Upper-rim-modified thioether thiacalix[4]arene used for liquid-liquid extraction of Au(Ⅲ)and Pd(Ⅱ)in hydrochloric acid medium

Gold(Au)and palladium(Pd)play an increasing role in the production and human life;Therefore,it is of great significance to study their recovery.A 5,11,17,23-tetra-ethylthio-25,26,27,28-tetra-hydroxyl thiacalix[4]arene(TCAET)was synthesized specifically for the capture of Au(Ⅲ)and Pd(Ⅱ)from HCl medium by liquid-liquid extraction.In a 0.1 mol·L^(-1)HCl medium,the transfer of Au(Ⅲ)and Pd(Ⅱ)from the aqueous phase to the organic phase was highly efficient,with a transfer ratio of 100%for Au(Ⅲ)and 98%for Pd(Ⅱ).Furthermore,the extraction equilibrium time for Au(Ⅲ)was just 5 min.Job's method data demonstrated that TCAET formed complexes with Au(Ⅲ)and Pd(Ⅱ)in a ratio of 2:3 and 1:1,respectively,during the extraction process.TCAET showed high selectivity toward Pd(Ⅱ)and Au(Ⅲ)over other competing metal ions.Moreover,both Au(Ⅲ)and Pd(Ⅱ)could be successfully stripped from the loaded organic phases with a 1.0 mol·L^(-1)thiourea in 0.5 mol·L^(-1)HCl and 0.5 mol·L^(-1)thiourea in 0.5 mol·L^(-1)HCl,respectively.Results obtained from five consecutive extraction-stripping cycles showed good reusability of TCAET toward Au(Ⅲ)and Pd(Ⅱ)recovery.The conclusion can provide a certain reference for thiacalixarene in the recovery of precious metal species.

An efficient and mild recycling of waste melamine formaldehyde foams by alkaline hydrolysis

Melamine formaldehyde foam(MFF)generates many poisonous chemicals through the traditional recycling methods for organic resin wastes.Herein,a high MFF degradation ratio of ca.97 wt.%was achieved under the mild conditions(160℃)in a NaOH–H2O system with ammelide and ammeline as the main degradation products.The alkaline solvent had an obvious corrosion effect for MFF,as indicated by scanning electron microscopy(SEM).The reaction process and products distribution were studied by Fourier-transform infrared spectroscopy(FTIR),X-ray photoelectron spectroscopy(XPS),and ^(13)C nuclear magnetic resonance(NMR).Besides,the MFF degradation products that have the similar chemical structures and bonding performances to those of melamine can be directly used as the raw material for synthesis of melamine urea-formaldehyde resins(MUFs).Moreover,the degradation system demonstrated here showed the high degradation efficiency after reusing for 7 times.The degradation process generated few harmful pollutants and no pre-or post-treatments were required,which proves its feasibility in the safe removal or recovery of waste MFF.

Preparation of Y^(3+)-doped Bi-_(2)MoO_(6) nanosheets for improved visible-light photocatalytic activity: Increased specific surface area, oxygen vacancy formation and efficient carrier separation

Although Bi_(2)Mo O_(6)(BMO) has recently received extensive attention, its visible-light photocatalytic activity remains poor due to its limited photoresponse range and low charge separation efficiency. In this work, a series of visible-light-driven Y^(3+)-doped BMO(Y-BMO) photocatalysts were synthesized via a hydrothermal method. Degradation experiments on Rhodamine B and Congo red organic pollutants revealed that the optimal degradation rates of Y-BMO were 4.3 and 5.3 times those of pure BMO, respectively. The degradation efficiency of Y-BMO did not significantly decrease after four cycle experiments. As a result of Y^(3+)doping, the crystal structure of BMO changed from a thick layer structure to a thin flower-like structure with an increased specific surface area. X-ray photoelectron spectroscopy showed the presence of highintensity peaks for the O 1s orbital at 531.01 and 530.06 eV, confirming the formation of oxygen vacancies in Y-BMO. Photoluminescence(PL) and electrochemical impedance spectroscopy measurements revealed that the PL intensity and interface resistances of composites decreased significantly, indicating reduced electron–hole pair recombination. This work provides an effective way to prepare high-efficiency Bibased photocatalysts by doping rare earth metal ions for improved photocatalytic performance.

Boosting electrocatalytic activity with the formation of abundant heterointerfaces and N, S dual-doped carbon nanotube for rechargeable Zn-air battery

Herein,a facile synthetic strategy is proposed to fabricate high-performance electrocatalysts for rechargeable Zn-air batteries(ZABs).Heterostructured NiCo/NiCo_(2)S_(4) nanoparticles encapsulated in N-,S-co-doped CNT(NiCo/NiCo_(2)S_(4)@NSCNT) are synthesized via co-precipitation,thermal carbonization,and partial sulfidation processes.The strongly coupled NiCo/NiCo_(2)S_(4) heterostructure can improve the redox property and charge transfer ability.Also,the CNTs with abundant foreign dopants provide high electrical conductivity and abundant defect sites for both the oxygen evolution reaction(OER) and oxygen reduction reaction(ORR).The prepared NiCo/NiCo_(2)S_(4)@NSCNT electrocatalyst exhibits a low overpotential of 349 mV at a current density of 10 mA cm-2 and a half-wave potential of 0.865 V for the OER and ORR,respectively.Moreover,the ZAB assembled using as-prepared NiCo/NiCo_(2)S_(4)@NSCNT can provide superior specific capacity(756.16 mA h g_(Zn)^(-1)],peak power density(155.82 mW cm^(-2)),and long-term cyclability compared to those of the precious metal-based electrocatalyst(Pt/C+RuO_(2)).

Depth profiling of arsenian pyrite in Carlin-type ores through wet chemistry

Enrichment of As and Au at the overgrowth rims of arsenian pyrite is a distinctive feature of Carlin-type gold ores.Revealing distribution of such key elements in high resolution is of fundamental importance yet often proves challenging.In this study,repeated non-oxidative acid etching of ore samples from Shuiyindong gold deposit was applied to enable elemental depth profiling of goldbearing arsenian pyrite grains.ICP-OES and AAS were used to determine the dissolved Fe,As,and Au concentrations in each of the etching solutions,and XPS was carried out to exam the etched mineral surfaces.In contrast to conventional ion beam etching that may cause substantial sample damage,our acid etching method does not seem to significantly alter the composition and chemical state of the samples.The etched depths directly converted from the measured elemental concentrations can reproducibly reach a very high resolution of~1 nm,and can be conveniently controlled through varying the etching time.While the Fe and As depth profiles consistently reflect the surface oxidation property of arsenian pyrite,the Au profile displaying an obvious upward trend reveals the ore fluid evolution at the late stage of mineralization.Based on our experimental results,we demonstrate that our wet chemistry method is capable of effective depth profiling of gold ore and perhaps other geological samples,with advantages surpassing many instrumental techniques including negligible sample damage,nanoscale resolution as well as isotropic etching.

Quantum-chemical Study on the Structures and Properties of Uracil-BX_3 (X = F,Cl) Complexes

For the uracil-BX3 （X = F, Cl） systems, geometries and binding energies have been calculated by using the Lee-Young-Parr correlation functionals （B3LYP） method of density functional theory （DFT） and the second-order Moller-Plesset （MP2） method of ab initio at the 6- 311 ＋G^＊ or 6-311 ＋＋G^＊ basis set. Four isomers were found for each system, and then the single-point energy evaluations were performed using the larger basis sets of （6-311 ＋G（2df, p） and aug-cc-pVDZ with DFF method. In the most stable isomer of uracil-BF3 or uracil-BCl3, the boron atom of BX3 （X = F, Cl） connects to the carbonyl oxygen O7 of uracil with a stabilization energy of -46.56 or -31.10 kJ/mol at the B3LYP/6-31 1＋G^＊ level （BSSE corrected）. The analyses for combining interaction between BX3 and uracil with the atom-in-molecule theory （AIM） and natural bond orbital method （NBO） have been performed. The results indicate that all isomers were formed with σ-p type interactions between uracil and BX3, in which the carbonyl oxygen offers its lone pair electrons to the empty p orbital of boron atom and the concomitances of charge transfer from uracil to BX3 occur. Moreover, there exists one or two hydrogen bonds in most isomers of uracil-BX3 system and these hydrogen bonds contribute to the stability of the complex systems. Frequency analysis suggests that the stretching vibration of BX3 undergoes a red shift in complexes. Uracil-BF3 complex is more stable than uracil-BCl3 although the distance of B-O is shorter in the latter. Besides, the conversion mechanisms between different isomers of uracil-BF3 have been obtained.

Synthesis, Crystal Structure and Chemical Bonding of a New Binary Lu-Sn Phase: Lu_(11)Sn_(10)

A new tetragonal phase of LunSnl0 is obtained from high temperature reaction of the pure elements in a welded tantalum tube. Its crystal structure was established by single-crystal X-ray diffraction. Lu11Sn10 crystallizes in the tetragonal space group 14/mmm （No. 139） with a = 11.2953（18）, c = 16.424（4） A, V= 2095.5（7）A3, Z= 4, Mr = 3111.57, Dc = 9.863 g/cm^3, p = 62.897 -1 mm , F（000） = 5124, and the final R = 0.0348 and wR = 0.0894 for 706 observed reflections with 1 〉 2σ（I）. The structure of LullSnl0 may be derived from the HonGel0 structural type. It is isostructural with DyllSn10, featuring a three-dimensional （3D） framework composed of [Sn4] squares and [Sn2] dimers interlinked via Sn-Sn bonds with two types of one-dimensional （1D） tunnels along the c-axis, which are occupied by isolated Sn atoms, [Sn2] dimers and all the Lu atoms Band structure calculation based on density functional theory method indicates that LUllSn10 is metallic.

Synthesis, Crystal Structure and Electrochemical Properties of [Ni(phen)_3]·(m-nitrobenzoic acid)_2·(H_2O)

A new nickel（Ⅱ） coordination complex [Ni（phen）a].（m-nitrobenzoic acid）2·（H2O） was synthesized by self-assembly of m-nitrobenzoic acid, 1,10-phenanthroline and nickelous perchlorate. It crystallizes in the monoclinic system, space group C2/c, with a = 2.4596（6）, b = 1.2124（3）, c = 1.9824（5） nm, fl = 97.088（5）°, V = 5.866（3） nm3, Dc = 1.474 g/cm3, Z = 4, Mr = 1301.82,μ（MoKa） = 0.417 mm^-1 F（000） = 2688, R = 0.0493 and wR = 0.1025. Structural determination indicates that the nickel（H） ion is coordinated with six nitrogen atoms from three phens, giving a distorted octaheclral coordination geometry. The cyclic voltametric analysis shows that the electron transfer in the electrode reaction is irreversible.

Efficient adsorption separation of methane from C_(2)-C_(3) hydrocarbons in a Co(Ⅱ)-nodes metal-organic framework

Methane(CH_(4))as a substitute for other mineral fuels plays a crucial role in reducing energy consumption and preventing environmental pollution.The present study employs a solvothermal method to fabricate a porous framework Co-metal-organic framework(Co-MOF)containing two distinct secondary building units(SBUs):an anionic[Co_(2)(μ_(2)-OH)(COO)_(4)(H_(2)O)]and a neutral[CoN_(2)(COO)_(2)].Notably,within the anionic SBUs,the coordinated water molecules induce the generation of divergent unsaturated Co(Ⅱ)centers in the unidirectional porous channels,thereby creating open metal sites.The adsorption performance of Co-MOF towards pure component gases was systematically investigated.The results demonstrated that Co-MOF exhibits superior adsorption capacity for C_(2)-C_(3) hydrocarbons compared to CH_(4),which offers the potential for efficient adsorption and separation of CH_(4) from C_(2)-C_(3) hydrocarbons.The gas selectivity separation ratios of Co-MOF for C_(2)H_(6)/CH_(4) and C_(3)H_8/CH_(4) were calculated using the ideal adsorbed solution theory method at 273/298 K and 0.1 MPa.The results revealed that Co-MOF achieved remarkable equilibrium separation selectivity for CH_(4) and C_(2)-C_(3) hydrocarbon gases among non-modified MOFs,signifying the potential of the synthesized Co-MOF for efficient recovery and purification of CH_(4) from C_(2)-C_(3) hydrocarbons.Breakthrough experiments further demonstrate the ability of Co-MOF to purify methane from C_(2)-C_(3) hydrocarbons in practical gas separation scenarios.Additionally,molecular simulation calculations further substantiate the propensity of anionic SBUs to interact with C_(2)-C_(3) hydrocarbon compounds.This study provides a novel paradigm for the development of porous MOF materials in the application of gas mixture separation.

Luminescence regulation of Sb^(3+)in 0D hybrid metal halides by hydrogen bond network for optical anti-counterfeiting

The Sb^(3+) doping strategy has been proven to be an effective way to regulate the band gap and improve the photophysical properties of organic-inorganic hybrid metal halides(OIHMHs).However,the emission of Sb^(3+) ions in OIHMHs is primarily confined to the low energy region,resulting in yellow or red emissions.To date,there are few reports about green emission of Sb^(3+)-doped OIHMHs.Here,we present a novel approach for regulating the luminescence of Sb^(3+) ions in 0D C_(10)H_(2)_(2)N_(6)InCl_(7)·H_(2)O via hydrogen bond network,in which water molecules act as agents for hydrogen bonding.Sb^(3+)-doped C_(10)H_(2)2N_(6)InCl_(7)·H_(2)O shows a broadband green emission peaking at 540 nm and a high photoluminescence quantum yield(PLQY)of 80%.It is found that the intense green emission stems from the radiative recombination of the self-trapped excitons(STEs).Upon removal of water molecules with heat,C_(10)H_(2)_(2)N_(6)In_(1-x)Sb_(x)Cl_(7) generates yellow emis-sion,attributed to the breaking of the hydrogen bond network and large structural distortions of excited state.Once water molecules are adsorbed by C_(10)H_(2)_(2)N_(6)In_(1-x)Sb_(x)Cl_(7),it can subsequently emit green light.This water-induced reversible emission switching is successfully used for optical security and information encryption.Our findings expand the under-standing of how the local coordination structure influences the photophysical mechanism in Sb^(3+)-doped metal halides and provide a novel method to control the STEs emission.

Synthesis, Structure and Electrochemical Property of a New 3D Ag(I) Coordination Polymer Constructed by Biphenyl-2,2ˊ,4,4ˊ-tetracarboxylate

A new 3D Ag（I） coordination polymer, [Ag8（btc）2（bpp）2]n（1, H4btc = biphenyl- 2,2ˊ,4,4ˊ-tetracarboxylic acid, bpp = 1,2-bis（4-pyridyl）propane）, has been hydrothermally synthesi- zed and characterized by single-crystal X-ray diffraction analysis, elemental analysis and IR spectroscopy. Complex 1 crystallizes in the triclinic system, space group P1 with a = 13.4899（8）, b = 13.4928（8）, c = 16.4575（10） , α = 102.7640（10）, β = 108.8100（10）, γ = 101.4940（10）°, V = 2644.1（3） 3, Z = 2, Dc = 2.401 Mg·m-3, μ = 2.978 mm-1, F（000） = 1840, the final R = 0.0481 and wR = 0.0955 for 6794 observed reflections with I 〉 2σ（I）. Complex 1 features a 3D framework formed by Ag（I）-carboxylate chains containing [Ag16（COO）16] secondary building block. Furthermore, thermal stability and electrochemical property of 1 are also investigated in detail.

Preparation and Characterization of Two-component Waterborne Polyurethane Comprised of Water-soluble Acrylic Resin and HDI Biuret

A two-component waterborne polyurethane(2K-WPU) was prepared by mixing water-soluble acrylic resin and hexamethylene diisocyanate biuret, and then diluted for phase inversion with water. Compared with water-soluble acrylic resin, the phase inversion of 2K-WPU occurs at lower water content. It is indicated by TEM that 2K-WPU parti-cles show a core-shell structure, in which HDI biuret is encapsulated by hydrophilic acrylic resin. 2K-WPU emulsion with HDI biuret has larger particle size and narrower distribution index, while for 2K-WPU emulsion with HDI iso-cyanurate, the latex not only has large particle size, but also has two-peak distribution. FTIR shows that the reaction be-tween HDI biuret and acrylic resin can complete in 12h. In addition, studies on effect of composition of acrylic resin on performance of 2K-WPU show that narrowing the polar difference between water-soluble acrylic resin and HDI biuret and improving the miscibility of two components are the key to prepare the transparent and high gloss films with high crosslinking density.

Determination of contents of eight alkaloids in fruits of Macleaya cordata (Willd) R. Br. from different habitats and antioxidant activities of extracts

A reliable ultrasound-assisted extraction (UAE) method combined with HPLC-UV for quantification of eight active alkaloids in fruits of Macleaya cordata (Willd) R. Br. was developed. The optimization conditions of UAE were obtained by using Box-Behnken design of response surface methodology. Chromatography was carried out using a Kromasil C_(18) column by gradient elution with 0.1% phosphoric acid aqueous solution for HPLC-UV. All calibration curves showed good linear correlation coefficients (R^2>0.999 6) and recoveries (from 97.3% to 104.9%) were acceptable. 1,1-diphenyl-2-picrylhydrazyl (DPPH) method was employed to test the antioxidant activity of the extract from the samples. The proposed method was successfully applied to quantifying eight components in nine samples of M.cordata, and significant variations of alkaloid contents and antioxidant activity of the samples from different habitats were demonstrated. It presents a powerful proof for the selection of the best sources to extract eight kinds of alkaloids.

Identification of Odor Volatile Compounds and Deodorization ofPaphia undulata Enzymatic Hydrolysate

Unfavorable fishy odour is an inevitable problem in aquatic products. In the present study, headspace solid-phase microextraction gas chromatography mass spectrometry(HS-SPME-GC-MS) analysis of volatiles from untreated samples and three deodorized samples(under the optimal conditions) of Paphia undulata enzymatic hydrolysate revealed that the compounds contributing to the distinctive odor were 1-octen-3-ol, n-hexanal, n-heptanal, 2,4-heptadienal, and 2,4-decadienal, whereas n-pentanal, n-octanal, n-octanol, benzaldehyde, 2-ethylfuran and 2-pentylfuran were the main contributors to the aromatic flavor. The deodorizing effects of activated carbon(AC) adsorption, yeast extract(YE) masking and tea polyphenol(TP) treatment on a P. undulata enzymatic hydrolysate were investigated using orthogonal experiments with sensory evaluation as the index. The following optimized deodorization conditions were obtained: AC adsorption(35 mg mL^(-1), 80℃, 40 min), YE masking(7 mg mL^(-1), 45℃, 30 min) and TP treatment(0.4 mg mL^(-1), 40℃, 50 min). AC adsorption effectively removed off-flavor volatile aldehydes and ketones. YE masking modified the odor profile by increasing the relative contents of aromatic compounds and decreasing the relative contents of aldehydes and ketones. The TP treatment was not effective in reducing the odor score, but it significantly reduced the relative content of aldehydes while increasing that of alkanes. It is also notable that TP effectively suppressed trimethylamine(TMA) formation in a P. undulate hydrolysate solution for a period of 72 h.

Applications of metal–organic frameworks for green energy and environment: New advances in adsorptive gas separation, storage and removal

The separation of gas molecules with similar physicochemical properties is of high importance but practically entails a substantial energy penalty in chemical industry. Meanwhile, clean energy gases such as H_2 and CH_4 are considered as promising candidates for the replacement of traditional fossil fuels. However, the technologies for the storage of these gases are still immature. In addition, the release of anthropogenic toxic gases into the atmosphere is a worldwide threat of growing concern. Both in academia and industry, considerable research efforts have been devoted to developing advanced porous materials for the effective and energy-efficient separation, storage, or capture of the related gases. In contrast to conventional inorganic porous materials such as zeolites and activated carbons, metal–organic frameworks(MOFs) are considered as a type of promising materials for gas separation and storage. In this contribution, we review the recent research advance of MOFs in some relevant applications, including CO_2 capture, O_2 purification, separation of light hydrocarbons, separation of noble gases, storage of gases(CH_4,H_2, and C_2 H_2) for energy, and removal of some gaseous air pollutants(NH_3, NO_2, and SO_2). Finally, an outlook regarding the challenges of the future research of MOFs in these directions is given.

Synthesis,characterization,and theoretical study of N,S-codoped nano-TiO_2 with photocatalytic activities

Nitrogen and sulfur doped titanium dioxide photocatalysts were prepared by the sol-gel method.The products were characterized by X-ray diffraction （XRD）,transmission electron microscopy （TEM）,and UV-visible diffuse reflectance spectra （DRS）.Photocatalytic activities of the samples were investigated on the degradation of methyl orange （MO）.The effect of the dopants on the electronic structure of TiO2 was studied by the first-principles calculations based on the density functional theory （DFT）.The orbital hybridization resulted in energy gap narrowing and electronic delocalization in the crystal of doped TiO2.Mobile electrons of varied energetic states could offer enhanced electron transfer,together with optical absorption improvement.The results show that the doping elements of N and S play a cooperative role in the modification of electronic structure,which enhances the photocatalytic performance.The experimentally observed absorption edges of N-doped TiO2,S-doped TiO2,and N,S-codoped TiO2 are 420,413,and 429 nm,respectively,which can be explained by the theoretical calculation results.

Synthesis and Crystal Structure of Bridging Complex [Cu_2(bipy)_2·OAc·Cl·OH]·TsTausH·3H_2O

The title complex [Cu2(bipy)2OAcClOH]TsTausH3H2O(C31H37Cl- Cu2N5O11S2) has been synthesized by the reaction of 2,2?bipyridine(bipy), N-P-tolysulfony taurine (TsTausH) and copper acetate in water-ethanol solution, and its crystal structure was determined by X-ray diffraction method. The crystal belongs to triclinic, space group P with a = 0.74485(14), b = 1.6094(3), c = 1.7472(3) nm, a = 114.662(4), b = 99.997(4), g = 93.218(4), V = 1.8551(6) nm3, Mr = 882.31, Z = 2, Dc = 1.580 g/cm3, m = 1.395 mm-1 and F(000) = 906. The complex is a binuclear copper compound, and the two copper ions nearly have the same coordination environment. There exists MM bond in the complex. The distance of Cu(1)Cu(2) is 0.29747(7) nm. The two ions form two distorted octahedral geometries.