MOF-808@PAN纳米纤维制备及其降解芥子气模拟剂性能

芥子气（HD）是难降解可致死的最广泛使用的化学战剂,锆基金属有机框架材料（Zr-MOFs）MOF-808对其有很好的降解效果。但现阶段研究MOF-808对HD的降解多以粉末态使用,易团聚难回收,为解决此问题,研究使用静电纺聚丙烯腈（PAN）来固定回收MOF-808,并验证了MOF-808@PAN对芥子气有优异的降解效果。以ZrOCl2、均苯三甲酸为原料,三氟乙酸为调节剂,基于水为溶剂无模板的合成了MOF-808@PAN纳米纤维材料。采用SEM、XRD、FTIR、TG及氮气吸脱附对催化剂结构进行了表征。实验结果表明,MOF-808@PAN纳米纤维具有441.5m2/g的比表面积。在5μL芥子气模拟剂（CEES）下暴露20个小时,CEES的降解效率可达83.7%。为芥子气的降解提供另一解决思路。     

Novel Topology in Semiconducting Tetrathiafulvalene Lanthanide Metal-Organic Frameworks

Tetrathiafulvalene tetrabenzoate (TTFTB) and several lanthanide ions self-assemble into metal-organic frameworks (MOFs) that exhibit a novel topology, a (3,3,3,6,6)-coordinated net, which features an unusual ligand coordination mode and stacking motif. The Yb and Lu MOFs are electrically conductive, with pellet conductivity values of 9(7) × 10⁻⁷ and 3(2) × 10⁻⁷ S/cm, respectively. The crystallographically-determined bond lengths indicate partial oxidation of the ligand, with close S ⋅ ⋅ ⋅ S contacts between ligands providing likely charge transport pathways in the material. Magnetometry reveals temperature-independent paramagnetism, consistent with the presence of ligand-based radicals, as well as weak antiferromagnetic coupling between Yb³⁺ centers. These results illustrate the diversity of MOF structures and properties that are accessible with the TTFTB ligand owing to its electroactive nature, propensity for intermolecular interactions, and conformational flexibility.     

Anticancer Potential of (Pentamethylcyclopentadienyl)chloridoiridium(III) Complexes Bearing κP and κP,κS‐Coordinated Ph2PCH2CH2CH2S(O)xPh (x=0–2) Ligands

Iridium(III) complexes of the type [Ir(η⁵‐C₅Me₅)Cl₂{Ph₂PCH₂CH₂CH₂S(O)_xPh‐κP}] (x=0–2; 1 – 3 ) and [Ir(η⁵‐C₅Me₅)Cl{Ph₂PCH₂CH₂CH₂S(O)_xPh‐κP,κS}][PF₆] (x=0–1; 4 and 5 ) with 3‐(diphenylphosphino)propyl phenyl sulfide, sulfoxide, and sulfone ligands Ph₂PCH₂CH₂CH₂S(O)_xPh were designed, synthesized, and characterized fully, including X‐ray diffraction analyses for complexes 3 and 4 . In vitro studies against human thyroid carcinoma (8505C), submandibular carcinoma (A253), breast adenocarcinoma (MCF‐7), colon adenocarcinoma (SW480), and melanoma (518A2) cell lines provided evidence for the high biological potential of the neutral and cationic iridium(III) complexes. Neutral iridium(III) complex 5 proved to be the most active, with IC₅₀ values up to about 0.1 μM , representing activities of up to one order of magnitude higher than cisplatin. Using 8505C cells, apoptosis was shown to be the main mechanism through which complex 5 exerts its tumoricidal action. The described iridium(III) complexes represent potential leads in the search for novel metal‐based anticancer agents.     

Synthesis of a carbamide-based dithiocarbamate chelator for the removal of heavy metal ions from aqueous solutions

This study was carried out to develop a carbamide-based dithiocarbamate (CDTC) chelator for the removal of heavy metal ions from wastewater. Its structural properties were characterized by FT-IR, ¹H NMR and ¹³C NMR. Results confirmed the functional groups of HNC(S)S existed. The adsorption isotherms showed CDTC had a high adsorption capability for Zn (119.8 mg/g) and Cu (63.1 mg/g). It exhibited a distinctive selectivity for the removal of metal ions (Cu²⁺ > Zn²⁺ > Cr³⁺ > Pb²⁺ > Cd²⁺) as they coexisted. The influence of initial pH of wastewater for the removal efficiency of metal ions was also investigated and a pH > 7 was preferred.     

Heavy metal ions retention by bi-functionalized lignin: Synthesis,applications, and adsorption mechanisms

Bi-functionalized lignin with amino and sulfonic groups (ASL) was synthesized via Mannich reaction and sulfomethylation. It was systematically characterized by FT-IR, element analysis, surface charge and XPS. Effects of initial pH, contact time and initial metal ion concentration on the adsorption of Cu(II) and Pb(II) onto ALS were studied. Results indicated that the biosorbent showed excellent performance for metals even from low pH solutions. The adsorption kinetics and isotherms could be described well with Pseudo-second-order and D–R model, respectively. Further investigation of the metal-loaded ASL by FT-IR and XPS elucidated the amino and sulfonic groups reacted with metals in different way.     

Removal of several metal ions from aqueous solution using powdered stem of Arundo donax L. as a new biosorbent

Arundo donax L., a member of Poaceae, was washed, dried, selected, pulverized, and then used for removal of Cu(II), Cd(II), Ni(II), Pb(II) and Zn(II) from aqueous solution. Series batch experiments were conducted to investigate the effects of contact time, pretreatment, particle size of biomass and solution pH on the biosorption capability of A. donax L. powder. The desorption characteristics and renewability of the biomass were also studied. The applicability of Langmuir and Freundlich isotherms was examined for the experimental data, so did the pseudo-first-order, pseudo-second-order and Elovich kinetic models. Results showed that alkali-treated A. donax L. biomass was more appropriate to be the bio-material for biosorption when compared to acid-treated, washed and virgin A. donax L. Owing to its fast adsorption rate, high uptake capacity and the renewability of facility, stem of A. donax L. treated with NaOH seems to be a promising biosorbent for removal of heavy metals from wastewater.     

Microstructure and electrical conductivity of Mo/TiN composite powder for alkali metal thermal to electric converter electrodes

A Mo/TiN composite powder has been synthesized by a sol–gel method to improve the electrical performance and microstructural stability of the alkali metal thermal to electric converter electrode. The core (TiN)–shell (Mo) structure of the composite powder is confirmed by energy-dispersive X-ray spectroscopy and scanning electron microscopy. The composite powder is primarily composed of submicron (400–800 nm) particles that are coated on a core (>3–5 μm) particle. The Mo/TiN composite electrode exhibits high electrical conductivities of 1000 Scm⁻¹ at 300 °C and 260 Scm⁻¹ at 700  °C in an Ar atmosphere. The electrode exhibits excellent tolerance against grain growth during thermal cycling tests (R.T.↔800 °C), where the average growth rate of Mo grains in the Mo/TiN composite electrodes is controlled less than 0.5%/time (0.62→0.65 μm), while the growth rate in Mo electrodes is 306.7%/time (0.24→3.92 μm). It can be concluded that the Mo/TiN composite powder will suppress the degradation of the electrode and enhance the performance and durability of the unit cell at elevated temperatures.     

Advanced Monte Carlo simulations of the adsorption of chiral alcohols in a homochiral metal‐organic framework

Grand canonical Monte Carlo (GCMC) simulations with configurational biasing were used to study the enantioselective adsorption of four alkanols in a homochiral metal‐organic framework, known as hybrid organic‐inorganic zeolite analogue HOIZA‐1. Conventional GCMC simulations are not able to converge satisfactorily for this system due to the tight fit of the chiral alcohols in the narrow pores. However, parallel tempering and parallel mole‐fraction GCMC simulations overcome this problem. The simulations show that the enantioselective adsorption of the different (R,S)‐alkanols is due to the specific geometry of the chiral molecules relative to the pore size and shape. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2324–2334, 2014     

Mini Liquid‐Liquid Extractor without Moving Parts Based on the Coanda Effect

A mini liquid‐liquid extractor was designed based on a feedback fluidic oscillator. According to the Coanda effect, the designed oscillator with two feedback channels enables good mixing of the aqueous and organic phases. Co‐current liquid‐liquid extraction was performed in the mini extractor, and it was visually observed that the aqueous phase was dispersed into small droplets because of fluidic oscillation and vortex formation. The aqueous phase was more effectively dispersed at the stage near the outlet and with increasing flow. Several tests were performed for evaluating the extraction performance of the extractor using 30 % tributyl phosphate‐kerosene and 3 M HNO₃ solutions as the organic and aqueous phases, respectively. The obtained extraction efficiency was close to the equilibrium efficiency, indicating that this extractor has the potential for liquid‐liquid extraction of hazardous liquids.