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
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
Efficient adsorption of gaseous radioiodine is pivotal for the sustainable development of nuclear energy and the long-termradiation safety of the ecological system.However,state-of-the-art adsorbents(e.g.metal-organic...Efficient adsorption of gaseous radioiodine is pivotal for the sustainable development of nuclear energy and the long-termradiation safety of the ecological system.However,state-of-the-art adsorbents(e.g.metal-organic frameworks and covalent-organic frameworks)currently under exploration suffer severely from limited adsorption capacity,especially under a real-world scenariowith extremely lowradioiodine concentration and elevated temperature.This mostly originates from the relatively weak sorption driving forces mainly determinedby the iodine-adsorbent interaction consistingof noncovalent interactionswith a small fraction of strong chemical bonding.Here,we document the discovery of an open metal-sulfide framework((NH_(4))_(2)(Sn_(3)S_(7)),donated as SCU-SnS)constructed by three different types of active sites as a superior iodine adsorbent.Benefiting from the ability of iodine for pre-enrichment into the framework by charge-balancing NH_(4)^(+)through N-H···I interaction,the efficient reduction of I^(2)affording I^(-)by S^(2-),and extremely high binding affinity between Sn_(4)^(+)and I^(-),SCU-SnS exhibit a record-breaking iodine adsorption capacity(2.12 g/g)under dynamic breakthrough conditions and the highest static capacity(6.12 g/g)among all reported inorganic adsorbents,both at 348 K.Its facile synthesis and low cost endow SCU-SnS with powerful application potential for the nuclear industry.展开更多
Separation of the minor actinides(Am and Cm)from lanthanides in high-level liquid wastes(HLLW)is one of the most challenging chemical separation tasks known owing to their chemical similarities and is highly significa...Separation of the minor actinides(Am and Cm)from lanthanides in high-level liquid wastes(HLLW)is one of the most challenging chemical separation tasks known owing to their chemical similarities and is highly significant in nuclear fuel reprocessing plants because it could practically lead to sustainable nuclear energy by closing the nuclear fuel cycle.The solid phase extraction is proposed to be a possible strategy but all reported sorbent materials severely suffer from limited stability and/or efficiency caused by the harsh conditions of high acidity coupled with intense irradiation.Herein,a phenanthroline-based polymeric organic framework(PhenTAPB-POF)was designed and tested for the separation of trivalent americium from lanthanides for the first time.Due to its fully conjugated structure,PhenTAPB-POF exhibits previously unachieved stability under the combined extreme conditions of strong acids and high irradiation field.The americium partitioning experiment indicates that PhenTAPB-POF possesses an ultrahigh adsorption selectivity towards Am(Ⅲ)over lanthanides(e.g.,SFAm(Ⅲ)/Eu(Ⅲ)=3326)in highly acidic simulated HLLW and relatively fast adsorption kinetics in both static and dynamic experiments.Am(Ⅲ)can be almost quantitatively eluted from the PhenTAPB-POF packed-column using a concentrated nitric acid elution.The high stability and superior separation performance endow PhenTAPB-POF with the promising alternative for separating minor actinides over lanthanides from highly acidic HLLW streams.展开更多
Technetium-99m(^(99m)Tc)is the most used(>80%)radionuclide in the clinical nuclear diagnostic imaging procedure.The traditional approach to preparing ^(99m)Tc-based imaging agents utilizes stannous chloride(SnCl_(2...Technetium-99m(^(99m)Tc)is the most used(>80%)radionuclide in the clinical nuclear diagnostic imaging procedure.The traditional approach to preparing ^(99m)Tc-based imaging agents utilizes stannous chloride(SnCl_(2))for the reduction of noncomplexing pertechnetate(^(99m)TcO_(4)^(−))to low-valent Tc[e.g.,Tc(IV)].This process,however,is difficult to control precisely and usually results in toxic SnCl_(2) residue and remaining 99mTc(VII),both of which are destructive to humans.Herein,we report a new strategy for preparing^(99m)TcO_(4)^(−)-labeled agents without adding any reductants.The deliberately designed nanoscale cationic polymeric network(SCU-CPN-3)shows excellent affinity for^(99m)TcO_(4)^(−)even at trace levels originating from the strong p-πinteraction with^(99m)TcO_(4)^(−).Impressively,record-fast labeling kinetics are observed,where almost quantitative labeling efficacy(>96%)can be achieved within 1 min,giving rise to a short labeling time and simple operation using a clinical kit.Both single-photon emission computed tomography(SPECT)images and ex vivo biodistribution of different tumor model analyses verify the potential feasibility of this strategy for tumor imaging.展开更多
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)+2 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 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The authors gratefully acknowledge the financial support from the National Key R&D Program of China(grant nos.2021YFB3200400 and 2018YFB1900203)the National Natural Science Foundation of China(grant nos.21825601,21790374,22176139,21906113,and 22176163)+2 种基金the Young Taishan Scholars Program(grant no.tsqn201909082)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(grant no.KYCX22_3212)This work is dedicated to Prof.Zhifang Chai on the occasion of his 80th birthday.
文摘Efficient adsorption of gaseous radioiodine is pivotal for the sustainable development of nuclear energy and the long-termradiation safety of the ecological system.However,state-of-the-art adsorbents(e.g.metal-organic frameworks and covalent-organic frameworks)currently under exploration suffer severely from limited adsorption capacity,especially under a real-world scenariowith extremely lowradioiodine concentration and elevated temperature.This mostly originates from the relatively weak sorption driving forces mainly determinedby the iodine-adsorbent interaction consistingof noncovalent interactionswith a small fraction of strong chemical bonding.Here,we document the discovery of an open metal-sulfide framework((NH_(4))_(2)(Sn_(3)S_(7)),donated as SCU-SnS)constructed by three different types of active sites as a superior iodine adsorbent.Benefiting from the ability of iodine for pre-enrichment into the framework by charge-balancing NH_(4)^(+)through N-H···I interaction,the efficient reduction of I^(2)affording I^(-)by S^(2-),and extremely high binding affinity between Sn_(4)^(+)and I^(-),SCU-SnS exhibit a record-breaking iodine adsorption capacity(2.12 g/g)under dynamic breakthrough conditions and the highest static capacity(6.12 g/g)among all reported inorganic adsorbents,both at 348 K.Its facile synthesis and low cost endow SCU-SnS with powerful application potential for the nuclear industry.
基金supported by the grants from the National Natural Science Foundation of China(Nos.21825601,21790374,and 21806117)。
文摘Separation of the minor actinides(Am and Cm)from lanthanides in high-level liquid wastes(HLLW)is one of the most challenging chemical separation tasks known owing to their chemical similarities and is highly significant in nuclear fuel reprocessing plants because it could practically lead to sustainable nuclear energy by closing the nuclear fuel cycle.The solid phase extraction is proposed to be a possible strategy but all reported sorbent materials severely suffer from limited stability and/or efficiency caused by the harsh conditions of high acidity coupled with intense irradiation.Herein,a phenanthroline-based polymeric organic framework(PhenTAPB-POF)was designed and tested for the separation of trivalent americium from lanthanides for the first time.Due to its fully conjugated structure,PhenTAPB-POF exhibits previously unachieved stability under the combined extreme conditions of strong acids and high irradiation field.The americium partitioning experiment indicates that PhenTAPB-POF possesses an ultrahigh adsorption selectivity towards Am(Ⅲ)over lanthanides(e.g.,SFAm(Ⅲ)/Eu(Ⅲ)=3326)in highly acidic simulated HLLW and relatively fast adsorption kinetics in both static and dynamic experiments.Am(Ⅲ)can be almost quantitatively eluted from the PhenTAPB-POF packed-column using a concentrated nitric acid elution.The high stability and superior separation performance endow PhenTAPB-POF with the promising alternative for separating minor actinides over lanthanides from highly acidic HLLW streams.
基金supported by the Intergovernmental International Cooperation of the National Key R&D Program of China(grant no.2022YFE0105300)the National Natural Science Foundation of China(grant nos.21825601,22306136,21790374,22176139,and 22206144)+4 种基金the China National Postdoctoral Program for Innovative Talents(grant no.BX2021206)the China Postdoctoral Science Foundation(grant no.2021M702390)the Natural Science Foundation of Jiangsu(grant no.BK20230510)the National Key R&D Program of China(grant no.2018YFB1900203)the New Cornerstone Science Foundation through the XPLORER PRIZE.
文摘Technetium-99m(^(99m)Tc)is the most used(>80%)radionuclide in the clinical nuclear diagnostic imaging procedure.The traditional approach to preparing ^(99m)Tc-based imaging agents utilizes stannous chloride(SnCl_(2))for the reduction of noncomplexing pertechnetate(^(99m)TcO_(4)^(−))to low-valent Tc[e.g.,Tc(IV)].This process,however,is difficult to control precisely and usually results in toxic SnCl_(2) residue and remaining 99mTc(VII),both of which are destructive to humans.Herein,we report a new strategy for preparing^(99m)TcO_(4)^(−)-labeled agents without adding any reductants.The deliberately designed nanoscale cationic polymeric network(SCU-CPN-3)shows excellent affinity for^(99m)TcO_(4)^(−)even at trace levels originating from the strong p-πinteraction with^(99m)TcO_(4)^(−).Impressively,record-fast labeling kinetics are observed,where almost quantitative labeling efficacy(>96%)can be achieved within 1 min,giving rise to a short labeling time and simple operation using a clinical kit.Both single-photon emission computed tomography(SPECT)images and ex vivo biodistribution of different tumor model analyses verify the potential feasibility of this strategy for tumor imaging.
