Construction of CuNiAl-LDHs electrocatalyst with rich-Cu^(+)and—OH for highly selective reduction of CO_(2) to methanol

In this work,a high-performance CuNiAl-LDHs catalyst was innovatively synthesized for electrochemical carbon dioxide reduction(CO_(2)RR)of methanol(CH3OH)through the modulated synthesis of Cu-based layered double hydroxide(LDHs).It was found that the optimal CuNiAl-LDHs has superior CH3OH selectivity compared to CuAl-LDHs and CuMgAl-LDHs,with the Faraday efficiency(FE)of 76.4%for CH3OH generation at1.2 V.And their FE and current density(4.8 mA·cm^(2))remained stable during up to 24 h of electrolysis.Meanwhile,this study confirms the significant performance advantages of CuNiAlLDHs over their derived composite oxides.Series characterization further proves that the excellent catalytic performance of CuNiAl-LDHs is importantly associated with their richness in Cu+and hydroxyl group(-OH).The research expands the application fields of LDHs compounds.Meanwhile,the series of discoveries provide a new insight for the preparation of CH3OH by constructing CO_(2)RR.

Growing Intact Membrane by Tuning Carbon Down to Ultrasmall 0.37 nm Microporous Structure for Confining Dissolution of Polysulfides Toward High-Performance Sodium–Sulfur Batteries

Room temperature sodium–sulfur(Na–S)batteries are severely hampered by dissolution of polysulfides into electrolytes.Herein,a facile approach is used to tune a biomass-derived carbon down to an ultrasmall 0.37 nm microporous structure for the first time as a cathode in sodium–sulfur batteries.This produced an intact uniform Na2S membrane to greatly confine the dissolution of polysulfides while realizing a direct solid phase conversion for complete reduction of sulfur to Na2S,which delivers a sulfur loading of 1 mg cm−2(50 wt.%),an excellent rate capacity(933 mAh g^(−1)@0.1 A g^(−1)and 410 mAh g^(−1)@2Ag^(−1)),long cycle performance(0.036%per cycle decay at 1 A g^(−1)after 1500 cycles),and a high energy density for 373 Wh kg^(−1)(0.1 A g^(−1))based on whole electrode weight(active sulfur loading+carbon),ranking the best among all reported plain carbon cathode-based room temperature sodium–sulfur batteries in terms of the cycle life and rate capacity.It is proposed that the solid Na2S produced in the ultrasmall pores(0.37 nm)can be squeezed out to grow an intact membrane on the electrode surface covering the outlet of the pores and greatly depressing the dissolution effect of polysulfides for the long cycle life.This work provides a green chemistry to recycle wastes for sustainable energies and sheds light on design of a unique pore structure to effectively block the dissolution of polysulfides for high-performance sodium–sulfur batteries.

Ferric acetylacetonate/covalent organic framework composite for high performance photocatalytic oxidation

Ferric acetylacetonate/covalent organic framework(Fe(acac)_(3)/COF)composite was synthesized by interfacial polymerization method at room temperature.The crystal structure,morphology and porosity property of the composite were characterized by X-ray diffraction,scanning electron microscope,transmission electron microscope and nitrogen adsorption.The interaction between Fe(acac)_(3) and COF was investigated by Fourier transform infrared spectra and X-ray photoelectron spectroscopy.The Fe(acac)_(3)/COF composite was used as a photocatalyst for the oxidation of benzyl alcohol under mild conditions.It exhibits high activity and selectivity for the reaction,of which the mechanism was investigated by determining its photoelectric properties.The Fe(acac)_(3)/COF catalyst developed in this work has application potential in other photocatalytic reactions.

Ultra-small UiO-66-NH_(2)nanoparticles immobilized on g-C_(3)N_(4)nanosheets for enhanced catalytic activity

UiO-66-NH_(2),an important metal-organic framework,is usually synthesized by solvothermal method and the particle size is generally larger than 200 nm,which limits its catalytic applications in chemical reactions.It is very meaningful to produce UiO-66-NH_(2) nanoparticles with ultrasmall size,but remains challenging.Herein,we synthesized UiO-66-NH_(2) nanoparticles in size of 8-15 nm that are immobilized on g-C_(3)N_(4)nanosheets.Compared with the UiO-66-NH_(2) synthesized by the traditional solvothermal method(>200 nm),the ultra-small UiO-66-NH_(2) nanoparticles immobilized on g-C_(3)N_(4)have more unsaturated coordination positions and increased Lewis acidity.Owing to these combined advantages,the ultra-small UiO-66-NH_(2)nanoparticles exhibit greatly improved catalytic activity for Meerwein-Ponndorf-Verley reaction than larger UiO-66-NH_(2)particles.

Amorphous NH_(2)-MIL-68 as an efficient electro-and photo-catalyst for CO_(2)conversion reactions

To produce metal-organic framework(MOF)catalysts with both high activity and durability is interesting but challenging.We report an amorphous MOF(NH_(2)-MIL-68),which combines the advantages of(1)a large number of open metal sites,(2)the basic building blocks and connectivity of crystalline NH_(2)-MIL-68,and(3)hierarchically meso-and microporous structure.It exhibits high performances in electrocatalytic reduction of CO_(2)and photochemical cycloaddition of CO_(2)under mild conditions.For the former reaction,the maximum Faradaic efficiency for product formic acid(FEHCOOH)reaches 93.3%with a current density of 34.2 mA·cm^(−2)at^(−2).05 V vs.Ag/Ag+catalyzed by amorphous NH_(2)-MIL-68,while the crystalline NH_(2)-MIL-68 shows FEHCOOH of 67.7%with considerable productions of CO and H_(2)at the same experimental conditions.For the photochemical cycloaddition of CO_(2)with styrene oxide,the yield by amorphous NH_(2)-MIL-68 can reach 94.1%at 12 h,which is higher than the reported value under similar conditions.The structure–efficiency relationship of the catalyst for the two reactions was investigated.This work opens up new possibility for designing high-performance MOF and MOF-based catalysts.

Dual ultrasound-guided totally implantable venous access ports via the right internal jugular vein in pediatric patients with cancer:a preliminary experience in a single institution

Objective To assess the efficacy and safety of dual ultrasound-guided(DUG)totally implantable venous access port(TIVAP)implantation(namely,using ultrasoundguided percutaneous puncture with transesophageal echocardiography-guided catheterization)via the right internal jugular vein(IJV)in pediatric patients with cancer.Methods Fifty-five children with cancer requiring chemotherapy underwent DUG-TIVAP implantation via the right IJV.Clinical data were recorded,including the procedure success rate,first attempt success rate,and perioperative and postoperative complications.Results All 55 cases were successfully operated on.The first puncture success rate was 100%.The operation time was 22–41min,with a mean time of 30.8±5.5min.The mean TIVAP implantation time was 253±145 days(range 42–520 days).There were no perioperative complications.The postoperative complication rate was 5.4%(3/55),including skin infections around the port in one case,catheter-related infection in one case,and fibrin sheath formation in one case.The ports were all preserved after anti-infection or thrombolytic therapy.No unplanned port withdrawal was recorded in this study.Conclusions DUG-TIVAP implantation is a technique with a high success rate and a low complication rate;therefore,it provides an alternative for children with cancer.Further randomized controlled studies are needed to confirm the efficacy and safety of DUG-TIVAP via the right IJV in children.

Ionic liquids produce heteroatom-doped Pt/TiO2 nanocrystals for efficient photocatalytic hydrogen production

It is of great importance to develop facile strategies to synthesize catalysts with desirable compositions and structures for high-performance photocatalytic hydrogen generation. In this work, we put forward an ionic liquid assisted one-pot route for the synthesis of heteroatom-doped Pt/TiO2 composite material. This route is simple, environmentally benign and adjustable owing to the designable properties of ionic liquids. The as-synthesized Pt/TiO2 nanocrystals exhibit high activity and stability for the photocatalytic hydrogen generation under simulated solar irradiation. This method can be easily applied to the synthesis of various kinds of metal/TiO2 composites doped with desirable heteroatoms (e.g., F, Cl, Br, etc).

Supercritical CO2 produces the visible-light-responsive TiO2/COF heterojunction with enhanced electron-hole separation for highperformance hydrogen evolution

To construct the heterojunctions of TiO2 with other compounds is of great importance for overcoming its inherent shortages and improving the visible-light photocatalytic performance.Here we propose the construction of TiO2/covalent organic framework(COF)heterojunction with tight connection by a supercritical CO2(SC CO2)method,which helps bridging the transformation paths for photo-induced charge between T i02 and COF.The produced T i02/COF heterojunction performs a H2 evolution of 3,962 nmol·g^-1·h^-1 under visible-light irradiation,which is-25 times higher than that of pure TiO2 and 4.5 folds higher than that of TiO2/COF synthesized by the conventional solvothermal method.This study opens up new possibilities for constructing heterojunctions for solar energy utilization.

Epigenetic regulation of phosphodiesterase 4d in restrictive cardiomyopathy mice with cTnI mutations

Epigenetic regulations play an important role in disease development.In this study,we have investigated epigenetic regulations in restrictive cardiomyopathy mice with cTnI 193 His mutation.Our results demonstrated that phosphodiesterase(PDEs)4d was down-regulated in the heart of these mice.Further studies showed that the epigenetic modifications were associated with enhanced acetylation of histone 3 lysine 4 and lysines 9,whereas tri-methylation of histone 3 lysine 4,were decreased in histones near the PDE4d gene promoter regions.The binding levels of histone transmethylase SMYD1 and histone deacetylase HDAC1 were increased in the gene promoter regions in cTnI193 His transgenic hearts.Using immune-fluorescent labeling we found an evidence of cTnI existence in the nucleus of cardiomyocytes and Western blotting further confirmed that both wild type and mutated cTnI could be detected in the cell nucleus of the hearts.Furthermore,an interaction between cTnI and SMYD1,or cTnI and HDAC1 was observed.Overexpression of the mutated cTnI in cultured cardiomyocytes reduced the expression of PDE4d.Our data suggest that the decrease of PDE4d expression in RCM mice caused by cTnI mutations may be related to epigenetic regulation,i.e.,histone acetylation and methylation,and cTnI might be involved in this procedure via an interaction with HDAC1 and SMAD1 in the hearts.