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...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.展开更多
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 conditi...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.展开更多
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,...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.展开更多
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...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)).展开更多
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...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.展开更多
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-o...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.展开更多
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 crystall...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.展开更多
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 th...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.展开更多
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 f...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.展开更多
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+) io...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.展开更多
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 sin...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.展开更多
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 ac...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.展开更多
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 ...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.展开更多
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 untreate...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.展开更多
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...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.展开更多
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 diffus...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.展开更多
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 ...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.展开更多
基金supported by the National Natural Science Foundation of China(U20A20268)Natural Science Foundation of Hunan Province(2020JJ1004)Hunan Provincial Innovation Foundation for Postgraduate(CX20211190)。
文摘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.
基金supported by the National Natural Science Foundation of China(No.21774139)China,Key Research and Development Program of Shanxi Province,China(No,202102040201009)special fund of Beijing Key Laboratory of Clean Fuels and Efficient Catalytic Emission Reduction Technology and the Fund for Shanxi“1331 Project”.Thanks to Ningbo Kejiang Culture Sci.&Tech.Development Co.,Ltd.for the help in schematic drawing。
文摘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.
基金financially supported by the National Natural Science Foundation of China (No.21271022)。
文摘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.
基金supported by the Korea Institute for Advancement of Technology (KIAT)the Ministry of Trade, Industry & Energy (MOTIE) of the Republic of Korea (P0017363)the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIT). (2023R1A2C1003312)。
文摘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)).
基金Financial supports from the B-type Strategic Priority Program of the Chinese Academy of Sciences(Grant No.XDB41000000)the National Natural Science Foundation of China(41872046,41902041 and 41173074)the Natural Science Research Project of Education Department of Guizhou Province(No.KY[2018]004)are sincerely acknowledged.
文摘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.
基金This work was supported by the National Natural Science Foundation of China (No. 20171031)
文摘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.
基金Supported by the National Natural Science Foundation of China (No. 21101075 and 21201081)the research foundation for excellent young and middle-aged scientists of Shandong Province (No. BS2011CL009 and BS2012CL008)+2 种基金the Science & Research Program foundation of high education of Shandong Province (No. J11LB52)the Rehearsal National Foundation of Jining University (Nos. 2011YYJJ06 and 2011YYJJ07)the Youths Science Foundation of Jining University (No. 2011QNKJ07)
文摘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.
基金the Foundation of Education Committee of Hunan Province (06C195) the Research Award Fund for Outstanding Young Teachers of Hengyang Normal University (2006)
文摘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.
基金supported by the National Natural Science Foundation of China(21401099)the Natural Science Foundation of Shanxi Province(202203021212331)+3 种基金Science and Technology Innovation Project of Colleges and Universities of Shanxi Province(2022L532)the National Natural Science Foundation of Anhui Province(2008085MB32 and KJ2021ZD0073)Natural Science Foundation of Shandong Province(ZR2021QB159)supported by the Talent Program Foundation of Dezhou University(2021xjrc102)。
文摘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.
基金National Natural Science Foundation of China(11974063)Graduate research innovation project,School of Optoelectronic Engineering,Chongqing University(GDYKC2023002)+1 种基金Fundamental Research Funds for the Central Universities(2022CDJQY-010)The authors extend their appreciation to the Deputyship for Research and Innovation,Ministry of Education in Saudi Arabia for funding this research work through the project no.(IFKSUOR3-073-9).
文摘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.
基金supported by the National Natural Science Foundation of China(No.21373178)the Natural Scientific Research Foundation of Shaanxi Provincial Education Office of China(No.13JS124)
文摘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.
文摘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.
基金Project(20576142) supposed by the National Natural Science Foundation of China Project(2009DFA31270) supported by the International Cooperation Project of Ministry of Science and Technology of China
文摘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.
基金supported by the Public Science and Technology Research Funds Projects of Ocean (No.201305018)the National Key Technology Research and Development Program for the 12th Five-Year Plan (No.2012BAD33B10)+3 种基金the National Natural Science Foundation of Guangdong, China (Nos. 2014A 030310351 and 2014A030310338)the Innovative Development of Marine Economy Regional Demonstration Projects of Guangdong (Nos.SZHY2012-B01-004 and GD2013-B03-001)the Science and Technology Planning Project of Guangdong Province, China (Nos.2013B 090800002 and 2015B090904003)the National Science Foundation for Young Scientists of China (No.31101271)
文摘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.
基金supported from the Natural Science Foundation of China (Grant Nos. 21771012, 21601008 and 21576006)the National Natural Science Fund for Innovative Research Groups (Grant No. 51621003)the China Postdoctoral Science Foundation (Grant No. 2016M600879)
文摘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.
基金supported by the Outstanding Adult-Young Scientific Research Encouraging Foundation of Shandong Province(No.2008BS09016)the Scientific Research Program of Shandong Province Education Department,China (No.J08LC55)
文摘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.
基金This work was supported by the NSF of Guangxi Province (0339034) and the Science Research Foundation of Guangxi Universities
文摘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.