Isotopic separation is of paramount importance for producing high-purity heavy hydrogen,yet the process remains hugely challenging.Here,we report on an Fe/ZSM-5 zeolite that was able to efficiently separate deuterium ...Isotopic separation is of paramount importance for producing high-purity heavy hydrogen,yet the process remains hugely challenging.Here,we report on an Fe/ZSM-5 zeolite that was able to efficiently separate deuterium from protium via chemical quantum sieving.Structural data showed that four types of Fe species were present in Fe/ZSM-5 and oligomeric Fe-O clusters in the zeolite pores were correlated directly with gas selectivity.Gas adsorption revealed that Fe-O species served as the main adsorption sites and interacted with D_(2) more strongly than with H_(2).D_(2)/H_(2)separation was exemplified using thermal desorption spectroscopy.D_(2)/H_(2) selectivity increased with Fe loading in Fe/ZSM-5 and a selectivity of 32.1 was obtained with an optimal loading of 7 wt%.The shift of desorption temperature supports the chemical affinity-based quantum sieving of D_(2)over H_(2).This study demonstrates an effective strategy for enhancing D_(2)/H_(2) separation and the high selectivity means that Fe/ZSM-5 has strong potential in hydrogen isotope separation.展开更多
Hydrogen isotope separation is a challenging task due to their similar properties.Herein,based on the chemical affinity quantum sieve(CAQS)effect,the D_(2)/H_(2)separation performance of M_(2)(m-dobdc)(M=Co,Ni,Mg,Mn;m...Hydrogen isotope separation is a challenging task due to their similar properties.Herein,based on the chemical affinity quantum sieve(CAQS)effect,the D_(2)/H_(2)separation performance of M_(2)(m-dobdc)(M=Co,Ni,Mg,Mn;m-dobdc^(4-)=4,6-dioxido-1,3-benzenedicarboxylate),a series of honeycomb-shaped MOFs with high stability and abundant open metal sites,are studied by gases sorption and breakthrough experiments,in which two critical factors,gas uptake and adsorption enthalpy,are taken into consideration.Among these MOFs,Co_(2)(m-dobdc)exhibits the longest D_(2)retention time of 180 min/g(H_(2)/D_(2)/Ne:1/1/98)at 77 K because of its second-highest adsorption enthalpy(10.7 kJ/mol for H_(2)and 11.8 kJ/mol for D_(2))and the best sorption capacity(5.22 mmol/g for H_(2)and 5.49 mmol/g for D_(2))under low pressure of 1 kPa and 77 K,which make it a promising material for industrial hydrogen isotope separation.Moreover,the results indicate that H_(2)and D_(2)capacities under low pressure(about 1 kPa)dominate the final D_(2)/H_(2)separation property of MOFs.展开更多
The synthesis of nanoporous materials that display a combination of molecular sieving(MS)and quantum sieving(QS)effects is still a challenging task.In this work,we have demonstrated the synthesis of a nanocaged metal...The synthesis of nanoporous materials that display a combination of molecular sieving(MS)and quantum sieving(QS)effects is still a challenging task.In this work,we have demonstrated the synthesis of a nanocaged metal–organic framework(MOF),ECUT-8,that has a dual-sieving capability.ECUT-8 afforded H_(2)/D_(2) isotope separation due to its extremely narrow window size(3.0Å),resulting in QS.Further,the framework flexibility of ECUT-8 was exploited for the separation of butane and hexane isomers due to its MS effect.Other desirable features of ECUT-8 include high thermal,water,and chemical stability,making it suitable for practical application.Herein,these results open up an avenue to design the effects of coexistence of multiple sieving in one material.展开更多
基金supported by the National Natural Science Foundation of China(22375031,22131004,U21A20330)the National Key R&D Program of China(2022YFB3805902)+2 种基金the“111”Program(B18012)Jilin Natural Science Fund for Excellent Young Scholars(20230508116RC)the Fundamental Research Funds for the Central Universities(JGPY202103,2412023YQ001)。
文摘Isotopic separation is of paramount importance for producing high-purity heavy hydrogen,yet the process remains hugely challenging.Here,we report on an Fe/ZSM-5 zeolite that was able to efficiently separate deuterium from protium via chemical quantum sieving.Structural data showed that four types of Fe species were present in Fe/ZSM-5 and oligomeric Fe-O clusters in the zeolite pores were correlated directly with gas selectivity.Gas adsorption revealed that Fe-O species served as the main adsorption sites and interacted with D_(2) more strongly than with H_(2).D_(2)/H_(2)separation was exemplified using thermal desorption spectroscopy.D_(2)/H_(2) selectivity increased with Fe loading in Fe/ZSM-5 and a selectivity of 32.1 was obtained with an optimal loading of 7 wt%.The shift of desorption temperature supports the chemical affinity-based quantum sieving of D_(2)over H_(2).This study demonstrates an effective strategy for enhancing D_(2)/H_(2) separation and the high selectivity means that Fe/ZSM-5 has strong potential in hydrogen isotope separation.
基金financially supported by the Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB20000000)the Key Research Program of Frontier Sciences,Chinese Academy of Sciences(No.QYZDB-SSW-SLH019)the National Natural Science Foundation of China(Nos.21771177,51603206 and 21203117).
文摘Hydrogen isotope separation is a challenging task due to their similar properties.Herein,based on the chemical affinity quantum sieve(CAQS)effect,the D_(2)/H_(2)separation performance of M_(2)(m-dobdc)(M=Co,Ni,Mg,Mn;m-dobdc^(4-)=4,6-dioxido-1,3-benzenedicarboxylate),a series of honeycomb-shaped MOFs with high stability and abundant open metal sites,are studied by gases sorption and breakthrough experiments,in which two critical factors,gas uptake and adsorption enthalpy,are taken into consideration.Among these MOFs,Co_(2)(m-dobdc)exhibits the longest D_(2)retention time of 180 min/g(H_(2)/D_(2)/Ne:1/1/98)at 77 K because of its second-highest adsorption enthalpy(10.7 kJ/mol for H_(2)and 11.8 kJ/mol for D_(2))and the best sorption capacity(5.22 mmol/g for H_(2)and 5.49 mmol/g for D_(2))under low pressure of 1 kPa and 77 K,which make it a promising material for industrial hydrogen isotope separation.Moreover,the results indicate that H_(2)and D_(2)capacities under low pressure(about 1 kPa)dominate the final D_(2)/H_(2)separation property of MOFs.
基金supported financially by the National Natural Science Foundations of China(nos.21966002,21871047,and 21861017)the Natural Science Foundation of Jiangxi Province of China(no.20181ACB20003)the Training Program for Academic and Technical Leaders of Major Disciplines in Jiangxi Province(no.20194BCJ22010).
文摘The synthesis of nanoporous materials that display a combination of molecular sieving(MS)and quantum sieving(QS)effects is still a challenging task.In this work,we have demonstrated the synthesis of a nanocaged metal–organic framework(MOF),ECUT-8,that has a dual-sieving capability.ECUT-8 afforded H_(2)/D_(2) isotope separation due to its extremely narrow window size(3.0Å),resulting in QS.Further,the framework flexibility of ECUT-8 was exploited for the separation of butane and hexane isomers due to its MS effect.Other desirable features of ECUT-8 include high thermal,water,and chemical stability,making it suitable for practical application.Herein,these results open up an avenue to design the effects of coexistence of multiple sieving in one material.
