The adsorptive separation of C_(2)H_(4)and C_(2)H_(6),as an alternative to distillation units consuming high energy,is a promising yet challenging research.The great similarity in the molecular size of C_(2)H_(4)and C...The adsorptive separation of C_(2)H_(4)and C_(2)H_(6),as an alternative to distillation units consuming high energy,is a promising yet challenging research.The great similarity in the molecular size of C_(2)H_(4)and C_(2)H_(6)brings challenges to the regulation of adsorbents to realize efficient dynamic separation.Herein,we reported the enhancement of the kinetic separation of C_(2)H_(4)/C_(2)H_(6)by controlling the crystal size of ZnAtzPO_(4)(Atz=3-amino-1,2,4-triazole)to amplify the diffusion difference of C_(2)H_(4)and C_(2)H_(6).Through adjusting the synthesis temperature,reactant concentration,and ligands/metal ions molar ratio,ZnAtzPO4 crystals with different sizes were obtained.Both single-component kinetic adsorption tests and binary-component dynamic breakthrough experiments confirmed the enhancement of the dynamic separation of C_(2)H_(4)/C_(2)H_(6)with the increase in the crystal size of ZnAtzPO_(4).The separation selectivity of C_(2)H_(4)/C_(2)H_(6)increased from 1.3 to 98.5 with the increase in the crystal size of ZnAtzPO_(4).This work demonstrated the role of morphology and size control of adsorbent crystals in the improvement of the C_(2)H_(4)/C_(2)H_(6)kinetic separation performance.展开更多
Carbon peaking and carbon neutralization trigger a technical revolution in energy&environment related fields.Development of new technologies for green energy production and storage,industrial energy saving and eff...Carbon peaking and carbon neutralization trigger a technical revolution in energy&environment related fields.Development of new technologies for green energy production and storage,industrial energy saving and efficiency reinforcement,carbon capture,and pollutant gas treatment is in highly imperious demand.The emerging porous framework materials such as metal–organic frameworks(MOFs),covalent organic frameworks(COFs)and hydrogen-bonded organic frameworks(HOFs),owing to the permanent porosity,tremendous specific surface area,designable structure and customizable functionality,have shown great potential in major energy-consuming industrial processes,including sustainable energy gas catalytic conversion,energy-efficient industrial gas separation and storage.Herein,this manuscript presents a systematic review of porous framework materials for global and comprehensive energy&environment related applications,from a macroscopic and application perspective.展开更多
Light hydrocarbons(C1–C4) are fundamental raw materials in the petroleum and chemical industry. Separation and purification of structurally similar paraffin/olefin/alkyne mixtures are important for the production of ...Light hydrocarbons(C1–C4) are fundamental raw materials in the petroleum and chemical industry. Separation and purification of structurally similar paraffin/olefin/alkyne mixtures are important for the production of highpurity or even polymer-grade light hydrocarbons. However, traditional methods such as cryogenic distillation and solvent absorption are energy-intensive and environmentally unfriendly processes. Ionic liquids(ILs) as a new alternative to organic solvents have been proposed as promising green media for light hydrocarbon separation due to their unique tunable structures and physicochemical properties resulting from the variations of the cations and anions such as low volatility, high thermal stability, large liquidus range, good miscibility with light hydrocarbons, excellent molecular recognition ability and adjustable hydrophylicity/hydrophobicity. In this review, the recent progresses on the light hydrocarbon separation using ILs are summarized, and some parameters of ILs that influence the separation performance are discussed.展开更多
Trans-/cis-olefin isomers play a vital role in the petrochemical industry.The paucity of energy-efficient technologies for their splitting is mainly due to the similarities of their physicochemical properties.Herein,t...Trans-/cis-olefin isomers play a vital role in the petrochemical industry.The paucity of energy-efficient technologies for their splitting is mainly due to the similarities of their physicochemical properties.Herein,two new tailor-made anion-pillared ultramicroporous metal–organic frameworks(MOFs),ZU-36-Ni and ZU-36-Fe(GeFSIX-3-Ni and GeFSIX-3-Fe)are reported for the first time for the efficient trans-/cis-2-butene(trans-/cis-C_(4)H_(8))mixture splitting by enhanced molecular exclusion.Notably,ZU-36-Ni unexpectedly exhibited smart guest-adaptive pore channels for trapping trans-C_(4)H_(8)with a remarkable adsorption capacity(2.45 mmol∙g^(−1))while effectively rejecting cis-C_(4)H_(8)with a high purity of 99.99%.The dispersion-corrected density functional theory(DFT-D)calculation suggested that the guest-adaptive behavior of ZU-36-Ni in response to trans-C_(4)H_(8)is derived from the organic linker rotation and the optimal pore dimensions,which not only improve the favorable adsorption/diffusion of trans-C_(4)H_(8)with optimal host–guest interactions,but also enhance the size-exclusion of cis-C_(4)H_(8).This work opens a new avenue for pore engineering in advanced smart or adaptive porous materials for specific applications involving guest molecular recognition.展开更多
With the increasing demand for synthetic rubber,the purification of 1,3-butadiene(C_(4)H_(6))is of great industrial significance.Herein,the successful removal of n-butene(n-C_(4)H_(8))and iso-butene(iso-C_(4)H_(8))fro...With the increasing demand for synthetic rubber,the purification of 1,3-butadiene(C_(4)H_(6))is of great industrial significance.Herein,the successful removal of n-butene(n-C_(4)H_(8))and iso-butene(iso-C_(4)H_(8))from 1,3-butadiene(C_(4)H_(6))was realized by synthesizing a novel TaOF_(5)^(2-) anion-pillared ultramicroporous material TaOFFIVE-3-Ni(also referred to as ZU-96,TaOFFIVE=TaOF_(5)^(2-),3=pyrazine).Single-component adsorption isotherms show that TaOFFIVE-3-Ni can achieve the exclusion of n-C_(4)H_(8) and iso-C_(4)H_(8) in the low pressure region(0–30 kPa),and uptake C_(4)H_(6) with a high capacity of 92.78 cm^(3)·cm^(-3)(298 K and 100 kPa).The uptake ratio of C_(4)H_(6)/iso-C_(4)H_(8) on TaOFFIVE-3-Ni was 20.83(298 K and 100 kPa),which was the highest among the state-of-the-art adsorbents reported so far.With the rotation of anion and pyrazine ring,the pore size changes continuously,which makes smaller-size C_(4)H_(6) enter the channel while larger-size n-C_(4)H_(8) and iso-C_(4)H_(8) are completely blocked.The excellent breakthrough performance of TaOFFIVE-3-Ni shows great potential in industrial separation of C4 olefins.The specific adsorption binding sites within ZU-96 was further revealed through the modeling calculation.展开更多
We have successfully prepared a series of Pd- Ni/TiO2 catalysts by a one-step impregnation-reduction method. Among these catalysts with different compositions of Ni and Pd, the one with the Ni:Pd ratio of 2.95 showed...We have successfully prepared a series of Pd- Ni/TiO2 catalysts by a one-step impregnation-reduction method. Among these catalysts with different compositions of Ni and Pd, the one with the Ni:Pd ratio of 2.95 showed the best activity. Small monodispersed Pd-Ni bimetallic nanoparticles were loaded on the surface of titanium oxide nanopowder as confirmed with TEM and EDS mapping. The XPS analysis demonstrated that Pd exists as 31% Pd(II) species and 69% Pd(0) species and all nickel is Ni(II). The prepared Pd-Ni/TiO2 exhibited enhanced catalytic activity compared to an equal amount of Pd/TiO2 for Suzuki-Miyaura reactions together with excellent applicability and reusability.展开更多
C5 olefin separation is of great importance and challenge in industry with the increasing demand for synthetic rubber.However,the related study is limited due to the complex compositions and the similar boiling points...C5 olefin separation is of great importance and challenge in industry with the increasing demand for synthetic rubber.However,the related study is limited due to the complex compositions and the similar boiling points.Here,we for the first time employ two anionpillared hybrid porous materials(ZU-62 and TIFSIX-2-Cu-i)towards the challenging separation of C5 olefin mixtures(trans-2-pentene,1-pentene and isoprene).These two adsorbents not only exhibit the unprecedented separation performance,but also show excellent recycle performance.Owing to the favorable electrostatic environment within a suitable confined space,TIFSIX-2-Cu-i is able to distinguish the three C5 olefins(frans-2-pentene,1-pentene and isoprene)with a high uptake of trans-2-pentene(3.1mmgol·g^(-1))ZU-62(also termed as NbOFFIVE-2-Cu-i)with contracted aperture size shows exclusion effect to the relatively large molecule of isoprene at low pressure range(0-6 kPa),contributing to the excellent separation selectivity of 1-pentene/isoprene(300).The excellent separation performance of ZU-62 and TIFSIX-2-Cu-i is verified by the breakthrough experiment.And interestingly,the regeneration tests show that C5 olefins can be easily desorbed from ZU-62,TIFSIX-2-Cu-i under 298 K.Moreover,the detailed adsorption behavior is further revealed by simulation studies.展开更多
Adsorptive separation of acetylene/carbon dioxide mixtures by porous materials is an important and challenging task due to their similar sizes and physical properties.Here,remarkable acetylene/carbon dioxide separatio...Adsorptive separation of acetylene/carbon dioxide mixtures by porous materials is an important and challenging task due to their similar sizes and physical properties.Here,remarkable acetylene/carbon dioxide separation featuring a high dynamic breakthrough capacity for acetylene(4.3 mmol·g^(–1))as well as an ultralow acetylene regeneration energy(29.5 kJ·mol^(–1))was achieved with the novel TiF_(6)^(2–)-pillared material ZU-100(TIFSIX-bpy-Ni).Construction of a pore structure with abundant TiF_(6)^(2–)anion sites and pores with appropriate sizes enabled formation of acetylene clusters through hydrogen bonds and intermolecular interactions,which afforded a high acetylene capacity(8.3 mmol·g^(–1))and high acetylene/carbon dioxide uptake ratio(1.9)at 298 K and 1 bar.Moreover,the NbO_(5)^(2–)anion-pillared material ZU-61 investigated for separation of acetylene/carbon dioxide.In addition,breakthrough experiments were also conducted to further confirm the excellent dynamic acetylene/carbon dioxide separation performance of ZU-100.展开更多
基金supported by the National Key Research and Development Program of China(2022YFB3806800)the National Natural Science Foundation of China(22122811,22008209)the Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering(2021SZ-TD008).
文摘The adsorptive separation of C_(2)H_(4)and C_(2)H_(6),as an alternative to distillation units consuming high energy,is a promising yet challenging research.The great similarity in the molecular size of C_(2)H_(4)and C_(2)H_(6)brings challenges to the regulation of adsorbents to realize efficient dynamic separation.Herein,we reported the enhancement of the kinetic separation of C_(2)H_(4)/C_(2)H_(6)by controlling the crystal size of ZnAtzPO_(4)(Atz=3-amino-1,2,4-triazole)to amplify the diffusion difference of C_(2)H_(4)and C_(2)H_(6).Through adjusting the synthesis temperature,reactant concentration,and ligands/metal ions molar ratio,ZnAtzPO4 crystals with different sizes were obtained.Both single-component kinetic adsorption tests and binary-component dynamic breakthrough experiments confirmed the enhancement of the dynamic separation of C_(2)H_(4)/C_(2)H_(6)with the increase in the crystal size of ZnAtzPO_(4).The separation selectivity of C_(2)H_(4)/C_(2)H_(6)increased from 1.3 to 98.5 with the increase in the crystal size of ZnAtzPO_(4).This work demonstrated the role of morphology and size control of adsorbent crystals in the improvement of the C_(2)H_(4)/C_(2)H_(6)kinetic separation performance.
基金the financial support from the National Natural Science Foundation of China(22090062,21922810,21825802,22138003,22108083,and 21725603)the Guangdong Pearl River Talents Program(2021QN02C8)+3 种基金the Science and Technology Program of Guangzhou(202201010118)Zhejiang Provincial Natural Science Foundation of China(LR20B060001)National Science Fund for Excellent Young Scholars(22122811)China Postdoctoral Science Foundation(2022M710123)。
文摘Carbon peaking and carbon neutralization trigger a technical revolution in energy&environment related fields.Development of new technologies for green energy production and storage,industrial energy saving and efficiency reinforcement,carbon capture,and pollutant gas treatment is in highly imperious demand.The emerging porous framework materials such as metal–organic frameworks(MOFs),covalent organic frameworks(COFs)and hydrogen-bonded organic frameworks(HOFs),owing to the permanent porosity,tremendous specific surface area,designable structure and customizable functionality,have shown great potential in major energy-consuming industrial processes,including sustainable energy gas catalytic conversion,energy-efficient industrial gas separation and storage.Herein,this manuscript presents a systematic review of porous framework materials for global and comprehensive energy&environment related applications,from a macroscopic and application perspective.
基金Supported by the National Natural Science Foundation of China(No.21725603)Zhejiang Provincial Natural Science Foundation of China(LZ18B060001)the National Program for Support of Top-notch Young Professionals(H.X.)
文摘Light hydrocarbons(C1–C4) are fundamental raw materials in the petroleum and chemical industry. Separation and purification of structurally similar paraffin/olefin/alkyne mixtures are important for the production of highpurity or even polymer-grade light hydrocarbons. However, traditional methods such as cryogenic distillation and solvent absorption are energy-intensive and environmentally unfriendly processes. Ionic liquids(ILs) as a new alternative to organic solvents have been proposed as promising green media for light hydrocarbon separation due to their unique tunable structures and physicochemical properties resulting from the variations of the cations and anions such as low volatility, high thermal stability, large liquidus range, good miscibility with light hydrocarbons, excellent molecular recognition ability and adjustable hydrophylicity/hydrophobicity. In this review, the recent progresses on the light hydrocarbon separation using ILs are summarized, and some parameters of ILs that influence the separation performance are discussed.
基金supported by the Zhejiang Provincial Natural Science Foundation of China (LZ18B060001)the National Natural Science Foundation of China (21725603, 21476192, and U1862110)
文摘Trans-/cis-olefin isomers play a vital role in the petrochemical industry.The paucity of energy-efficient technologies for their splitting is mainly due to the similarities of their physicochemical properties.Herein,two new tailor-made anion-pillared ultramicroporous metal–organic frameworks(MOFs),ZU-36-Ni and ZU-36-Fe(GeFSIX-3-Ni and GeFSIX-3-Fe)are reported for the first time for the efficient trans-/cis-2-butene(trans-/cis-C_(4)H_(8))mixture splitting by enhanced molecular exclusion.Notably,ZU-36-Ni unexpectedly exhibited smart guest-adaptive pore channels for trapping trans-C_(4)H_(8)with a remarkable adsorption capacity(2.45 mmol∙g^(−1))while effectively rejecting cis-C_(4)H_(8)with a high purity of 99.99%.The dispersion-corrected density functional theory(DFT-D)calculation suggested that the guest-adaptive behavior of ZU-36-Ni in response to trans-C_(4)H_(8)is derived from the organic linker rotation and the optimal pore dimensions,which not only improve the favorable adsorption/diffusion of trans-C_(4)H_(8)with optimal host–guest interactions,but also enhance the size-exclusion of cis-C_(4)H_(8).This work opens a new avenue for pore engineering in advanced smart or adaptive porous materials for specific applications involving guest molecular recognition.
基金supported by Natural Science Foundation of Zhejiang Province(LR20B060001 and LZ18B060001)the National Natural Science Foundation of China(21725603,21938011),the Entrepreneur Team Introduction Program of Zhejiang(2019R01006)the Research Computing Center in College of Chemical and Biological Engineering at Zhejiang University.
文摘With the increasing demand for synthetic rubber,the purification of 1,3-butadiene(C_(4)H_(6))is of great industrial significance.Herein,the successful removal of n-butene(n-C_(4)H_(8))and iso-butene(iso-C_(4)H_(8))from 1,3-butadiene(C_(4)H_(6))was realized by synthesizing a novel TaOF_(5)^(2-) anion-pillared ultramicroporous material TaOFFIVE-3-Ni(also referred to as ZU-96,TaOFFIVE=TaOF_(5)^(2-),3=pyrazine).Single-component adsorption isotherms show that TaOFFIVE-3-Ni can achieve the exclusion of n-C_(4)H_(8) and iso-C_(4)H_(8) in the low pressure region(0–30 kPa),and uptake C_(4)H_(6) with a high capacity of 92.78 cm^(3)·cm^(-3)(298 K and 100 kPa).The uptake ratio of C_(4)H_(6)/iso-C_(4)H_(8) on TaOFFIVE-3-Ni was 20.83(298 K and 100 kPa),which was the highest among the state-of-the-art adsorbents reported so far.With the rotation of anion and pyrazine ring,the pore size changes continuously,which makes smaller-size C_(4)H_(6) enter the channel while larger-size n-C_(4)H_(8) and iso-C_(4)H_(8) are completely blocked.The excellent breakthrough performance of TaOFFIVE-3-Ni shows great potential in industrial separation of C4 olefins.The specific adsorption binding sites within ZU-96 was further revealed through the modeling calculation.
基金Acknowledgements We are grateful for financial support from the National Key R&D Program of China (Grant No. 2016YFA0202900), the National Natural Science Foundation of China (Grant Nos. 21376212 and 21436010).
文摘We have successfully prepared a series of Pd- Ni/TiO2 catalysts by a one-step impregnation-reduction method. Among these catalysts with different compositions of Ni and Pd, the one with the Ni:Pd ratio of 2.95 showed the best activity. Small monodispersed Pd-Ni bimetallic nanoparticles were loaded on the surface of titanium oxide nanopowder as confirmed with TEM and EDS mapping. The XPS analysis demonstrated that Pd exists as 31% Pd(II) species and 69% Pd(0) species and all nickel is Ni(II). The prepared Pd-Ni/TiO2 exhibited enhanced catalytic activity compared to an equal amount of Pd/TiO2 for Suzuki-Miyaura reactions together with excellent applicability and reusability.
基金the Zhejiang Provincial Natural Science Foundation of China(No.LR20B060001)the Key Research and Development Program of Ningxia(No.2018BDE02057)+1 种基金the National Natural Science Foundation of China(No.U1862110,21938011)Zhejiang University Academic Award for Out-standing Doctoral Candidates,and the Research Computing Center in College of Chemical and Biological Engineering at Zhejiang University.The single-crystal X-ray diffraction data of TIFSIX-2-Cu-i have been deposited in the Cambridge Crystallographic Data Centre under accession num ber CCDC:1857691.
文摘C5 olefin separation is of great importance and challenge in industry with the increasing demand for synthetic rubber.However,the related study is limited due to the complex compositions and the similar boiling points.Here,we for the first time employ two anionpillared hybrid porous materials(ZU-62 and TIFSIX-2-Cu-i)towards the challenging separation of C5 olefin mixtures(trans-2-pentene,1-pentene and isoprene).These two adsorbents not only exhibit the unprecedented separation performance,but also show excellent recycle performance.Owing to the favorable electrostatic environment within a suitable confined space,TIFSIX-2-Cu-i is able to distinguish the three C5 olefins(frans-2-pentene,1-pentene and isoprene)with a high uptake of trans-2-pentene(3.1mmgol·g^(-1))ZU-62(also termed as NbOFFIVE-2-Cu-i)with contracted aperture size shows exclusion effect to the relatively large molecule of isoprene at low pressure range(0-6 kPa),contributing to the excellent separation selectivity of 1-pentene/isoprene(300).The excellent separation performance of ZU-62 and TIFSIX-2-Cu-i is verified by the breakthrough experiment.And interestingly,the regeneration tests show that C5 olefins can be easily desorbed from ZU-62,TIFSIX-2-Cu-i under 298 K.Moreover,the detailed adsorption behavior is further revealed by simulation studies.
基金This work was financially supported by the Zhejiang Provincial Natural Science Foundation of China(Grant No.LR20B060001)the National Natural Science Foundation of China(Grant Nos.22122811,21938011,and 21890764)the Research Computing Center in College of Chemical and Biological Engineering at Zhejiang University.
文摘Adsorptive separation of acetylene/carbon dioxide mixtures by porous materials is an important and challenging task due to their similar sizes and physical properties.Here,remarkable acetylene/carbon dioxide separation featuring a high dynamic breakthrough capacity for acetylene(4.3 mmol·g^(–1))as well as an ultralow acetylene regeneration energy(29.5 kJ·mol^(–1))was achieved with the novel TiF_(6)^(2–)-pillared material ZU-100(TIFSIX-bpy-Ni).Construction of a pore structure with abundant TiF_(6)^(2–)anion sites and pores with appropriate sizes enabled formation of acetylene clusters through hydrogen bonds and intermolecular interactions,which afforded a high acetylene capacity(8.3 mmol·g^(–1))and high acetylene/carbon dioxide uptake ratio(1.9)at 298 K and 1 bar.Moreover,the NbO_(5)^(2–)anion-pillared material ZU-61 investigated for separation of acetylene/carbon dioxide.In addition,breakthrough experiments were also conducted to further confirm the excellent dynamic acetylene/carbon dioxide separation performance of ZU-100.