for highly efficient oxygen evolution reaction.

As an efficient non-precious metal catalyst for the oxygen evolution reaction (OER), phosphides suffer from poor electrical conductivity, so it is still a challenge to reasonably design their structures to further improve their conductivity and OER performances. Here, we present a novel Ni5P4/N-doped carbon@CoFeP/N-doped carbon composite (Ni5P4/NC@CoFeP/NC) as electrocatalysts for OER. This elaborate structure consists of Ni5P4/NC derived from Ni-MOF and CoFeP/NC derived from CoFe-Prussian blue analog MOF (Co-Fe PBA). The cube-like CoFeP/NC are scattered and uniformly coated on the sheet of Ni5P4/NC flowers. Among them, NC can enhance the conductivity of phosphides, while CoFeP/NC can increase the electrochemical active area, which benefit the properties of Ni5P4/NC@CoFeP/NC. Notably, the Ni5P4/NC@CoFeP/NC catalyst possesses outstanding OER performances with a low overpotential of 260 and 303 mV at a current density of 10 and 100 mA·cm-2, an ultra-low Tafel slope of 31.1 mV·dec-1 and excellent stability in 1 M KOH. XPS analysis shows that proper chemical composition promotes the oxidation of transition metal species and the chemisorption of OH-, thus accelerating the OER kinetics. Therefore, this work provides a hopeful method for designing and preparing transition metal phosphide/carbon composite as OER electrocatalysts.

Preparation of polyvinylidene fluoride composite ultrafiltration membrane for micro-polluted surface water treatment.

Blending modification of graphene oxide (GO) and deposition of silver carbonate (Ag2CO3) on the membrane surface by suction filtration was used to prepare polyvinylidene fluoride (PVDF) composite ultrafiltration (UF) membranes (denoted as PGA membranes). The effect of this strategy on the morphology and performance of the pure PVDF membrane was investigated. Owing to an increased hydrophilicity and the formation of a more open pore, the pollution resistance and permeability of the PGA membrane were improved. The pure water flux of the PGA-3 membrane (254 LMH) was increased to more than 2-fold compared to that of the neat PVDF membrane (126 LMH). In addition, the results of antifouling experiments showed that the flux recovery rate, flux decay rate, and antibacterial performance of the PGA-3 membrane was superior to those of the other membranes synthesized in this study. Finally, after conducting multi-cycle filtration experiments with lake water, the flux and recovery rate of the PGA-3 membrane was observed to be the highest, and the water quality of the lake water filtered by the PGA-3 membrane was the best. Thus, the above results indicate that this membrane modification strategy is extraordinarily effective in improving the antifouling properties and permeability of the PVDF UF membranes in practical applications.

Dispersive solid-phase extraction of racemic drugs using chiral ionic liquid-metal-organic framework composite sorbent.

Nowadays, enantioseparation of racemic pharmaceuticals in preparations is a prime concern by drug authorities across the globe. In the present work, it was attempted to develop novel enantioselective extraction method for five clinically used drugs (atenolol, propranolol, metoprolol, racecadotril, and raceanisodamine in their tablets) as racemates. The enantioselective solid-liquid extraction of these racemic drugs was carried out successfully by the use of chiral ionic liquid (CIL) in combination with a metal organic framework (MOF) for the first time. The composite CIL@MOF was synthesized from tropine based chiral ionic liquids with L-proline anion ([CnTr][L-Pro], n=3-6) and HKUST-1 type MOF, which was comprehensively characterized before being used as sorbent for enantioselective dispersive solid-liquid extraction. Preliminary selection of appropriate CIL was carried out on thin layer chromatography (TLC); under the joint participation of copper ion in the developing reagent, [C3Tr][L-Pro] ionic liquid showed better resolution performance with ΔRf value of 0.35 between the enantiomers was obtained for racemic atenolol. Moreover, the effect of copper salt dosage, amount of CIL, soli-liquid ratio and extraction time were investigated. The optimal conditions were obtained after thorough investigations; i.e. sample solution: ethanol, elution solvent: methanol, solid-liquid ratio: 12.5 mg:50 mL, amount of copper salt: 8 mg L-1, amount of impregnated CIL: 30% and extraction time of 30 min. As a result, enantiomeric excess values are 90.4%, 95%, 92%, 81.6% and 83.2% for atenolol, propranolol, metoprolol, racecadotril and raceanisodamine, respectively. The developed enantioselective method was validated following ICH guidelines and it was proved to be simple, effective and enantioselective way for separation of racemic pharmaceuticals with similar behaviors.