Design of a Single-Atom In-N3-S site to Modulate Exciton Behavior in Carbon Nitride for Enhanced Photocatalytic Performance.

Rational tailoring of the local coordination environment of single atoms has demonstrated a significant impact on the electronic state and catalytic performance, but the development of catalysts beyond noble/transition metals is profoundly significant and highly desired. Herein, the main-group metal indium (In) single atom is immobilized on sulfur-doped porous carbon nitride nanosheets (In@CNS) in the form of three nitrogen atoms coordinated with one sulfur atom (In-N3-S). Both theoretical calculations and advanced characterization investigations clearly elucidated that the single-atomic In-N3-S structures on In@CNS are powerful in promoting the dissociation of excitons into more free carriers as well as the charge separation, synergistically elevating electron concentration by 2.19 times with respect to pristine CNS. Meanwhile, the loading of In single atoms on CNS is responsible for altering electronic structure and lowering the Gibbs free energy for hydrogen adsorption. Consequently, the optimized In@CNS-5.0 exhibited remarkable photocatalytic performance, remarkable water-splitting and tetracycline hydrochloride degradation. The H2 production achieved to 10.11 mmol h-1g-1 with a notable apparent quantum yield of 19.70% at 400 nm and remained at 10.40% at 420 nm. These findings open a new perspective for in-depth comprehending the effect of the main-group metal single-atom coordination environment on promoting photocatalytic performance.

High Selectivity and Reusability of Biomass-Based Adsorbent for Chloramphenicol Removal.

Recently, biomass-based materials have attracted increasing attention because of their advantages of low cost, environment-friendly and nonpollution. Herein, the feasibility of using corn stalk biomass fiber (CF) and Fe3O4 embedded chitosan (CS) as a novel biomass-based adsorbent (CFS) to remove chloramphenicol (CAPC) from aqueous solution. Structure of CFS was characterized by using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM) and zeta potential techniques. The effects of solution pH, adsorption time and ion strength on the adsorption capacity were examined. Adsorption isotherms obtained from batch experiments were better fitted by Langmuir model compared with Freundlich model, Dubinin-Radushkevich model and Temkin model. Adsorption kinetic data matched well to the pseudo-second order kinetic model. CAPC adsorption was endothermic, spontaneous, and entropy-increasing nature on CFS. In addition, the CFS could be separated by an external magnetic field, recycled, and reused without any significant loss in the adsorption capacity of CAPC. Based on these excellent performances, there is potential that CFS can be considered as a proficient and economically suitable material for the CAPC removal from the water environment.

Incorporation of Nonmetal Group Dopants into g-C3N4 Framework for Highly Improved Photocatalytic H2 Production.

The incorporation of nonmetal group dopants into a graphitic carbon nitride (g-C3N4) framework is fabricated by adding a small amount of hexamethylenetetramine during the thermal polymerization process. The material shows an excellent visible-light photocatalytic H2 production performance that is eight times higher than bulk g-C3N4. This outstanding performance is ascribed to the introducing of N-doped carbon, which not only enhances the light absorption and favorsa narrower band gap, but also upshifts the conductionband (CB) potential, resulting in a better reduction ability of electrons. This discovery has potential significancefor the designing of high performance, economic, and environmental friendly photocatalyst for solar energy conversion.

Surface Permeability of Membrane and Catalytic Performance Based on Redox-Responsive of Hybrid Hollow Polymeric Microcapsules.

"Smart" polymeric microcapsules with excellent permeability of membranes have drawn considerable attention in scientific and industrial research such as drug delivery carriers, microreactors, and artificial organelles. In this work, hybrid hollow polymeric microcapsules (HPs) containing redox-active gold-sulfide bond were prepared with bovine serum albumin, inorganic metal cluster (AuNCs), and poly(N-isopropylacrylamide) conjugates by using Pickering emulsion method. HPs were transferred from water-in-oil to water-in-water by adding PEGbis(N-succinimidylsuccinate). To achieve redox-responsive membrane, the Au-S bond units incorporated into the microcapsules' membranes, allowed us to explore the effects of a new stimuli, that is, the redox Au-S bond breaking on the microcapsules' membranes. The permeability of these hybrid hollow polymeric microcapsules could be sensitively tuned via adding environment-friendly hydrogen peroxide (H2O2), resulting from a fast fracture of Au-S bond. Meanwhile, AuNCs and conjugates could depart from the microcapsules, and enhance the permeability of the membrane. Based on the excellent permeability of the membrane, phosphatase was encapsuled into HPs and p-nitrophenyl phosphate as a substrate. After adding 1 × 10-2 and 1 × 10-4 M H2O2, the catalytic efficiency was nearly 4.06 and 2.22 times higher than that of HPs in the absence of H2O2, respectively. Hence, the unique redox-responsive HPs have potential applications in biocatalytic reaction, drug delivery, and materials as well as in bioscience.

Rational Synthesis of Amorphous Iron-Nickel Phosphonates for Highly Efficient Photocatalytic Water Oxidation with Almost 100 % Yield.

A simple solvent ligation effect was successfully used to disrupt the growth of a model compound, Fe[(OH)(O3 P(CH2 )2 CO2 H)]⋅H2 O (MIL-37), into an extended 2D structure by replacing water with dimethylformamide (DMF) as the solvent during the synthesis. Owing to the lack of -OH group, which provides the corner-sharing (binding) oxygen atoms for the octahedra, an amorphous and porous structure is formed. When Fe3+ is partially replaced by Ni2+ , the amorphous structure remains and the resultant binary metal catalyst displays excellent photocatalytic oxygen evolution activity with almost 100 % yield achieved under visible light irradiation using [Ru(bpy)3 ]2+ as the photosensitizer. This study opens up new possibilities of using the simple solvent effect to synthesize high surface area metal phosphonates for catalytic and other applications.

Corrigendum: Highly Ordered Mesoporous NiCo2O4 as a High Performance Anode Material for Li-Ion Batteries.

[This corrects the article DOI: 10.3389/fchem.2019.00521.].

Highly Ordered Mesoporous NiCo2O4 as a High Performance Anode Material for Li-Ion Batteries.

The controlled synthesis of highly ordered mesoporous structure has attracted considerable attention in the field of electrochemistry because of its high specific surface area which can contribute the transportation of ions. Herein, a general nano-casting approach is proposed for synthesizing highly ordered mesoporous NiCo2O4 microspheres. The as-synthesized mesoporous NiCo2O4 microsphere materials with high Brunner-Emmett-Teller (BET) surface area (~97.77 m2g-1) and uniform pore size distribution around 4 nm exhibited a high initial discharge capacity of ~1,467 mAhg-1, a good rate capability as well as cycling stability. The superior electrochemical performance was mainly because of the highly porous nature of NiCo2O4, which rendered volume expansion during the process of cycling and shortened lithium-ions transport pathways. These properties showcase the inherent potential for use of highly ordered mesoporous NiCo2O4 microspheres as a potential anode material for lithium-ion batteries in the future.

Mimicking π Backdonation in Ce-MOFs for Solar-Driven Ammonia Synthesis.

π Backdonation is the core process to break through the kinetically complex and energetic hurdle for catalyzing effectively the NH3 synthesis but only occurs on certain transition metals with empty and filled d orbitals. Herein, mimicking π backdonation enables MOF-76(Ce) materials to convert N2/NH3 effectively. Note that, by virtue of the intrinsic mechanism of ligand-to-metal charge transfer, metal cerium species in MOF-76(Ce) serve as an electron sink for accumulating the photogenerated electrons. Taken together, experimental and theoretical analyses reveal that such metal cerium species with coordination unsaturated state (Ce-CUS) on a MOF-76(Ce) nanorod surface can also provide unoccupied and occupied 4f orbitals to accept from and then donate electrons back to nitrogen molecules. Remarkably, it shows outstanding photocatalytic nitrogen reduction performance with high average NH3 yield (34 µmol g-1 h-1) under ambient conditions. This work provides fresh insights into rational designing and engineering highly active catalysts with rare earth elements.

Shockley Partial Dislocation-Induced Self-Rectified 1D Hydrogen Evolution Photocatalyst.

Photocatalytic stability and efficient charge separation are key factors to photocatalytic performance for visible-light-driven H2 evolution from water. Here, we report a whole novel self-rectified photocatalyst constructed from the Shockley partial dislocation-induced multiple faults, using a ternary chalcogenide, that is, Cd0.8Zn0.2S nanorod as a model material. The introduction of multiple faults, which are typical planar defects, constructs a nanorectifier that aligns along the axial direction and constitutes a relatively ordered superstructure. The band bending and Fermi-level flattening at the nanorectifier would cause the photogenerated charge carriers to be transferred reversely at the axial direction on account of the charge type and then realize the separation of the charge carriers.

Anchoring Active Pt2+ /Pt0 Hybrid Nanodots on g-C3 N4 Nitrogen Vacancies for Photocatalytic H2 Evolution.

A Pt2+ /Pt0 hybrid nanodot-modified graphitic carbon nitride (CN) photocatalyst (CNV-P) was fabricated for the first time using a chemical reduction method, during which nitrogen vacancies in g-C3 N4 assist to stabilize Pt2+ species. It is elucidated that the coexistence of metallic Pt0 and Pt2+ species in the Pt nanodots loaded on g-C3 N4 results in superior photocatalytic H2 evolution performance with very low Pt loadings. The turnover frequencies (TOFs) are 265.91 and 116.38 h-1 for CNV-P-0.1 (0.1 wt % Pt) and CNV-P-0.5 (0.5 wt % Pt), respectively, which are much higher than for other g-C3 N4 -based photocatalysts with Pt co-catalyst reported previously. The excellent photocatalytic H2 evolution performance is a result of i) metallic Pt0 facilitating the electron transport and separation and Pt2+ species preventing the undesirable H2 backward reaction, ii) the strong interfacial contact between Pt2+ /Pt0 hybrid nanodots and nitrogen vacancies of CNV facilitating the interfacial electron transfer, and iii) the highly dispersed Pt2+ /Pt0 hybrid nanodots exposing more active sites for photocatalytic H2 evolution. Our findings are useful for the design of highly active semiconductor-based photocatalysts with extremely low precious metal content to reduce the catalyst cost while achieving good activity.

Biocoordination Polymer Cross-Linking Structure to a 3D Star Topology Inorganic Photocatalyst Nanocrystal with Improved Hydrogen Evolution Performance.

An inorganic photocatalyst with a novel 3D star topology (ST) framework was obtained via multiple cross-linking of biocoordination polymers in one-step solvothermal conditions. It possessesd a large surface area (149.36 m2·g-1), among the highest value of the current reports, and represented the quantum size effect because of its 3D ST structure. The amino acid l-cysteine was introduced into the synthesis system to lead generation of the biometic coordination polymer through the amino acid dehydrate condensation and multiple cross-linking.

Amino-Assisted Anchoring of CsPbBr3 Perovskite Quantum Dots on Porous g-C3 N4 for Enhanced Photocatalytic CO2 Reduction.

Halide perovskite quantum dots (QDs) have great potential in photocatalytic applications if their low charge transportation efficiency and chemical instability can be overcome. To circumvent these obstacles, we anchored CsPbBr3 QDs (CPB) on NHx -rich porous g-C3 N4 nanosheets (PCN) to construct the composite photocatalysts via N-Br chemical bonding. The 20 CPB-PCN (20 wt % of QDs) photocatalyst exhibits good stability and an outstanding yield of 149 µmol h-1 g-1 in acetonitrile/water for photocatalytic reduction of CO2 to CO under visible light irradiation, which is around 15 times higher than that of CsPbBr3 QDs. This study opens up new possibilities of using halide perovskite QDs for photocatalytic application.

Doping effect of non-metal group in porous ultrathin g-C3N4 nanosheets towards synergistically improved photocatalytic hydrogen evolution.

Searching for effective approaches of accelerating charge separation and broadening optical absorption is critical for designing a high-performance photocatalytic system. Herein, a photocatalyst based on the non-metal group doped porous ultrathin g-C3N4 nanosheets (CNB NS) was prepared through a combined methodology of precursor reforming and thermal condensation. The synergistic effect of non-metal group doping and porous ultrathin nanosheet-architecture not only endow the material with improved light harvesting and regulated band structure, but also facilitate the electron-hole pair separation, supplying numerous active reactive sites and electron diffusion channels. As a result, the CNB NS photocatalyst exhibits a highly efficient photocatalytic H2 performance (the apparent quantum efficiency is 7.45% at 420 nm) and stability in water under the visible light, which is approximately 13 times higher than that of pure g-C3N4. This study may open a new perspective for designing the non-metal group doped g-C3N4 photocatalyst and further fabricate other advanced photocatalytic materials.

The effects of cell death-inducing DNA fragmentation factor-α-like effector C (CIDEC) on milk lipid synthesis in mammary glands of dairy cows.

Adequate lipid synthesis by the mammary gland during lactation is essential for the survival of mammalian offspring. Cell death-inducing DNA fragmentation factor-α-like effector C (CIDEC) is a lipid droplet-associated protein and functions to promote lipid accumulation and inhibit lipolysis in mice and human adipocytes. However, the function of CIDEC in regulation of milk lipid synthesis in dairy cow mammary gland remains largely unknown. In this study, 6 multiparous Holstein cows (parity = 3) in early lactation were allocated to high-fat milk (milk yield 33.9 ± 2.1 kg/d, milk fat >3.5%, n = 3) and low-fat milk (milk yield 33.7 ± 0.5 kg/d, milk fat <3.5%, n = 3) groups according to their milk fat content. Lactating cows were slaughtered at 90 d in milk and mammary tissues were collected to detect CIDEC localization. Immunofluorescence staining of sections of lactating mammary glands with high- and low-fat milk showed that CIDEC was expressed in the cytoplasm of epithelial cells and localized to lipid droplets. Lipid droplets and CIDEC protein were also detected in isolated lactating mammary epithelial cells of dairy cows. Immunostaining of CIDEC in isolated mammary epithelial cells also confirmed its presence in the nucleus. The knockdown of CIDEC in cultured bovine mammary epithelial cells decreased milk lipid content and reduced expression of genes associated with mammary de novo fatty acid synthesis, short- and long-chain intracellular fatty acid activation, triacylglycerol synthesis, and transcription regulation. These genes included those for acetyl-CoA carboxylase (ACC, -60%), fatty acid synthase (FASN, -65%), acyl-CoA synthetase short-chain family member 2 (ACSS2, -50%), acyl-CoA synthetase long-chain family member 1 (ACSL1, -30%), diacylglycerol acyltransferase 1 (DGAT1, -60%), sterol regulatory element-binding protein 1 (SREBP1, -45%), and SREBP cleavage activating protein (SCAP, -66%). Conversely, in cells overexpressing CIDEC, triacylglycerol content was increased, and transcription of those genes involved in milk lipid synthesis was coordinately upregulated. These results suggest that CIDEC plays an important role in regulating milk lipid synthesis in dairy cow mammary gland via a mechanism involving gene expression, which provides further insight into the mechanisms regulating mammary lipogenesis in ruminants.

Spleen tyrosine kinase regulates mammary epithelial cell proliferation in mammary glands of dairy cows.

Spleen tyrosine kinase (SYK) is a nonreceptor tyrosine kinase that has been considered a hematopoietic cell-specific signal transducer involved in cell proliferation and differentiation. However, the role of SYK in normal mammary gland is still poorly understood. Here we show that SYK is expressed in mammary glands of dairy cows. Expression of SYK was higher in dry period mammary tissues than in lactating mammary tissues. Knockdown and overexpression of SYK affected dairy cow mammary epithelial cell proliferation as well as the expression of signal molecules involved in proliferation, including protein kinase B (PKB, also known as AKT1), p42/44 mitogen-activated protein kinase (MAPK), and signal transducer and activator of transcription 5 (STAT5). Dual-luciferase reporter assay showed that SYK increased the transcriptional activity of the AKT1 promoter, and cis-elements within the AKT1 promoter region from -439 to -84 bp mediated this regulation. These results suggest that SYK affects mammary epithelial cell proliferation by activating AKT1 at the transcriptional level in mammary glands of dairy cows, which is important for the mammary remodeling process in dry cows as well as for increasing persistency of lactation in lactating cows.