Efficient photocatalytic hydrogen peroxide production over S-scheme In2S3/molten salt modified C3N5 heterojunction.

Graphitic phase carbon nitride (g-C3N5), as a novel n-type metal-free material, is employed as a visible light-receptive catalyst because of its narrow band gap and abundant nitrogen. To overcome the low carrier mobility efficiency of g-C3N5, its modification by K ions was adopted. In addition, In2S3 was selected to couple with modified g-C3N5 to overcome the recombination of photogenerated e-/h+. As a novel photocatalytic material, it was proven to possess a high visible light absorption capacity and a strong H2O2 production ability (up to 3.89 mmol⋅L-1 in 2 h). Moreover, a S-scheme heterojunction structure was successfully constructed between the two materials, which was tested and confirmed to be successful in raising the photogenerated e-/h+ separation efficiency. Ultimately, the primary processes of photocatalytic H2O2 production were summarized by superoxide radical and rotating disc electron measurements. This research provides a fresh perspective for the synthesis of C3N5-based S-scheme heterojunction photocatalysts for producing H2O2.

Efficient Photocatalytic H2 O2 Production Ability of a Novel Graphitic Carbon Nitride/Carbon Composites under Visible Light.

In the present work, using one-step calcination of a mixture made of potassium hydroxide (KOH), melamine, and microplastics, this work prepares a novel graphitic carbon nitride/carbon (g-C3 N4 /C) composite, which can be employed to photo-catalytically produce hydrogen peroxide (H2 O2 ) at a high rate up to 6.146 mmol g-1 h-1 under visible light irradiation. By analyzing the energy band structure of the catalyst, the production of H2 O2 in this system consists of two single-electron reactions. The modification of KOH makes abundant N-vacancies caused by cyano-groups in g-C3 N4 , enhancing the electron absorption ability. Moreover, the introduction of graphitic carbon increases its specific surface area and porosity and improves the adsorption ability of O2 . Simultaneously, their synergism reduces the g-C3 N4 band gap, making both the conduction-band and valence-band positions more negative, showing enhanced reduction ability, lowering the energy barrier for oxygen reduction, and greatly improving the photogeneration performance of H2 O2 .

Facile synthesis of NiAl2O4/g-C3N4 composite for efficient photocatalytic degradation of tetracycline.

Designing high-efficiency photocatalysts responsive to visible light is important for the degradation of antibiotics in water. Heterojunction engineering is undoubtedly an effective strategy to improve the photocatalytic performance. In this work, spinel-type metal oxides (NiAl2O4, NAO) are synthesized by a simple sol-gel and calcination process. After compounding graphitic carbon nitride (g-C3N4), NAO/g-C3N4 heterojunction is obtained, which then is used as the photocatalyst for tetracycline hydrochloride (TC). The effects of photocatalyst dosage, the initial concentration of TC, and solution pH on photodegradation performance are systematically studied. The removal rate of TC on NAO/g-C3N4 reach up to ∼90% after visible light irradiation for 2 hr and the degradation rate constant is ∼7 times, and ∼32 times higher than that of pure NAO and g-C3N4. The significantly improved photocatalytic activity can be attributed to the synergistic effect between well matched energy levels in NAO/g-C3N4 heterojunctions, improvement of interfacial charge transfer, and enhancement of visible light absorption. This study provides a way for the synthesis of efficient photocatalysts and an economic strategy for removing antibiotics contamination in water.

Preparation and characterization of novel Niln2S4/UiO-66 photocatalysts for the efficient degradation of antibiotics in water.

Photocatalysis is considered an economical, environmentally friendly, and effective technology for removing pollutants. The construction of Z-Scheme heterojunctions has been identified as one of the feasible solutions capable of enhancing the photocatalytic activity. Herein, a series of visible light responsive photocatalysts (NiIn2S4/UiO-66 composites) with excellent activity and stability were prepared by using a solvothermal process. It is found that 20 mg L-1 of tetracycline (TC) could be almost completely degraded under visible light irradiation within 1 h, when the mass ratio of NiIn2S4 to UiO-66 is 0.5:1 (NISU-0.5) and the solution pH = 11. In addition, after six cycles, the degradation rate of tetracycline photocatalyzed by NISU-0.5 still reach up to 90%. Ultraviolet photoelectron spectra (UPS), X-ray photoelectron spectra (XPS) and electron spin resonance measurements (ESR) confirm the formation of the Z-Scheme heterostructure between NiIn2S4 and UiO-66. The synergistic effect between built-in electric field, energy band bending and coulomb interactions in interface of Z-Scheme heterojunction is conducive to restrain the recombination of photogenerated electrons and holes, which greatly improve the photocatalytic activity. In conclusion, this study offers a new thought for design and synthesis of Z-Scheme heterojunctions and provides a cost-effective strategy for solving environmental pollution and energy problems in the future.

Implanting Cobalt Atom Clusters within Nitrogen-Doped Carbon Network as Highly Stable Cathode for Lithium-Sulfur Batteries.

Realization of highly efficient sulfur electrochemistry, as well as the high capacity of lithium-sulfur (Li-S) batteries, can be achieved by the scientific construction of electrode host materials. In this study, using molten NaCl, a 3D porous nitrogen-doped carbon with uniformly embedded Co atom clusters (Co/PNC) is developed by pyrolyzing the precursors with NaCl at high temperatures. In the composite structure, a network carbon skeleton containing hierarchical pores acts as an advanced matrix for sulfur electrodes, and the doping of N and Co is subject to inhibit the shuttle of long-chain lithium polysulfides through chemical adsorption. The Co/PNC, with the optimized amount of Co, delivers an initial specific capacity of 1105.4 mAh g-1 at 0.2 C with a capacity drop of only 0.064% after the cell is charged and discharged for 300 cycles at 1 C, revealing its potential in promoting the large-scale application of Li-S batteries.

Self-standing heterostructured NiC x -NiFe-NC/biochar as a highly efficient cathode for lithium-oxygen batteries.

Lithium-oxygen batteries have attracted research attention due to their low cost and high theoretical capacity. Developing inexpensive and highly efficient cathode materials without using noble metal-based catalysts is highly desirable for practical applications in lithium-oxygen batteries. Herein, a heterostructure of NiFe and NiC x inside of N-doped carbon (NiC x -NiFe-NC) derived from bimetallic Prussian blue supported on biochar was developed as a novel self-standing cathode for lithium-oxygen batteries. The specific discharge capacity of the best sample was 27.14 mAh·cm-2 at a stable discharge voltage of 2.75 V. The hybridization between the d-orbital of Ni and s and p-orbitals of carbon in NiC x , formed at 900 °C, enhanced the electrocatalytic performance due to the synergistic effect between these components. The structure of NiC x -NiFe-NC efficiently improved the electron and ion transfer between the cathode and the electrolyte during the electrochemical processes, resulting in superior electrocatalytic properties in lithium-oxygen batteries. This study indicates that nickel carbide supported on N-doped carbon is a promising cathode material for lithium-oxygen batteries.

Tailoring hollow structure within NiCoP nanowire arrays via nanoscale Kirkendall diffusion to enhance hydrogen evolution reaction.

Hollow structured nanomaterials with void space available inside the shells can effectively enhance electrocatalytic activity due to their high specific surface area, volume buffer and shell permeability properties. In this study, low-cost and hollow structured bimetal phosphide nanowires are synthesized directly on Ni foam via the Kirkendall effect by using NaH2PO2 as a phosphorizing agent at 350 °C. Both the crystal and hollow structures of the obtained phosphide can be efficiently tuned by controlling the amount of phosphorizing agent and the phosphorizing time. The morphology and microstructure of the obtained phosphides are characterised using various techniques, which indicate that the formation mechanism of the hollow structure is consistent with the Kirkendall effect. The optimized bimetal phosphide sample demonstrates a low onset potential (59 mV) at a current density of 10 mA cm-2, low charge transfer resistance (0.83 Ω) and superior durability in the hydrogen evolution reaction (HER) for water electrolysis. The electrochemical results clearly demonstrate that the hollow structure can efficiently improve the HER properties and the obtained phosphide is a promising HER catalysts for water splitting in KOH or seawater electrolytes.

CNTs-Modified Nb3O7F Hybrid Nanocrystal towards Faster Carrier Migration, Lower Bandgap and Higher Photocatalytic Activity.

Novel semiconductor photocatalysts have been the research focus and received much attention in recent years. The key issues for novel semiconductor photocatalysts are to effectively harvest solar energy and enhance the separation efficiency of the electron-hole pairs. In this work, novel Nb3O7F/CNTs hybrid nanocomposites with enhanced photocatalytic activity have been successfully synthesized by a facile hydrothermal plus etching technique. The important finding is that appropriate pH values lead to the formation of Nb3O7F nanocrystal directly. A general strategy to introdue interaction between Nb3O7F and CNTs markedly enhances the photocatalytic activity of Nb3O7F. Comparatively, Nb3O7F/CNTs nanocomposites exhibit higher photodegradation efficiency and faster photodegradation rate in the solution of methylene blue (MB) under visible-light irradiation. The higher photocatalytic activity may be attributed to more exposed active sites, higher carrier migration and narrower bandgap because of good synergistic effect. The results here may inspire more engineering, new design and facile fabrication of novel photocatalysts with highly photocatalytic activity.

miR-424(322) reverses chemoresistance via T-cell immune response activation by blocking the PD-L1 immune checkpoint.

Immune checkpoint blockade of the inhibitory immune receptors PD-L1, PD-1 and CTLA-4 has emerged as a successful treatment strategy for several advanced cancers. Here we demonstrate that miR-424(322) regulates the PD-L1/PD-1 and CD80/CTLA-4 pathways in chemoresistant ovarian cancer. miR-424(322) is inversely correlated with PD-L1, PD-1, CD80 and CTLA-4 expression. High levels of miR-424(322) in the tumours are positively correlated with the progression-free survival of ovarian cancer patients. Mechanistic investigations demonstrated that miR-424(322) inhibited PD-L1 and CD80 expression through direct binding to the 3'-untranslated region. Restoration of miR-424(322) expression reverses chemoresistance, which is accompanied by blockage of the PD-L1 immune checkpoint. The synergistic effect of chemotherapy and immunotherapy is associated with the proliferation of functional cytotoxic CD8+ T cells and the inhibition of myeloid-derived suppressive cells and regulatory T cells. Collectively, our data suggest a biological and functional interaction between PD-L1 and chemoresistance through the microRNA regulatory cascade.