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
A new paradigm to remove toxic chromate anions from aqueous solution by crystallization of chromatewater clusters with imine-linked guanidinium cationic ligands is introduced.The guanidium-based cationic ligand was ea...A new paradigm to remove toxic chromate anions from aqueous solution by crystallization of chromatewater clusters with imine-linked guanidinium cationic ligands is introduced.The guanidium-based cationic ligand was easily prepared through the imine condensation of an alde hyde and aminoguanidine hydrochloride.The cationic imine-linked guanidinium liga nd(BBIG-CI)showed a high re moval capacity(292.5 mg/g)in the solutions.Rapid decontamination of chromate anions from the wastewater by this cationic ligand was resulted from an instantaneous crystallization.The produced guanidium chromate salts have an extremely low solubility(Ksp,BBIG=8.19×10^9).Such superior removal performance of these mate rials was attributed to the cha rge-assisted hydrogen bonding between the cationic ligand and chromate-water hydrate anions,which was revealed by the single-crystal X-ray diffraction analysis and density functional theory(DFT)calculations.In addition,the succes s ful recove ry of the guanidium-based ligand makes it more attractive for real-world applications.展开更多
Effective remediation of radioactive IO3−is highly desirable for fuel reprocessing,medical waste disposal,and nuclear accidents.However,the nature of high solubility,strong mobility,and extremely hard to bind with min...Effective remediation of radioactive IO3−is highly desirable for fuel reprocessing,medical waste disposal,and nuclear accidents.However,the nature of high solubility,strong mobility,and extremely hard to bind with minerals for IO3−makes this task an enormous challenge.Herein,a metal-organic framework material[Ce(IV)-MOF-808]with available Ce(IV)sites was used to efficiently remove IO3−.Ce(IV)-MOF-808 exhibits superior selectivity and one of the highest adsorption capacities(623 mg·g^(-1))for IO3−removal.Moreover,Ce(IV)-MOF-808 shows great adsorption performance for IO3−at low concentrations,and the distribution coefficient(Kd)value was calculated to be 2.60×10^(6)mL·g^(-1).The exceptional IO3−uptake performance is attributed to the high affinity between Ce(IV)cluster and the oxyanion based on the comprehensive analysis of zeta potential and X-ray photoelectron spectroscopy(XPS)results,in which IO3−can easily replace the weakly coordinated ligand and form a strong coordination structure of Ce-O-I-O2.More importantly,Ce(IV)-MOF-808 exhibits excellent uptake performance for IO3−from both the simulated Beishan groundwater system and Hanford groundwater system in the dynamic column separation test,indicating the highly promising practical application of Ce(IV)-MOF-808 in IO3−remediation from actual radioactive wastes.展开更多
Efficient removal of trace radiostrontium from contaminated highly saline wastewater,such as seawater,remains a critical but challenging task due to the coexistence of large excess of hard cations like Na^(+),K^(+),Mg...Efficient removal of trace radiostrontium from contaminated highly saline wastewater,such as seawater,remains a critical but challenging task due to the coexistence of large excess of hard cations like Na^(+),K^(+),Mg^(2+)and particularly Ca^(2+),which shares similar physicochemical properties with Sr2+.Herein,we successfully boosted the selectivity by a sulfhydryl-functionalized NaA zeolite(SH-NaA)via ion exchange coupled with reinforced soft-soft interactions between sulfhydryl groups and Sr2+.Remarkably,SH-NaA achieved a 99.8%removal efficiency of Sr2+in the presence of a tenfold excess of Ca^(2+),with a distribution coefficient(Kd)of 4.98×10^(5)mL/g.The effectiveness of SH-NaA in accurately capturing Sr2+was further validated by its superior dynamic adsorption performance in natural seawater compared to pristine NaA zeolite.Batch experiments highlighted SH-NaA’s exceptional Sr2+removal efficiency(qm=233.36 mg/g),rapid adsorption kinetics(1 min),superior decontamination depth(Kd=6.71×10^(5)mL/g),and robust irradiation stability(400 kGyγ-ray).X-ray photoelectron spectroscopy(XPS)and in situ Fouriertransform infrared(FTIR)analyses underscored the pivotal role of sulfhydryl groups in Sr2+capture.Density functional theory(DFT)calculations revealed that the sulfhydryl-functionalized NaA zeolite exhibits the best selectivity toward Sr2+,with an interaction energy of-2.55 eV.These findings demonstrate that organic group functionalized zeolites hold significant promise for environmental remediation applications.展开更多
As a class of functional crystalline porous materials,metal-organic frameworks(MOFs)gained rapid development in the past three decades and a large number of MOFs with ordered structures,high surface areas,and function...As a class of functional crystalline porous materials,metal-organic frameworks(MOFs)gained rapid development in the past three decades and a large number of MOFs with ordered structures,high surface areas,and functionalized channels have been investigated.MOFs and MOF-derived/composite materials show great potential in many application fields.In this review,we discussed the main applications of MOFs and MOF-derived/composite materials in small molecule storage,separation,luminescence,sensing,multitype catalysis,and energy storage.In addition,challenges and problems in the future research of MOFs-related fields are also discussed.展开更多
Efficient segregation of TcO_(4)^(-)from high-level radioactive wastes(HLW)is critical for robust nuclear waste management and environmental protection.However,achieving deep decontamination is especially challenging ...Efficient segregation of TcO_(4)^(-)from high-level radioactive wastes(HLW)is critical for robust nuclear waste management and environmental protection.However,achieving deep decontamination is especially challenging in complex conditions of strong basicity,high radiation,and excessively competitive anions.Herein,we addressed the long-term challenge by modifying the imidazolium core with phenyl,trimethylphenyl,and benzyl groups in a flexible polymer chain,which constructs a precisely targeted microenvironment for selective TcO_(4)^(-)capture.This custom-engineered material(SCU-CPN-7)exhibits fast kinetics,high adsorption capacity(314.7 mg/g),excellent distribution coefficient(1.3×10^(7) mL/g),and remarkable efficiency in TcO_(4)^(-)uptake under the combining extreme conditions of strong alkalinity(1 M NaOH)and high radioactivity.More importantly,owing to the synergistic effects of the hydrophobic effect,electrostatic affinity,and p-πinteractions,SCU-CPN-7 demonstrates exceptional selectivity,capable of almost quantificationally removing TcO_(4)^(-)in the coexistence of a large excess of NO_(3)^(-)and SO_(4)^(2-),leading to an unparalleled uptake performance of TcO_(4)^(-)from simulated HLW in both batch and dynamic column separation tests.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
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
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
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the National Natural Science Foundation of China(Nos.21790374,21825601,U1732112,21876124)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)the Fundamental Research Funds for the Central Universities(No.2019QNA4047)。
文摘A new paradigm to remove toxic chromate anions from aqueous solution by crystallization of chromatewater clusters with imine-linked guanidinium cationic ligands is introduced.The guanidium-based cationic ligand was easily prepared through the imine condensation of an alde hyde and aminoguanidine hydrochloride.The cationic imine-linked guanidinium liga nd(BBIG-CI)showed a high re moval capacity(292.5 mg/g)in the solutions.Rapid decontamination of chromate anions from the wastewater by this cationic ligand was resulted from an instantaneous crystallization.The produced guanidium chromate salts have an extremely low solubility(Ksp,BBIG=8.19×10^9).Such superior removal performance of these mate rials was attributed to the cha rge-assisted hydrogen bonding between the cationic ligand and chromate-water hydrate anions,which was revealed by the single-crystal X-ray diffraction analysis and density functional theory(DFT)calculations.In addition,the succes s ful recove ry of the guanidium-based ligand makes it more attractive for real-world applications.
基金supported by the Intergovernmental International Cooperation of the National Key R&D Program of China(2022YFE0105300)the National Key R&D Program of China (2021YFB3200400)+5 种基金the National Natural Science Foundation of China (22306136, 22425061, 22176139, U2267222, and U1967217)the China National Postdoctoral Program for Innovative Talents (BX2021206)the China Postdoctoral Science Foundation (2021M702390)the Natural Science Foundation of Jiangsu (BK20230510)the New Cornerstone Science Foundation through the XPLORER PRIZEthe Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)
文摘Effective remediation of radioactive IO3−is highly desirable for fuel reprocessing,medical waste disposal,and nuclear accidents.However,the nature of high solubility,strong mobility,and extremely hard to bind with minerals for IO3−makes this task an enormous challenge.Herein,a metal-organic framework material[Ce(IV)-MOF-808]with available Ce(IV)sites was used to efficiently remove IO3−.Ce(IV)-MOF-808 exhibits superior selectivity and one of the highest adsorption capacities(623 mg·g^(-1))for IO3−removal.Moreover,Ce(IV)-MOF-808 shows great adsorption performance for IO3−at low concentrations,and the distribution coefficient(Kd)value was calculated to be 2.60×10^(6)mL·g^(-1).The exceptional IO3−uptake performance is attributed to the high affinity between Ce(IV)cluster and the oxyanion based on the comprehensive analysis of zeta potential and X-ray photoelectron spectroscopy(XPS)results,in which IO3−can easily replace the weakly coordinated ligand and form a strong coordination structure of Ce-O-I-O2.More importantly,Ce(IV)-MOF-808 exhibits excellent uptake performance for IO3−from both the simulated Beishan groundwater system and Hanford groundwater system in the dynamic column separation test,indicating the highly promising practical application of Ce(IV)-MOF-808 in IO3−remediation from actual radioactive wastes.
基金supported by the National Natural Science Foundation of China(22425061,22176139,22203023,22206144,22306136,U2267222,and U1967217)the Natural Science Foundation of Guangdong Province(2022A1515011859)+3 种基金the Postdoctoral Science Foundation of China(BX20230252,2023M742538)the Natural Science Foundation of Jiangsu Province(BK20230510)the Open Project of State Key Laboratory of Environment-friendly Energy Materials(22kfhg02)the New Cornerstone Science Foundation through the XPLORER PRIZE。
文摘Efficient removal of trace radiostrontium from contaminated highly saline wastewater,such as seawater,remains a critical but challenging task due to the coexistence of large excess of hard cations like Na^(+),K^(+),Mg^(2+)and particularly Ca^(2+),which shares similar physicochemical properties with Sr2+.Herein,we successfully boosted the selectivity by a sulfhydryl-functionalized NaA zeolite(SH-NaA)via ion exchange coupled with reinforced soft-soft interactions between sulfhydryl groups and Sr2+.Remarkably,SH-NaA achieved a 99.8%removal efficiency of Sr2+in the presence of a tenfold excess of Ca^(2+),with a distribution coefficient(Kd)of 4.98×10^(5)mL/g.The effectiveness of SH-NaA in accurately capturing Sr2+was further validated by its superior dynamic adsorption performance in natural seawater compared to pristine NaA zeolite.Batch experiments highlighted SH-NaA’s exceptional Sr2+removal efficiency(qm=233.36 mg/g),rapid adsorption kinetics(1 min),superior decontamination depth(Kd=6.71×10^(5)mL/g),and robust irradiation stability(400 kGyγ-ray).X-ray photoelectron spectroscopy(XPS)and in situ Fouriertransform infrared(FTIR)analyses underscored the pivotal role of sulfhydryl groups in Sr2+capture.Density functional theory(DFT)calculations revealed that the sulfhydryl-functionalized NaA zeolite exhibits the best selectivity toward Sr2+,with an interaction energy of-2.55 eV.These findings demonstrate that organic group functionalized zeolites hold significant promise for environmental remediation applications.
基金supported by the National Key Research and Development Program of China(2022YFA1502901)the National Natural Science Foundation of China(22035003,22201137,22371137)the Fundamental Research Funds for the Central Universities(63243115)。
文摘As a class of functional crystalline porous materials,metal-organic frameworks(MOFs)gained rapid development in the past three decades and a large number of MOFs with ordered structures,high surface areas,and functionalized channels have been investigated.MOFs and MOF-derived/composite materials show great potential in many application fields.In this review,we discussed the main applications of MOFs and MOF-derived/composite materials in small molecule storage,separation,luminescence,sensing,multitype catalysis,and energy storage.In addition,challenges and problems in the future research of MOFs-related fields are also discussed.
基金supported by the National Natural Science Foundation of China(22306136,22176139,22425061,22406137,U2267222,U1967217,12305397)the Natural Science Foundation of Jiangsu(BK20230510)+2 种基金the Sichuan Science and Technology Program(2024YFCY0006)the New Cornerstone Science Foundation through the XPLORER PRIZEthe Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)。
文摘Efficient segregation of TcO_(4)^(-)from high-level radioactive wastes(HLW)is critical for robust nuclear waste management and environmental protection.However,achieving deep decontamination is especially challenging in complex conditions of strong basicity,high radiation,and excessively competitive anions.Herein,we addressed the long-term challenge by modifying the imidazolium core with phenyl,trimethylphenyl,and benzyl groups in a flexible polymer chain,which constructs a precisely targeted microenvironment for selective TcO_(4)^(-)capture.This custom-engineered material(SCU-CPN-7)exhibits fast kinetics,high adsorption capacity(314.7 mg/g),excellent distribution coefficient(1.3×10^(7) mL/g),and remarkable efficiency in TcO_(4)^(-)uptake under the combining extreme conditions of strong alkalinity(1 M NaOH)and high radioactivity.More importantly,owing to the synergistic effects of the hydrophobic effect,electrostatic affinity,and p-πinteractions,SCU-CPN-7 demonstrates exceptional selectivity,capable of almost quantificationally removing TcO_(4)^(-)in the coexistence of a large excess of NO_(3)^(-)and SO_(4)^(2-),leading to an unparalleled uptake performance of TcO_(4)^(-)from simulated HLW in both batch and dynamic column separation tests.
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 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.
