MAX phases are gaining attention as precursors of two-dimensional MXenes that are intensively pursued in applications for electrochemical energy storage.Here,we report the preparation of V_(2)SnC MAX phase by the molt...MAX phases are gaining attention as precursors of two-dimensional MXenes that are intensively pursued in applications for electrochemical energy storage.Here,we report the preparation of V_(2)SnC MAX phase by the molten salt method.V_(2)SnC is investigated as a lithium storage anode,showing a high gravimetric capacity of 490 mAh g−1 and volumetric capacity of 570 mAh cm^(−3) as well as superior rate performance of 95 mAh g^(−1)(110 mAh cm^(−3))at 50 C,surpassing the ever-reported performance of MAX phase anodes.Sup-ported by operando X-ray diffraction and density functional theory,a charge storage mechanism with dual redox reaction is proposed with a Sn-Li(de)alloying reaction that occurs at the edge sites of V_(2)SnC particles where Sn atoms are exposed to the electrolyte followed by a redox reaction that occurs at V_(2)C layers with Li.This study offers promise of using MAX phases with M-site and A-site elements that are redox active as high-rate lithium storage materials.展开更多
Ni-based metallic foams possessing large specific surfaces and open cell structures are of specific interest as catalysts or catalyst carriers for electrolysis of water.Traditional fabrication of Nickel foam limits th...Ni-based metallic foams possessing large specific surfaces and open cell structures are of specific interest as catalysts or catalyst carriers for electrolysis of water.Traditional fabrication of Nickel foam limits the element modification choices to several inert transition metals only on polymer foam precursor and subsequent preparation of foam-based catalysts in aqueous solution or organic electrolyte.To expand the modification horizon,molten salt with wide electrochemical window and fast ion diffusion can achieve the reduction of highly active elements.Herein,we reported is a general and facile method to deposit directly of highly reactive element La and prepare hierarchical honeycomb LaNi_(5) alloy on Ni foam(ho-LaNi_(5)/NF).This self-supporting electrode presents excellent electrical coupling and conductivity between the Ni foam and LaNi_(5),which provides a 3D self-supported heterostructure with outstanding electrocatalytic activity and excellent durability for the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).It exhibits excellent overpotential(1.86 V)comparable to commercial coupled IrO_(2)//Pt/C(1.85 V)at a high current density of 100 m A cm^(-2).This work may pave the way for fabricating novel 3D self-supported honeycomb alloy that can be applied as electrode for usage of clean energy.展开更多
The adsorption of uranyl on hydroxylated α-SiO_2(001) in the presence of a series of anionic ligands, i.e. OH^-, CO_3^(2-), NO_3^-, H_2PO_4^-, HPO_4^(2-),CH_3COO^-(Ac^-), C_6H_5COO^-(PhCO_2^-), C_6H_5O^-(PhO^-), was ...The adsorption of uranyl on hydroxylated α-SiO_2(001) in the presence of a series of anionic ligands, i.e. OH^-, CO_3^(2-), NO_3^-, H_2PO_4^-, HPO_4^(2-),CH_3COO^-(Ac^-), C_6H_5COO^-(PhCO_2^-), C_6H_5O^-(PhO^-), was studied by the periodic density functional theory(DFT) implemented in the Vienna ab initio simulation package(VASP). For the ligands other than OH^-and PhO^-, only the bidentate coordination modes to the uranyl were considered. The excess charge effect of a charged system was first evaluated by constructing models with net charge as is or neutralized by creating defect at the bottom of silica, and the results show that a neutralized model, even with defects, is more realistic than the charged ones.All uranyl species prefer to bind with the deprotonated site(—O^-) rather than the protonated one(—O_H), which suggests that the increase of pH,which leads to the deprotonation of the surface, may enhance the uranyl adsorption. On the other hand, the anionic ligands, which are formed at higher pH, have negative effects. The weaker acidic ligands, such as H_2CO_3, H_3PO_4 and H_2O, whose speciation in solutions is sensitive to the fluctuation of pH, have more complex effect on the uranyl adsorption than strong acids or bases. Humic substances may coordinate with uranyl through carboxyl and phenolic groups, with the carboxyl group bound stronger. The ternary complexes with one bidentate(or monodentate)anion and one(or two) H20 as ligands, which leads to the uranyl penta-coordinated in its equatorial plane, are more favorable than other configurations when bound to the same anionic ligand. Both the charged nature and the coordination behavior of an anionic ligand are relevant to its ability to influence the adsorption of uranyl on the mineral surface. In addition, the uranyl species adsorbed at the surface functionalized by anionic ligands were also addressed, and the functionalized surfaces have weaker interaction with hydrated uranyl dication.展开更多
OBJECTIVE The antioxidative system in human hepatocellular carcinoma was investigated. METHODS The activities of cytosolic catalase (CAT), superoxide dismu-tase, glutathione peroxidase (GSH-Px), glutathione S-tranfera...OBJECTIVE The antioxidative system in human hepatocellular carcinoma was investigated. METHODS The activities of cytosolic catalase (CAT), superoxide dismu-tase, glutathione peroxidase (GSH-Px), glutathione S-tranferase and levels of reduced glutathione, total protein thiols and malondialdehyde were assayed in 10 cases of hepatocellular carcinoma and adjacent normal liver. RESULTS Hepatoma tissues showed higher activities of CAT, GSH -Px and lower content of total antioxidative capacity compared to adjacent normal liver tissue (P<0.05). CONCLUSION These findings suggest that the antioxidative defense-related enzymes and antioxidants are largely regulated in hepatoma cells. However, the mechanism which is not clear requires further investigation.展开更多
The development of adsorbent materials for effective capture of radioactive iodomethane(CH_(3)I) from the off-gas of used nuclear fuel reprocessing, remains a significant and challenging line of research because curre...The development of adsorbent materials for effective capture of radioactive iodomethane(CH_(3)I) from the off-gas of used nuclear fuel reprocessing, remains a significant and challenging line of research because currently state-of-art adsorbents still suffer from low binding affinity with CH_(3)I. Here, we proposed a brand-new adsorption topological structure by developing a 2D interdigitated layered framework, named SCU-20, featuring slide-like channel with multiple active sites for CH_(3)I capture. The responsive rotating-adaptive aperture of SCU-20 enables the optimal utilization of all active sites within the pore for highly selective recognition and capture of CH_(3)I. A record-breaking CH_(3)I uptake capacity of 1.84 g/g was achieved under static sorption conditions with saturated CH_(3)I vapor. Both experimental and theoretical findings demonstrated that the exceptional uptake of SCU-20 towards CH_(3)I can be attributed to the confined physical electrostatic adsorption of F sites, coupled with the chemical nitrogen methylation reaction with uncoordinated N atoms of pyrazine. Moreover, dynamic CH_(3)I uptake capacity potentially allows for the capture of CH_(3)I in simulated real-world off gas reprocessing conditions. This study highlights the potential of SCU-20 as a promising candidate for efficient capture of iodine species and contributes to the development of effective solutions for radioactive iodine remediation.展开更多
Developing efficient adsorbents for radon(Rn)capture from the ambient environment is of paramount importance for public health.However,it poses a great challenge due to the chemical inertness and extremely low molar c...Developing efficient adsorbents for radon(Rn)capture from the ambient environment is of paramount importance for public health.However,it poses a great challenge due to the chemical inertness and extremely low molar concentration of Rn in air.Herein,we report a zeolite imidazolate frameworkderived metallic carbon adsorbent(Zn@NPC)with record high Rn removal performance under ambient conditions.Upon one-step pyrolysis,the prepared Zn@NPC possesses pores with a preference for Rn and atomically dispersed Zn sites,achieving a high Rn removal efficiency that doubles in adsorption coefficient(9.47 L·g^(−1))and triples in adsorption kinetic coefficient(20.25 mL·g^(−1)·min^(−1))over the benchmark Rn adsorbent coconut activated charcoal.Density functional theory calculations elucidate the important role of the metal polarization effect,which cooperates with the pore size confinement effect to boost the overall Rn adsorption performance.This work launches a promising alternative for practical Rn capture.展开更多
The second example of tetravalent plutonium carboxyl-based organic framework,^(242)Pu(OH)[PO[(C_(6)H_(4))COO]_(3)]·H_(2)O,termed as PuTPO(TPO=tris(4-carboxylphenyl)-phosphineoxide),was reported in this work.A ser...The second example of tetravalent plutonium carboxyl-based organic framework,^(242)Pu(OH)[PO[(C_(6)H_(4))COO]_(3)]·H_(2)O,termed as PuTPO(TPO=tris(4-carboxylphenyl)-phosphineoxide),was reported in this work.A series of characterizations of PuTPO,such as X-ray crystallography and solid-state UV-Vis-NIR spectroscopy,were carried out to expatiate its structure and physicochemical properties.PuTPO is constructed by dimers of the plutonium-oxygen subunit of[Pu_(2)O_(16)].Characteristic peaks located at approximately 1100 nm can be considered to be the fingerprint peaks of tetravalent plutonium.While PuTPO can maintain high crystallinity within several months after synthesis,it exhibits a radiation-induced swelling effect probed by the expansion of cell parameter of b axis after self-irradiation fromα-decay of ^(242)Pu.This result enriches the inventory of tetravalent plutonium compounds and provides an insight into the irradiation resistance of metal-organic frameworks.展开更多
Uranium and molybdenum are important strategic elements. The production of ^(99)Mo and the hydrometallurgical process of uranium ore face difficult problems of separation of uranium and molybdenum.In this study, the f...Uranium and molybdenum are important strategic elements. The production of ^(99)Mo and the hydrometallurgical process of uranium ore face difficult problems of separation of uranium and molybdenum.In this study, the four phenanthroline diamide ligands were synthesized, and extraction and stripping experiments were performed under different conditions to evaluate the potential application of these ligands for separation of U(Ⅵ) over Mo(Ⅵ). With the growth of alkyl chain, the solubility of ligands could be greatly improved, and the separation effect of U(Ⅵ) over Mo(Ⅵ) gradually increased. The SF_(U/Mo) were around 10,000 at 4 mol/L HNO3. Three stripping agents were tested with the stripping efficiency of Na_(2)CO_(3)(5%) > H_(2)O > HNO_(3)(0.01 mol/L). The stripping percentages of the three stripping agents were all close to unity, indicating that the ligands had the potential to be recycled. The chemical stoichiometry of U(Ⅵ) complexes with ligands was evaluated as 1:1 using electrospray ionization mass spectrometry,ultraviolet visible spectroscopy and single-crystal X-ray diffraction. The consistency between theoretical calculation and experimental results further explains the coordination mechanism.展开更多
Post-synthetic functionalization of covalent organic frameworks(COFs)is an alternative way to enhance and broaden their properties and potential applications.However,the chemical functionalization of COFs is a great c...Post-synthetic functionalization of covalent organic frameworks(COFs)is an alternative way to enhance and broaden their properties and potential applications.However,the chemical functionalization of COFs is a great challenge because traditional procedures are often time-and energy-consuming,while the crystallinity of COFs can be damaged under harsh conditions.Here we report the in-situ introduction of functional graft chains onto the skeleton of COFs during the synthesis process through the combination of radiation-induced synthesis and graft polymerization techniques under ^(60)Co gamma-ray radiation.The synthesis and functionalization of COFs are simultaneously accomplished in a chemical system under ambient conditions yielding a large number of different functionalized COFs.The obtained carboxyl-functionalized COFs exhibit excellent radioactive uranium removal capabilities from aqueous solution with fast uptake dynamics,high adsorption capacity,and excellent selectivity over other competing metal ions.展开更多
Platinum recovery from waste electrical and electronic equipment(WEEE) in highly acidic solutions is significant to the electronics industry and environmental remediation. However, the lack of ingenious design and syn...Platinum recovery from waste electrical and electronic equipment(WEEE) in highly acidic solutions is significant to the electronics industry and environmental remediation. However, the lack of ingenious design and synergetic coordination gives rise to unsatisfied PtCl_(4)^(2-)extraction capacities and selectivities in most previously reported adsorbents(e.g., polymeric and inorganic materials). Herein, we proposed a synergistic strategy that realizes highly selective PtCl_(4)^(2-)uptake through first-and second-sphere coordinations. The proof-of-concept imine-linked covalent organic framework(SCU-COF-3) was found to chelate Pt Cl42-via the direct N…Pt coordination and the synergistically interlaminar N–H…Cl hydrogen bonds, which was disclosed by the comprehensive analysis of extended X-ray adsorption fine structure(EXAFS) characterizations and density functional theory(DFT) calculations. The unique adsorption mechanism imparts a superior adsorption capacity(168.4 mg g-1)and extraordinary Pt(II) selectivity to SCU-COF-3 under static conditions. In addition, SCU-COF-3 exhibits an upgraded distribution coefficient of 1.62 × 10^(5)mL· g^(-1), one order of magnitude higher than those of reported natural adsorbents. Specifically, SCU-COF-3 can extract PtCl_(4)^(2- )quantitatively from a simulated acidic waste solution coexisting with other 12 competitive ions, suggesting its promising application in practical scenarios.展开更多
MAX phases and its derived two-dimensional MXenes have attracted considerable interest because of their rich structural chemistry and multifunctional applications.Lewis acid molten salt route provides an opportunity f...MAX phases and its derived two-dimensional MXenes have attracted considerable interest because of their rich structural chemistry and multifunctional applications.Lewis acid molten salt route provides an opportunity for structure design and performance manipulation of new MAX phases and MXenes,Although a series of new MAX phases and MXenes were successfully prepared via Lewis acid melt route in recent years,few work is explored on nitride MAX phases and MXenes.Herein,a new copper-based 413-type Ti_(4)CuN_(3)MAX phase was synthesized through isomorphous replacement reaction using Ti_(4)CuN_(3)MAX phase precursor in molten CuCl2.In addition,it was found that at high temperature Ti4N3Clx MXene will transform into two-dimensional cubic TiNa nanosheets with improved structural stability.展开更多
Two-dimensional layered transition metal carbides(MXenes),have huge potential advantage for applications in hydrogen evolution reaction(HER).However,the hindered hydrogen evolution at large current densities and the i...Two-dimensional layered transition metal carbides(MXenes),have huge potential advantage for applications in hydrogen evolution reaction(HER).However,the hindered hydrogen evolution at large current densities and the instability of MXenes during HER remains major challenges.Herein,we report the MoS_(2)/Mo_(2)CT_(x) nanoarray with aerophobic structure via molten salt synthesis.In situ vertical distribution of MoS_(2)nanoarray on the surface of Mo_(2)CT_(x) accelerates hydrogen gas release from the electrode,exhibiting significantly enhanced catalytic activity and stability to bare MoS_(2)and Mo_(2)CT_(x).The MoS_(2)/Mo_(2)CT_(x) nanoarray possesses excellent stability at100 mA/cm^(2)for 100 h with only 3%overpotential increase.Our work provides guidance for developing high-stability MXene-based catalysts by virtue of in situ bonding between nanoarray and MXene.展开更多
In recent years,with the wide applications and mineral exploitation of rare earth elements,their potential environmental and health effects have caused increasing public concern.Effect of rare earth elements La and Yb...In recent years,with the wide applications and mineral exploitation of rare earth elements,their potential environmental and health effects have caused increasing public concern.Effect of rare earth elements La and Yb on the morphological and functional development of zebrafish embryos were studied.The embryos were exposed to La3+ or Yb3+ at 0,0.01,0.1,0.3,0.5 and 1.0 mmol/L,respectively.Early life stage parameters such as egg and embryo mortality,gastrula development,tail detachment,eyes,somite formation,circulatory system,pigmentation,malformations,hatching rate,length of larvae and mortality were investigated.The results showed La3+ and Yb3+ delayed zebrafish embryo and larval development,decreased survival and hatching rates,and caused tail malformation in a concentration-dependent way.Moreover,heavy rare-earth ytterbium led to more severe acute toxicity of zebrafish embryo than light rare-earth lanthanum.展开更多
基金supported by the National Natural Science Foundation of China(Grants No.51902215,91426304,21671195,21805295,51902320,51902319,21875271,and U2004212)the China Postdoctoral Science Foundation(Grant No.2020M680082)+7 种基金the International Partnership Program of Chinese Academy of Sciences(Grants 174433KYSB20190019)the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(Grant No.2019R01003)the Ningbo top-talent team program for financial supportsupport from the Swedish Government Strategic Research Area in Materials Science on Functional Materials at Link?ping University(Faculty Grant SFO Mat LiU No.200900971)support of the electron microscopy laboratory in Link?ping(Grant KAW 2015.0043)an Academy Fellow Grant(P.E.,2020.0196)the Swedish Foundation for Strategic Research(SSF)through project funding(EM16-0004)a Research Infrastructure Fellow Grant(RIF 14-0074)。
文摘MAX phases are gaining attention as precursors of two-dimensional MXenes that are intensively pursued in applications for electrochemical energy storage.Here,we report the preparation of V_(2)SnC MAX phase by the molten salt method.V_(2)SnC is investigated as a lithium storage anode,showing a high gravimetric capacity of 490 mAh g−1 and volumetric capacity of 570 mAh cm^(−3) as well as superior rate performance of 95 mAh g^(−1)(110 mAh cm^(−3))at 50 C,surpassing the ever-reported performance of MAX phase anodes.Sup-ported by operando X-ray diffraction and density functional theory,a charge storage mechanism with dual redox reaction is proposed with a Sn-Li(de)alloying reaction that occurs at the edge sites of V_(2)SnC particles where Sn atoms are exposed to the electrolyte followed by a redox reaction that occurs at V_(2)C layers with Li.This study offers promise of using MAX phases with M-site and A-site elements that are redox active as high-rate lithium storage materials.
基金supported by the National Science Fund for Distinguished Young Scholars(No.21925603)support of the Major Program of the National Natural Science Foundation of China(No.21790373)。
文摘Ni-based metallic foams possessing large specific surfaces and open cell structures are of specific interest as catalysts or catalyst carriers for electrolysis of water.Traditional fabrication of Nickel foam limits the element modification choices to several inert transition metals only on polymer foam precursor and subsequent preparation of foam-based catalysts in aqueous solution or organic electrolyte.To expand the modification horizon,molten salt with wide electrochemical window and fast ion diffusion can achieve the reduction of highly active elements.Herein,we reported is a general and facile method to deposit directly of highly reactive element La and prepare hierarchical honeycomb LaNi_(5) alloy on Ni foam(ho-LaNi_(5)/NF).This self-supporting electrode presents excellent electrical coupling and conductivity between the Ni foam and LaNi_(5),which provides a 3D self-supported heterostructure with outstanding electrocatalytic activity and excellent durability for the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).It exhibits excellent overpotential(1.86 V)comparable to commercial coupled IrO_(2)//Pt/C(1.85 V)at a high current density of 100 m A cm^(-2).This work may pave the way for fabricating novel 3D self-supported honeycomb alloy that can be applied as electrode for usage of clean energy.
基金financially supported by the National Natural Science Foundation of China to Z.Chai(91026000) to D.Wang(91226105)by the CAS Hundred Talents Program to D.Wang(Y2291810S3)
文摘The adsorption of uranyl on hydroxylated α-SiO_2(001) in the presence of a series of anionic ligands, i.e. OH^-, CO_3^(2-), NO_3^-, H_2PO_4^-, HPO_4^(2-),CH_3COO^-(Ac^-), C_6H_5COO^-(PhCO_2^-), C_6H_5O^-(PhO^-), was studied by the periodic density functional theory(DFT) implemented in the Vienna ab initio simulation package(VASP). For the ligands other than OH^-and PhO^-, only the bidentate coordination modes to the uranyl were considered. The excess charge effect of a charged system was first evaluated by constructing models with net charge as is or neutralized by creating defect at the bottom of silica, and the results show that a neutralized model, even with defects, is more realistic than the charged ones.All uranyl species prefer to bind with the deprotonated site(—O^-) rather than the protonated one(—O_H), which suggests that the increase of pH,which leads to the deprotonation of the surface, may enhance the uranyl adsorption. On the other hand, the anionic ligands, which are formed at higher pH, have negative effects. The weaker acidic ligands, such as H_2CO_3, H_3PO_4 and H_2O, whose speciation in solutions is sensitive to the fluctuation of pH, have more complex effect on the uranyl adsorption than strong acids or bases. Humic substances may coordinate with uranyl through carboxyl and phenolic groups, with the carboxyl group bound stronger. The ternary complexes with one bidentate(or monodentate)anion and one(or two) H20 as ligands, which leads to the uranyl penta-coordinated in its equatorial plane, are more favorable than other configurations when bound to the same anionic ligand. Both the charged nature and the coordination behavior of an anionic ligand are relevant to its ability to influence the adsorption of uranyl on the mineral surface. In addition, the uranyl species adsorbed at the surface functionalized by anionic ligands were also addressed, and the functionalized surfaces have weaker interaction with hydrated uranyl dication.
基金This work was supported by the National Natural Science Foundation of China (Major Project No.10490180) Chinese Academy of Sciences (No. KJCX-N01).
文摘OBJECTIVE The antioxidative system in human hepatocellular carcinoma was investigated. METHODS The activities of cytosolic catalase (CAT), superoxide dismu-tase, glutathione peroxidase (GSH-Px), glutathione S-tranferase and levels of reduced glutathione, total protein thiols and malondialdehyde were assayed in 10 cases of hepatocellular carcinoma and adjacent normal liver. RESULTS Hepatoma tissues showed higher activities of CAT, GSH -Px and lower content of total antioxidative capacity compared to adjacent normal liver tissue (P<0.05). CONCLUSION These findings suggest that the antioxidative defense-related enzymes and antioxidants are largely regulated in hepatoma cells. However, the mechanism which is not clear requires further investigation.
基金supported by the Intergovernmental International Cooperation of the National Key R&D Program of China(2022YFE0105300)the National Natural Science Foundation of China(21790374, 22276130, 22176139, 21825601)the New Cornerstone Science Foundation through the XPLORER PRIZE。
文摘The development of adsorbent materials for effective capture of radioactive iodomethane(CH_(3)I) from the off-gas of used nuclear fuel reprocessing, remains a significant and challenging line of research because currently state-of-art adsorbents still suffer from low binding affinity with CH_(3)I. Here, we proposed a brand-new adsorption topological structure by developing a 2D interdigitated layered framework, named SCU-20, featuring slide-like channel with multiple active sites for CH_(3)I capture. The responsive rotating-adaptive aperture of SCU-20 enables the optimal utilization of all active sites within the pore for highly selective recognition and capture of CH_(3)I. A record-breaking CH_(3)I uptake capacity of 1.84 g/g was achieved under static sorption conditions with saturated CH_(3)I vapor. Both experimental and theoretical findings demonstrated that the exceptional uptake of SCU-20 towards CH_(3)I can be attributed to the confined physical electrostatic adsorption of F sites, coupled with the chemical nitrogen methylation reaction with uncoordinated N atoms of pyrazine. Moreover, dynamic CH_(3)I uptake capacity potentially allows for the capture of CH_(3)I in simulated real-world off gas reprocessing conditions. This study highlights the potential of SCU-20 as a promising candidate for efficient capture of iodine species and contributes to the development of effective solutions for radioactive iodine remediation.
基金funding support from the National Key R&D Program of China (grant nos.2021YFB3200400 and 2022YFE0105300)the New Cornerstone Science Foundation through the XPLORER PRIZE,the National Natural Science Foundation of China (grant nos.22276131,21825601,U21A20296,U1967217,12275190,U1932124,and 22206144)+1 种基金the Science Foundation of Jiangsu Province (grant no.BK20220026),the China-Portugal Joint Laboratory of Cultural Heritage Conservation Science (grant no.2021YFE0200100)Soochow University-Western University Centre for Synchrotron Radiation Research.
文摘Developing efficient adsorbents for radon(Rn)capture from the ambient environment is of paramount importance for public health.However,it poses a great challenge due to the chemical inertness and extremely low molar concentration of Rn in air.Herein,we report a zeolite imidazolate frameworkderived metallic carbon adsorbent(Zn@NPC)with record high Rn removal performance under ambient conditions.Upon one-step pyrolysis,the prepared Zn@NPC possesses pores with a preference for Rn and atomically dispersed Zn sites,achieving a high Rn removal efficiency that doubles in adsorption coefficient(9.47 L·g^(−1))and triples in adsorption kinetic coefficient(20.25 mL·g^(−1)·min^(−1))over the benchmark Rn adsorbent coconut activated charcoal.Density functional theory calculations elucidate the important role of the metal polarization effect,which cooperates with the pore size confinement effect to boost the overall Rn adsorption performance.This work launches a promising alternative for practical Rn capture.
基金supported by grants from the National Natural Science Foundation of China(21825601,21790374,21906113,21727801)a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘The second example of tetravalent plutonium carboxyl-based organic framework,^(242)Pu(OH)[PO[(C_(6)H_(4))COO]_(3)]·H_(2)O,termed as PuTPO(TPO=tris(4-carboxylphenyl)-phosphineoxide),was reported in this work.A series of characterizations of PuTPO,such as X-ray crystallography and solid-state UV-Vis-NIR spectroscopy,were carried out to expatiate its structure and physicochemical properties.PuTPO is constructed by dimers of the plutonium-oxygen subunit of[Pu_(2)O_(16)].Characteristic peaks located at approximately 1100 nm can be considered to be the fingerprint peaks of tetravalent plutonium.While PuTPO can maintain high crystallinity within several months after synthesis,it exhibits a radiation-induced swelling effect probed by the expansion of cell parameter of b axis after self-irradiation fromα-decay of ^(242)Pu.This result enriches the inventory of tetravalent plutonium compounds and provides an insight into the irradiation resistance of metal-organic frameworks.
基金supported by the National Natural Science Foundation of China(Nos.U1967216,22076188,U20B2019,21876174)the National Science Fund for Distinguished Young Scholars(No.21925603).
文摘Uranium and molybdenum are important strategic elements. The production of ^(99)Mo and the hydrometallurgical process of uranium ore face difficult problems of separation of uranium and molybdenum.In this study, the four phenanthroline diamide ligands were synthesized, and extraction and stripping experiments were performed under different conditions to evaluate the potential application of these ligands for separation of U(Ⅵ) over Mo(Ⅵ). With the growth of alkyl chain, the solubility of ligands could be greatly improved, and the separation effect of U(Ⅵ) over Mo(Ⅵ) gradually increased. The SF_(U/Mo) were around 10,000 at 4 mol/L HNO3. Three stripping agents were tested with the stripping efficiency of Na_(2)CO_(3)(5%) > H_(2)O > HNO_(3)(0.01 mol/L). The stripping percentages of the three stripping agents were all close to unity, indicating that the ligands had the potential to be recycled. The chemical stoichiometry of U(Ⅵ) complexes with ligands was evaluated as 1:1 using electrospray ionization mass spectrometry,ultraviolet visible spectroscopy and single-crystal X-ray diffraction. The consistency between theoretical calculation and experimental results further explains the coordination mechanism.
基金supported by the National Key R&D Program of China(2021YFB3200400)the National Natural Science Foundation of China(21825601,21790374)+2 种基金the fellowship of China National Postdoctoral Program for Innovative Talents(BX20220223)the fellowship of China Postdoctoral Science Foundation(2022M710103)Jiangsu Postdoctoral Program for Excellence(2022ZB588)。
文摘Post-synthetic functionalization of covalent organic frameworks(COFs)is an alternative way to enhance and broaden their properties and potential applications.However,the chemical functionalization of COFs is a great challenge because traditional procedures are often time-and energy-consuming,while the crystallinity of COFs can be damaged under harsh conditions.Here we report the in-situ introduction of functional graft chains onto the skeleton of COFs during the synthesis process through the combination of radiation-induced synthesis and graft polymerization techniques under ^(60)Co gamma-ray radiation.The synthesis and functionalization of COFs are simultaneously accomplished in a chemical system under ambient conditions yielding a large number of different functionalized COFs.The obtained carboxyl-functionalized COFs exhibit excellent radioactive uranium removal capabilities from aqueous solution with fast uptake dynamics,high adsorption capacity,and excellent selectivity over other competing metal ions.
基金supported by the National Natural Science Foundation of China (21825601, 21790374, U1967217, 21906116, 22176139, 21906114)the National Key R&D Program of China (2018YFB1900203)+2 种基金the Postgraduate Research & Practice Innovation Program of Jiangsu Province (KYCX22_3212)the Postdoctoral Science Foundation of China (2021M692346, 2021M702390)the Foundation of Science and Technology on Surface Physics and Chemistry Laboratory (WDZC202102)
文摘Platinum recovery from waste electrical and electronic equipment(WEEE) in highly acidic solutions is significant to the electronics industry and environmental remediation. However, the lack of ingenious design and synergetic coordination gives rise to unsatisfied PtCl_(4)^(2-)extraction capacities and selectivities in most previously reported adsorbents(e.g., polymeric and inorganic materials). Herein, we proposed a synergistic strategy that realizes highly selective PtCl_(4)^(2-)uptake through first-and second-sphere coordinations. The proof-of-concept imine-linked covalent organic framework(SCU-COF-3) was found to chelate Pt Cl42-via the direct N…Pt coordination and the synergistically interlaminar N–H…Cl hydrogen bonds, which was disclosed by the comprehensive analysis of extended X-ray adsorption fine structure(EXAFS) characterizations and density functional theory(DFT) calculations. The unique adsorption mechanism imparts a superior adsorption capacity(168.4 mg g-1)and extraordinary Pt(II) selectivity to SCU-COF-3 under static conditions. In addition, SCU-COF-3 exhibits an upgraded distribution coefficient of 1.62 × 10^(5)mL· g^(-1), one order of magnitude higher than those of reported natural adsorbents. Specifically, SCU-COF-3 can extract PtCl_(4)^(2- )quantitatively from a simulated acidic waste solution coexisting with other 12 competitive ions, suggesting its promising application in practical scenarios.
基金supported by“Pioneer”and“Leading Goose”R&D Program of Zhejiang(Grant No.2022C01236)National Natural Science Foundation of China(No.52202325,52162020,52172254,U2004212)+3 种基金International Partnership Program of Chinese Academy of Sciences(Grant No.174433KYSB20190019)Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(Grant No.2019R01003)Zhejiang Province Natural Science Foundation of China(No.LQ22E020008)Ningbo Top-talent Team Program,and China Postdoctoral Science Foundation(Grant No.2020M680082).
文摘MAX phases and its derived two-dimensional MXenes have attracted considerable interest because of their rich structural chemistry and multifunctional applications.Lewis acid molten salt route provides an opportunity for structure design and performance manipulation of new MAX phases and MXenes,Although a series of new MAX phases and MXenes were successfully prepared via Lewis acid melt route in recent years,few work is explored on nitride MAX phases and MXenes.Herein,a new copper-based 413-type Ti_(4)CuN_(3)MAX phase was synthesized through isomorphous replacement reaction using Ti_(4)CuN_(3)MAX phase precursor in molten CuCl2.In addition,it was found that at high temperature Ti4N3Clx MXene will transform into two-dimensional cubic TiNa nanosheets with improved structural stability.
基金supported by the National Science Fund for Distinguished Young Scholars(No.21925603)the National Natural Science Foundation of China(No.22176190)the Ningbo Toptalent Team Program(No.2018A610005).
文摘Two-dimensional layered transition metal carbides(MXenes),have huge potential advantage for applications in hydrogen evolution reaction(HER).However,the hindered hydrogen evolution at large current densities and the instability of MXenes during HER remains major challenges.Herein,we report the MoS_(2)/Mo_(2)CT_(x) nanoarray with aerophobic structure via molten salt synthesis.In situ vertical distribution of MoS_(2)nanoarray on the surface of Mo_(2)CT_(x) accelerates hydrogen gas release from the electrode,exhibiting significantly enhanced catalytic activity and stability to bare MoS_(2)and Mo_(2)CT_(x).The MoS_(2)/Mo_(2)CT_(x) nanoarray possesses excellent stability at100 mA/cm^(2)for 100 h with only 3%overpotential increase.Our work provides guidance for developing high-stability MXene-based catalysts by virtue of in situ bonding between nanoarray and MXene.
基金supported by the National Natural Science Foundation of China (No. 10875136,10905062,11005118)the Ministry of Science and Technology of China (No. 2011CB933400)
文摘In recent years,with the wide applications and mineral exploitation of rare earth elements,their potential environmental and health effects have caused increasing public concern.Effect of rare earth elements La and Yb on the morphological and functional development of zebrafish embryos were studied.The embryos were exposed to La3+ or Yb3+ at 0,0.01,0.1,0.3,0.5 and 1.0 mmol/L,respectively.Early life stage parameters such as egg and embryo mortality,gastrula development,tail detachment,eyes,somite formation,circulatory system,pigmentation,malformations,hatching rate,length of larvae and mortality were investigated.The results showed La3+ and Yb3+ delayed zebrafish embryo and larval development,decreased survival and hatching rates,and caused tail malformation in a concentration-dependent way.Moreover,heavy rare-earth ytterbium led to more severe acute toxicity of zebrafish embryo than light rare-earth lanthanum.