Biochar has been widely recognized as a promising solid CO_(2)adsorbent with economic and ecological benefits.Industrial CO_(2)emissions originate from diverse sources,while the pore structure and chemical functional ...Biochar has been widely recognized as a promising solid CO_(2)adsorbent with economic and ecological benefits.Industrial CO_(2)emissions originate from diverse sources,while the pore structure and chemical functional groups of biochar exhibit varying degrees of influence on CO_(2)adsorption and separation performance under different adsorption conditions.Therefore,exploring the matching relationship between the physicochemical properties of biochar and its adsorption and separation performance at different adsorption conditions is essential for the development and optimization of carbon-based adsorbents.This study selected the high-performance extreme gradient boosting(XGB)algorithm from various algorithms and utilized it to develop CO_(2),N_(2),CH_(4)adsorption prediction models.Based on this,coupled prediction models were developed for CO_(2)/N_(2)and CO_(2)/CH_(4)adsorption selectivity.Furthermore,feature importance and partial dependence analysis were performed using SHAP values.The results indicate that during CO_(2)adsorption,the influence of the pore structure of biochar outweighs that of its chemical composition.Specifically,the pore structure of 0.4–0.6 nm is the most important property influencing CO_(2)adsorption at low and medium pressure(0–0.6 bar),and the pore structure of 0.6–0.8 nm,as well as the specific surface area contribute the most at high pressure(0.6–1 bar).During CO_(2)selective separation,the CO_(2)/N_(2)mixture is primarily separated through the selective adsorption of CO_(2)by nitrogen functional groups.In contrast,for CO_(2)/CH_(4)mixtures,pore structure<1 nm plays a more critical role in determining adsorption selectivity.In addition,molecular simulation studies further revealed the adsorption filling mechanisms of CO_(2)molecules within different pore sizes and functional groups.Finally,nitrogen-doped biochar was synthesized using de-alkalize lignin as the precursor,KOH as the activating agent,and urea as the nitrogen dopant.CO_(2),N_(2),and CH_(4)isothermal adsorption experiments were conducted,and the experimental results confirmed that the developed prediction models exhibit high accuracy(R^(2)>0.9).展开更多
The high price and toxicity of ionic liquids(ILs) have limited the design and application of supported ionic liquid membranes(SILMs) for CO_2 separation in both academic and industrial fields. In this work, [Choline][...The high price and toxicity of ionic liquids(ILs) have limited the design and application of supported ionic liquid membranes(SILMs) for CO_2 separation in both academic and industrial fields. In this work, [Choline][Pro]/polyethylene glycol 200(PEG200) mixtures were selected to prepare novel SILMs because of their green and costeffective characterization, and the CO_2/N_2 separation with the prepared SILMs was investigated experimentally at temperatures from 308.15 to 343.15 K. The temperature effect on the permeability, solubility and diffusivity of CO_2 was modeled with the Arrhenius equation. A competitive performance of the prepared SILMs was observed with high CO_2 permeability ranged in 343.3–1798.6 barrer and high CO_2/N_2 selectivity from 7.9 to 34.8.It was also found that the CO_2 permeability increased 3 times by decreasing the viscosity of liquids from 370 to38 m Pa·s. In addition, the inherent mechanism behind the significant permeability enhancement was revealed based on the diffusion-reaction theory, i.e. with the addition of PEG200, the overall resistance was substantially decreased and the SILMs process was switched from diffusion-control to reaction-control.展开更多
Separating oil/water mixtures via superhydrophobic stainless steel mesh(SSM)is a kind of efficient methods of treating oily wastewater,and the superhydrophobic SSM with a low cost,simple fabrication process and robust...Separating oil/water mixtures via superhydrophobic stainless steel mesh(SSM)is a kind of efficient methods of treating oily wastewater,and the superhydrophobic SSM with a low cost,simple fabrication process and robust usability remains a challenge.Herein,urushiol-based benzoxazine(U-D)with a strong substrate adhesion and low surface free energy was used to anchor SiO_(2) particles on the SSM surface to obtain a durable superhydrophobic SSM(PU-D/SiO_(2)/SSM)through a simple dip-coating process,meanwhile,epoxy resin was also introduced to further improve the adhesion between coating and SSM.PU-D/SiO_(2)/SSM could successfully separate various immiscible oil-water mixtures with a separation efficiency of over 96%and a flux up to 27100 L/m^(2) h only by gravity,respectively.Especially,the modified SSM could effectively remove water from water-in-oil emulsion with a separation efficiency of 99.7%.Moreover,PU-D/SiO_(2)/SSM had an outstanding reusability,whose water contact angle and separation efficiency only slightly decreased after 20 cycles of separating oil/water mixture.In addition,the modified SSM also displayed a satisfactory abrasion resistance,chemical stability and self-cleaning property.Thereby,the robust PU-D/SiO_(2)/SSM prepared by cheap raw materials and facile dip-coating method exhibits a high potential for separating oil/water mixtures.展开更多
Removing H_(2)S and CO_(2)is of great significance for natural gas purification.With excellent gas affinity and tunable structure,ionic liquids(ILs) have been regarded as nontrivial candidates for fabricating polymer-...Removing H_(2)S and CO_(2)is of great significance for natural gas purification.With excellent gas affinity and tunable structure,ionic liquids(ILs) have been regarded as nontrivial candidates for fabricating polymer-based membranes.Herein,we firstly reported the incorporation of protic ILs (PILs) having ether-rich and carboxylate sites (ECPILs) into poly(ether-block-amide)(Pebax) matrix for efficient separation H_(2)S and CO_(2)from CH_(4).Notably,the optimal permeability of H_(2)S reaches up to 4310 Barrer (40C,0.50 bar) in Pebax/ECPIL membranes,along with H_(2)S/CH_(4)and (H_(2)StCO_(2))/CH_(4)selectivity of 97.7 and 112.3,respectively.These values are increased by 1125%,160.8%and 145.9%compared to those in neat Pebax membrane.Additionally,the solubility and diffusion coefficients of the gases were measured,demonstrating that ECPIL can simultaneously strengthen the dissolution and diffusion of H_(2)S and CO_(2),thus elevating the permeability and permselectivity.By using quantum chemical calculations and FT-IR spectroscopy,the highly reversible multi-site hydrogen bonding interaction between ECPILs and H_(2)S was revealed,which is responsible for the fast permeation of H_(2)S and good selectivity.Furthermore,H_(2)S/CO_(2)/CH_(4)(3/3/94 mol/mol) ternary mixed gas can be efficiently and stably separated by Pebax/ECPIL membrane for at least 100 h.Overall,this work not only illustrates that PILs with ether-rich and carboxylate hydrogen bonding sites are outstanding materials for simultaneous removal of H_(2)S and CO_(2),but may also provide a novel insight into the design of membrane materials for natural gas upgrading.展开更多
The crisis of excessive increase in CO_(2)emissions has quickly become a serious issue and requires low-cost and bio-compatible solutions.The employee of membrane technology for CO_(2)gas separation has garnered signi...The crisis of excessive increase in CO_(2)emissions has quickly become a serious issue and requires low-cost and bio-compatible solutions.The employee of membrane technology for CO_(2)gas separation has garnered significant interest among researchers.However,this method encounters challenges related to selectivity and permeability.Therefore,modifying and reinforcing the polymer membranes to improve gas separation performance seems essential.Among the various methods for polymer membrane modification,modification with magnesium-based fillers to prepare a mixed matrix membrane(MMM)is considered an efficient method.Owing to magnesium metal's low weight,low density,high strength,and good selectivity,magnesium-based materials(Mg-based materials)have more porosity,higher available surface area,more adsorption sites,lighter weight,and more gas absorption tendency than other fillers,which makes them an attractive choice for the preparation of gas separation MMMs.This research deals with the introduction of Mg-based materials,various methods of synthesis of Mg-based materials,different methods of introducing Mg-based materials into the membrane matrix,and their effect on the performance of MMMs in CO_(2)gas separation applications.Therefore,this review can provide researchers with light horizons in using the high potential of Mg-based materials as efficient fillers in MMMs to achieve excellent permeability and selectivity and generally improve their performance in CO_(2)gas separation applications.展开更多
Due to the similar physicochemical properties of acetylene(C_(2)H_(2))and carbon dioxide(CO_(2)),separating C_(2)H_(2)from a CO_(2)/C_(2)H_(2)mixture poses a significant challenge in the petrochemical industry.Herein,...Due to the similar physicochemical properties of acetylene(C_(2)H_(2))and carbon dioxide(CO_(2)),separating C_(2)H_(2)from a CO_(2)/C_(2)H_(2)mixture poses a significant challenge in the petrochemical industry.Herein,we successfully synthesized a novel SiF_(6)^(2) anion pillared cage metal-organic framework ZNU-15 possessing a new crs topological structure for the selective capture of C_(2)H_(2).As a linear bidentate linker,the fluorinated SiF_(6)^(2) anion partitions the pores into various sized cages.ZNU-15 displays moderate adsorption for C_(2)H_(2)with a capacity of 36.0 cm^(3)g^(-1)at 298 K and 1 bar,which is 2.7 times higher than the CO_(2)uptake.The IAST selectivity of C_(2)H_(2)/CO_(2)for ZNU-15 at 298 K and 100 kPa is 10.5,surpassing that of most reported materials.The Qst values for C_(2)H_(2)and CO_(2)at zero coverage are 54.0 and 42.8 kJ mol^(-1),respectively.Moreover,breakthrough experimental tests show that ZNU-15 is capable of effectively separating C_(2)H_(2)from a C_(2)H_(2)/CO_(2)mixture.Theoretical calculations further indicate that C_(2)H_(2)is preferentially trapped by the small cage with four cooperative hydrogen bonds.展开更多
The production of high-purity H_(2) is the building block of hydrogen economy,which can greatly promote the construction of related technologies and infrastructure.Efficient H_(2)/CH_(4) separation is a necessary unit...The production of high-purity H_(2) is the building block of hydrogen economy,which can greatly promote the construction of related technologies and infrastructure.Efficient H_(2)/CH_(4) separation is a necessary unit in producing high-purity energy and reducing greenhouse gas emissions,which can meet the industrial demand and help to address the energy issue and achieve global carbon neutrality goals.Membrane separation technology,as a promising strategy for H_(2) purification,has attracted much attention due to its high efficiency,energy conservation and versatile applications.This article reviews the latest research advances in the high-performance membranes for H_(2)/CH_(4) separation,and elu-cidates the effect of membrane materials,preparation methods and membrane structure on separation performance from the perspective of separation mechanisms.It also summarized the essential aspects of membrane design,such as microstructural regulation,multiphase coupling,the optimal usage conditions and simple analysis of economic benefits.Finally,the current challenges and future directions of membranes for H_(2)/CH_(4) separation were discussed,intending to provide in-depth reference and inspiration for the theoretical research and practical application of membrane separation technology.展开更多
Achieving efficient adsorption and separation of C_(2)H_(2)/CO_(2)mixtures is a goal that people have always pursued to improve the situation of high energy consumption brought by traditional separation technologies i...Achieving efficient adsorption and separation of C_(2)H_(2)/CO_(2)mixtures is a goal that people have always pursued to improve the situation of high energy consumption brought by traditional separation technologies in industry today.High-nuclearity metal cluster-based MOFs with different functionalities are promising for this separation,but it is a complicated and difficult task to precisely control their structures.The strategy of pore-space partition(PSP)is a powerful way to construct this type MOFs,which has the characteristic of isostructural relationship,and can be resulted in a similar performance for them.Therefore,it is an interesting work to explore the effect of MOFs property by adjusting the size of PSP dividers.Herein,three tetranuclear Cu(Ⅱ)cluster-based MOFs(FJU-112/113/114)with dual functionalities has been successfully obtained by PSP strategy with various lengths of divider units.With the highest microporosity and unique functional site,FJU-114 realized a good improvement in the adsorption and separation performance of C_(2)H_(2)/CO_(2).The gas adsorption and lab-scale C_(2)H_(2)/CO_(2)breakthrough experiments demonstrated that FJU-114 exhibits the highest adsorption uptake of 77 cm^(3)/g for C_(2)H_(2),and shows the best separation factor of 4.2 among three MOFs.The GCMC simulation reveals that a stronger adsorption binding site of C_(2)H_(2)in FJU-114a located in the cage II near the unchanged tetranuclear copper node,combined with its high microporosity to achieve the effect of dual functionalities for the improvement performance of C_(2)H_(2)adsorption and separation.展开更多
Zeolitic imidazole frameworks(ZIFs)are a class of three-dimensional(3D)skeletalmaterials with zeolitic topology composed of metal ions and imidazolium ligands,which combine the advantages of zeolites and metal-organic...Zeolitic imidazole frameworks(ZIFs)are a class of three-dimensional(3D)skeletalmaterials with zeolitic topology composed of metal ions and imidazolium ligands,which combine the advantages of zeolites and metal-organic frameworks.ZIFs are widely used for adsorption of carbon dioxide(CO_(2))from flue gas due to its excellent hydrophobicity,chemical stability,thermal stability and gas adsorption properties.This study focuses on the effects of structures of ZIFs on CO_(2)capture and separation from the viewpoints of topologies,pore channels,ligand functional groups and composite structures.On this basis,the mechanisms of CO_(2)adsorption and selective separation are reviewed,as well as the challenges such as hydrophobicity,thermal and chemical stability faced by ZIFs in practical applications.展开更多
Cooperative coupling of photocatalytic hydrogen peroxide production with organic pollutants degradation has an expansive perspective in energy storage and environmental conservation.Herein,an S-scheme het-erojunction ...Cooperative coupling of photocatalytic hydrogen peroxide production with organic pollutants degradation has an expansive perspective in energy storage and environmental conservation.Herein,an S-scheme het-erojunction is constructed by hybridizing a 3D flower like Schiff-based covalent organic framework(COF)with a porous structure g-C_(3)N_(4),and a comprehensive strategy is proposed to achieve efficient H_(2)O_(2)pro-duction yield coupling highly Rhodamine B(RhB)degradation rate.The charge carrier transfer mechanism is validated by an in-situ X-ray photoelectron spectroscopy,the density functional theory calculation,and a femtosecond transient absorption spectroscopy.Interestingly,the COF/g-C_(3)N_(4)S-scheme heterojunction exhibits better charge separation efficiency compared to bare COF and pure g-C_(3)N_(4),resulting in ameliora-tive photocatalytic activity.In addition,RhB is employed to consume photogenerated holes.Remarkably,2307μmol g^(-1)h^(-1)H_(2)O_(2)achieved over 10%-COF/g-C_(3)N_(4)composite in RhB solution and O_(2)atmosphere,and 100%-RhB degradation rate obtained at 45 min.This work improves a facile strategy to ameliorate SchiffCOF-based S-scheme heterojunction for efficient H_(2)O_(2)production with full hole-electron utilization ability.展开更多
One of the main challenges in oil-water separation of traditional Chinese medicines(TCM)is to obtain essential oils from the aromatic water of TCM.In this study,silicon dioxide/polyvinylidene fluoride(SiO_(2)/PVDF)mem...One of the main challenges in oil-water separation of traditional Chinese medicines(TCM)is to obtain essential oils from the aromatic water of TCM.In this study,silicon dioxide/polyvinylidene fluoride(SiO_(2)/PVDF)membranes were prepared using nonsolvent induce phase separation.Then polydimethylsiloxane(PDMS)was coated to obtain PDMS/SiO_(2/)PVDF membranes.Separated essential oils and water from aromatic water in the gaseous state by vapor permeation membrane separation technology.The relationship between membrane structure and membrane separation effect was investigated.Response surface methodology was used to develop a quadratic model for the separation factor,membrane permeation separation index and membrane preparation process.The optimal process parameters for the membrane separation were 12.31%(mass)concentration of PVDF solution,9.6%(mass)of N,Ndimethylacetamide in the solidification bath,and 0.2 g hydrophobic nano-SiO_(2)incorporation,with a separation factor of 14.45,and a membrane flux of 1203.04 g·m^(-2)·h^(-1).Compared with the PDMS/PVDF membranes,the separation factor and membrane flux were increased by 68.59%and 3.46%,respectively.Compared with the SiO_(2)/PVDF membranes,the separation factor and membrane flux were increased by478%and 79.33%,respectively.Effectively mitigated the limitations of traditional polymer membrane material performance affected by the"trade-off"effect.Attenuated total internal reflection-Fourier transform infrared spectroscopy,contact angle,scanning electron microscopy and energy dispersive spectroscopy were used to characterize the PDMS/SiO_(2)/PVDF membranes,and gas chromatography was used to characterize the permeate.In addition,the contents of L-menthol,L-menthone,menthyl acetate and limonene in the permeate,conformed to the European Pharmacopoeia standards.This study provided an effective preparation strategy of a feasible hydrophobic powder polymer membrane for the separation of essential oils from gaseous peppermint aromatic water.展开更多
The lime-Cu^(2+)-xanthate process is commonly used for the flotation separation of sphalerite from pyrite.In this process,lime is added to the pulp to inhibit the floatability of pyrite.However,the excessive use of li...The lime-Cu^(2+)-xanthate process is commonly used for the flotation separation of sphalerite from pyrite.In this process,lime is added to the pulp to inhibit the floatability of pyrite.However,the excessive use of lime can result in pipeline blockage and inadequate recovery of associated precious metals.Therefore,it is necessary to develop new flotation process that minimizes or eliminates the use of lime.In this paper,a novel Fe^(3+)-Cu^(2+)-butyl xanthate process was developed as an alternative to lime for separating of sphalerite from pyrite.The flotation results indicated that with the artificially-mixed minerals,the flotation recovery of pyrite was lower than 16%and that of sphalerite was higher than 47%at pH 5.0−10.0.The zeta potential measurements revealed that ferric ion preferred to adsorb on pyrite,and copper ion displaced with zinc ion from the lattice at the interface of sphalerite.The wettability analyses indicated that the hydrophobicity of sphalerite surface increased apparently after being treated with Fe^(3+)-Cu^(2+)-BX,while the hydrophobicity of pyrite surface remained nearly unchanged.With XPS analysis,Cu-S bond and hydrophilic ferric hydroxide were detected separately on the surface of sphalerite and pyrite after conditioning with Fe^(3+)-Cu^(2+)-BX,which facilitated the flotation separation of sphalerite from pyrite with butyl xanthate collector.展开更多
In this study,Pebax■2533 polymer was used as the continuous phase and UiO-67 was employed as the filler to prepare mixed matrix membranes.UiO-67 is usually synthesized using two ligands:biphenyl-4,4'-dicarboxylat...In this study,Pebax■2533 polymer was used as the continuous phase and UiO-67 was employed as the filler to prepare mixed matrix membranes.UiO-67 is usually synthesized using two ligands:biphenyl-4,4'-dicarboxylate(bpdc)and 2,2'-bipyridine-5,5'-dicarboxylic acid(bpy).In this research,UiO-67 was synthesized not only with these two ligands but also using a mixed ligand approach(50% bpdc and 50% bpy).The synthesized UiOs were incorporated into the polymer matrix at mass percentages ranging from 0% to 2% to form the mixed matrix membranes(MMMs).Membranes containing UiO-67 with mixed ligands exhibited a greater affinity for CO_(2) compared to other membranes.Various analytical techniques,including X-ray diffraction,thermogravimetric analyzer,Fourier transform infrared spectroscope(FTIR),field emission scanning electron micro scope(FESEM),and differential scanning calorimetry,were used to analyze the properties of the prepared membranes.The FTIR spectrum confirmed all desired bands of Pebax?2533 and UiO-67 in the MMMs.The FESEM images showed that the pure Pebax membrane has a uniform structure,and the developed membranes are uniformly incorporated with the synthesized UiO-67 nanoparticles.Gas permeation measurements indicated that CO_(2) permeability and CO_(2)/CH_4 selectivity increased from 402.7 Barrer(1 Barrer=1.33×10^(-14)m^(3)(STP)·m·m^(-2)·s^(-1)·kPa^(-1))and 9.32 for the pure Pebax membrane at 1.0 MPa to 770.1 Barrer and 16.96 in the modified membrane.Additionally,the gas permeation test results demonstrated that adding functionalized porous nanofillers increases the CO_(2)separation performance.Permeability tests at different temperatures revealed that as temperature was raised,at constant pressure,CO_(2) permeability for the membrane containing the mixed ligand increased from 682.2 Barrer to 733.5 Barrer,While CO_(2)/CH_(4) selectivity decreased from 15.46 to 13.43.展开更多
Simultaneously inducing dual built-in electric fields(EFs)both within a single component and at the heterojunction interface creates a dual-driving force that is crucial for promoting spatial charge separation.This is...Simultaneously inducing dual built-in electric fields(EFs)both within a single component and at the heterojunction interface creates a dual-driving force that is crucial for promoting spatial charge separation.This is particularly significant in challenging coupled systems,such as CO_(2)photoreduction integrated with selective oxidation of toluene to benzaldehyde.However,developing such a system is quite challenging and often requires a precise design and engineering.Herein,we demonstrate a unique Ni-CdS@Ni(OH)_(2)heterojunction synthesized via an in-situ self-assembly method.Comprehensive mechanistic and theoretical investigations reveal that the NiCdS@Ni(OH)_(2)heterojunction induces dual electric fields(EFs):an intrinsic polarized electric-field within the CdS lattice from Ni doping and an interfacial electric-field from the growth of ultrathin nanosheets of Ni(OH)_(2)on NiCdS nanorods,enabling efficient spatial charge separation and enhanced redox potential.As proof of concept,the Ni-CdS@Ni(OH)_(2)heterojunction simultaneously exhibits outstanding bifunctional photocatalytic performance,producing CO at a rate of 427μmol g^(-1)h^(-1)and selectively oxidizing toluene to benzaldehyde at a rate of 1476μmol g^(-1)h^(-1)with a selectivity exceeding 85%.This work offers a promising strategy to optimize the utilization of photogenerated carriers in heterojunction photocatalysts,advancing synergistic photocatalytic redox systems.展开更多
Covalent organic skeletons(COFs)have been widely used in gas separation due to their excellent pore structure,high crystallinity,and high specific surface area.In this work,Dha Tab-COF was synthesized by solvothermal ...Covalent organic skeletons(COFs)have been widely used in gas separation due to their excellent pore structure,high crystallinity,and high specific surface area.In this work,Dha Tab-COF was synthesized by solvothermal method and filled in polyether block polyamide(PEBAX)to form mixed matrix membranes(MMMs).Various characterization methods such as Fourier transform infrared spectroscopy(FT-IR),Xray photoelectron spectroscopy(XPS),scanning electron microscopy(SEM)and X-ray diffractometry(XRD)were used to characterize the structure of Dha Tab-COF as well as the MMMs.The effects of operating pressure,operating temperature and the content of Dha Tab-COF particles on the CO_(2)/CH_(4)separation performance of the membranes were investigated.The best separation performance with a CO_(2)permeability of 295.8 barrer(1 barrer=7.52×10^(-18)m^(3)·(STP)·m^(-2)·m·s^(-1)·Pa^(-1))and a CO_(2)/CH_(4)selectivity of 21.6 was achieved when the Dha Tab-COF content is 2%(mass),which were 45.7%and 108.1%higher than that of the pure PEBAX membrane,respectively.展开更多
基金supported by the Fundamental Research Funds for the Central Universities(No.2025JC008)the National Natural Science Foundation of China(grant number 52176105)+2 种基金the Science and Technology Project of Hebei Education Department-China(BJK2022063)the Hebei Natural Science Foundation-China(grant number E2025502038)the Funding Program for Cultivating Innovative Abilities of Graduate Students in Hebei Province of China(CXZZBS2025184).
文摘Biochar has been widely recognized as a promising solid CO_(2)adsorbent with economic and ecological benefits.Industrial CO_(2)emissions originate from diverse sources,while the pore structure and chemical functional groups of biochar exhibit varying degrees of influence on CO_(2)adsorption and separation performance under different adsorption conditions.Therefore,exploring the matching relationship between the physicochemical properties of biochar and its adsorption and separation performance at different adsorption conditions is essential for the development and optimization of carbon-based adsorbents.This study selected the high-performance extreme gradient boosting(XGB)algorithm from various algorithms and utilized it to develop CO_(2),N_(2),CH_(4)adsorption prediction models.Based on this,coupled prediction models were developed for CO_(2)/N_(2)and CO_(2)/CH_(4)adsorption selectivity.Furthermore,feature importance and partial dependence analysis were performed using SHAP values.The results indicate that during CO_(2)adsorption,the influence of the pore structure of biochar outweighs that of its chemical composition.Specifically,the pore structure of 0.4–0.6 nm is the most important property influencing CO_(2)adsorption at low and medium pressure(0–0.6 bar),and the pore structure of 0.6–0.8 nm,as well as the specific surface area contribute the most at high pressure(0.6–1 bar).During CO_(2)selective separation,the CO_(2)/N_(2)mixture is primarily separated through the selective adsorption of CO_(2)by nitrogen functional groups.In contrast,for CO_(2)/CH_(4)mixtures,pore structure<1 nm plays a more critical role in determining adsorption selectivity.In addition,molecular simulation studies further revealed the adsorption filling mechanisms of CO_(2)molecules within different pore sizes and functional groups.Finally,nitrogen-doped biochar was synthesized using de-alkalize lignin as the precursor,KOH as the activating agent,and urea as the nitrogen dopant.CO_(2),N_(2),and CH_(4)isothermal adsorption experiments were conducted,and the experimental results confirmed that the developed prediction models exhibit high accuracy(R^(2)>0.9).
基金Supported by the National Basic Research Program of China(2013CB733501)the National Natural Science Foundation of China(21136004,21176112,21476106,and21428601)+1 种基金Specialized Research Fund for the Doctoral Program of Higher Education(No.20133221110001)the Project of Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)
文摘The high price and toxicity of ionic liquids(ILs) have limited the design and application of supported ionic liquid membranes(SILMs) for CO_2 separation in both academic and industrial fields. In this work, [Choline][Pro]/polyethylene glycol 200(PEG200) mixtures were selected to prepare novel SILMs because of their green and costeffective characterization, and the CO_2/N_2 separation with the prepared SILMs was investigated experimentally at temperatures from 308.15 to 343.15 K. The temperature effect on the permeability, solubility and diffusivity of CO_2 was modeled with the Arrhenius equation. A competitive performance of the prepared SILMs was observed with high CO_2 permeability ranged in 343.3–1798.6 barrer and high CO_2/N_2 selectivity from 7.9 to 34.8.It was also found that the CO_2 permeability increased 3 times by decreasing the viscosity of liquids from 370 to38 m Pa·s. In addition, the inherent mechanism behind the significant permeability enhancement was revealed based on the diffusion-reaction theory, i.e. with the addition of PEG200, the overall resistance was substantially decreased and the SILMs process was switched from diffusion-control to reaction-control.
基金Funded by the National Natural Science Foundation of China(No.22165019)。
文摘Separating oil/water mixtures via superhydrophobic stainless steel mesh(SSM)is a kind of efficient methods of treating oily wastewater,and the superhydrophobic SSM with a low cost,simple fabrication process and robust usability remains a challenge.Herein,urushiol-based benzoxazine(U-D)with a strong substrate adhesion and low surface free energy was used to anchor SiO_(2) particles on the SSM surface to obtain a durable superhydrophobic SSM(PU-D/SiO_(2)/SSM)through a simple dip-coating process,meanwhile,epoxy resin was also introduced to further improve the adhesion between coating and SSM.PU-D/SiO_(2)/SSM could successfully separate various immiscible oil-water mixtures with a separation efficiency of over 96%and a flux up to 27100 L/m^(2) h only by gravity,respectively.Especially,the modified SSM could effectively remove water from water-in-oil emulsion with a separation efficiency of 99.7%.Moreover,PU-D/SiO_(2)/SSM had an outstanding reusability,whose water contact angle and separation efficiency only slightly decreased after 20 cycles of separating oil/water mixture.In addition,the modified SSM also displayed a satisfactory abrasion resistance,chemical stability and self-cleaning property.Thereby,the robust PU-D/SiO_(2)/SSM prepared by cheap raw materials and facile dip-coating method exhibits a high potential for separating oil/water mixtures.
基金sponsored by the National Natural Science Foundation of China (Nos. 22308145, 22208140, 22178159, 22078145)Natural Science Foundation of Jiangsu Province (BK20230791)Postgraduate Research Innovation Program of Jiangsu Province (KYCX24_0165)。
文摘Removing H_(2)S and CO_(2)is of great significance for natural gas purification.With excellent gas affinity and tunable structure,ionic liquids(ILs) have been regarded as nontrivial candidates for fabricating polymer-based membranes.Herein,we firstly reported the incorporation of protic ILs (PILs) having ether-rich and carboxylate sites (ECPILs) into poly(ether-block-amide)(Pebax) matrix for efficient separation H_(2)S and CO_(2)from CH_(4).Notably,the optimal permeability of H_(2)S reaches up to 4310 Barrer (40C,0.50 bar) in Pebax/ECPIL membranes,along with H_(2)S/CH_(4)and (H_(2)StCO_(2))/CH_(4)selectivity of 97.7 and 112.3,respectively.These values are increased by 1125%,160.8%and 145.9%compared to those in neat Pebax membrane.Additionally,the solubility and diffusion coefficients of the gases were measured,demonstrating that ECPIL can simultaneously strengthen the dissolution and diffusion of H_(2)S and CO_(2),thus elevating the permeability and permselectivity.By using quantum chemical calculations and FT-IR spectroscopy,the highly reversible multi-site hydrogen bonding interaction between ECPILs and H_(2)S was revealed,which is responsible for the fast permeation of H_(2)S and good selectivity.Furthermore,H_(2)S/CO_(2)/CH_(4)(3/3/94 mol/mol) ternary mixed gas can be efficiently and stably separated by Pebax/ECPIL membrane for at least 100 h.Overall,this work not only illustrates that PILs with ether-rich and carboxylate hydrogen bonding sites are outstanding materials for simultaneous removal of H_(2)S and CO_(2),but may also provide a novel insight into the design of membrane materials for natural gas upgrading.
文摘The crisis of excessive increase in CO_(2)emissions has quickly become a serious issue and requires low-cost and bio-compatible solutions.The employee of membrane technology for CO_(2)gas separation has garnered significant interest among researchers.However,this method encounters challenges related to selectivity and permeability.Therefore,modifying and reinforcing the polymer membranes to improve gas separation performance seems essential.Among the various methods for polymer membrane modification,modification with magnesium-based fillers to prepare a mixed matrix membrane(MMM)is considered an efficient method.Owing to magnesium metal's low weight,low density,high strength,and good selectivity,magnesium-based materials(Mg-based materials)have more porosity,higher available surface area,more adsorption sites,lighter weight,and more gas absorption tendency than other fillers,which makes them an attractive choice for the preparation of gas separation MMMs.This research deals with the introduction of Mg-based materials,various methods of synthesis of Mg-based materials,different methods of introducing Mg-based materials into the membrane matrix,and their effect on the performance of MMMs in CO_(2)gas separation applications.Therefore,this review can provide researchers with light horizons in using the high potential of Mg-based materials as efficient fillers in MMMs to achieve excellent permeability and selectivity and generally improve their performance in CO_(2)gas separation applications.
基金supported by the National Natural Science Foundation of China(Nos.22205207 and 22378369)major project of NSF of Zhejiang Province(LD24B060001).
文摘Due to the similar physicochemical properties of acetylene(C_(2)H_(2))and carbon dioxide(CO_(2)),separating C_(2)H_(2)from a CO_(2)/C_(2)H_(2)mixture poses a significant challenge in the petrochemical industry.Herein,we successfully synthesized a novel SiF_(6)^(2) anion pillared cage metal-organic framework ZNU-15 possessing a new crs topological structure for the selective capture of C_(2)H_(2).As a linear bidentate linker,the fluorinated SiF_(6)^(2) anion partitions the pores into various sized cages.ZNU-15 displays moderate adsorption for C_(2)H_(2)with a capacity of 36.0 cm^(3)g^(-1)at 298 K and 1 bar,which is 2.7 times higher than the CO_(2)uptake.The IAST selectivity of C_(2)H_(2)/CO_(2)for ZNU-15 at 298 K and 100 kPa is 10.5,surpassing that of most reported materials.The Qst values for C_(2)H_(2)and CO_(2)at zero coverage are 54.0 and 42.8 kJ mol^(-1),respectively.Moreover,breakthrough experimental tests show that ZNU-15 is capable of effectively separating C_(2)H_(2)from a C_(2)H_(2)/CO_(2)mixture.Theoretical calculations further indicate that C_(2)H_(2)is preferentially trapped by the small cage with four cooperative hydrogen bonds.
基金financially supported by the Strategic Priority Research Program(A)of the Chinese Academy of Sciences(XDA0390000)open research fund of State Key Laboratory of Mesoscience and Engineering(MESO-23-D11).
文摘The production of high-purity H_(2) is the building block of hydrogen economy,which can greatly promote the construction of related technologies and infrastructure.Efficient H_(2)/CH_(4) separation is a necessary unit in producing high-purity energy and reducing greenhouse gas emissions,which can meet the industrial demand and help to address the energy issue and achieve global carbon neutrality goals.Membrane separation technology,as a promising strategy for H_(2) purification,has attracted much attention due to its high efficiency,energy conservation and versatile applications.This article reviews the latest research advances in the high-performance membranes for H_(2)/CH_(4) separation,and elu-cidates the effect of membrane materials,preparation methods and membrane structure on separation performance from the perspective of separation mechanisms.It also summarized the essential aspects of membrane design,such as microstructural regulation,multiphase coupling,the optimal usage conditions and simple analysis of economic benefits.Finally,the current challenges and future directions of membranes for H_(2)/CH_(4) separation were discussed,intending to provide in-depth reference and inspiration for the theoretical research and practical application of membrane separation technology.
基金financially supported by the National Natural Science Foundation of China(Nos.21975044,21971038,21922810 and 22271046)the Fujian Provincial Department of Science and Technology(Nos.2023J01355,2023J011106 and 2022R1022001).
文摘Achieving efficient adsorption and separation of C_(2)H_(2)/CO_(2)mixtures is a goal that people have always pursued to improve the situation of high energy consumption brought by traditional separation technologies in industry today.High-nuclearity metal cluster-based MOFs with different functionalities are promising for this separation,but it is a complicated and difficult task to precisely control their structures.The strategy of pore-space partition(PSP)is a powerful way to construct this type MOFs,which has the characteristic of isostructural relationship,and can be resulted in a similar performance for them.Therefore,it is an interesting work to explore the effect of MOFs property by adjusting the size of PSP dividers.Herein,three tetranuclear Cu(Ⅱ)cluster-based MOFs(FJU-112/113/114)with dual functionalities has been successfully obtained by PSP strategy with various lengths of divider units.With the highest microporosity and unique functional site,FJU-114 realized a good improvement in the adsorption and separation performance of C_(2)H_(2)/CO_(2).The gas adsorption and lab-scale C_(2)H_(2)/CO_(2)breakthrough experiments demonstrated that FJU-114 exhibits the highest adsorption uptake of 77 cm^(3)/g for C_(2)H_(2),and shows the best separation factor of 4.2 among three MOFs.The GCMC simulation reveals that a stronger adsorption binding site of C_(2)H_(2)in FJU-114a located in the cage II near the unchanged tetranuclear copper node,combined with its high microporosity to achieve the effect of dual functionalities for the improvement performance of C_(2)H_(2)adsorption and separation.
基金supported by the Fundamental Research Program of Shanxi Province(Nos.20210302124003 and 20210302124015)the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(No.2021L032)+2 种基金the National Natural Science Foundation of China(No.52103307)China Postdoctoral Science Foundation(No.2023M742575)the General Program of Shanxi Province(No.202203021211150).
文摘Zeolitic imidazole frameworks(ZIFs)are a class of three-dimensional(3D)skeletalmaterials with zeolitic topology composed of metal ions and imidazolium ligands,which combine the advantages of zeolites and metal-organic frameworks.ZIFs are widely used for adsorption of carbon dioxide(CO_(2))from flue gas due to its excellent hydrophobicity,chemical stability,thermal stability and gas adsorption properties.This study focuses on the effects of structures of ZIFs on CO_(2)capture and separation from the viewpoints of topologies,pore channels,ligand functional groups and composite structures.On this basis,the mechanisms of CO_(2)adsorption and selective separation are reviewed,as well as the challenges such as hydrophobicity,thermal and chemical stability faced by ZIFs in practical applications.
基金supported by the National Natural Science Foundation of China(Nos.22409128,22378103,and 52202376)the China Postdoctoral Science Foundation(No.2022TQ0316).
文摘Cooperative coupling of photocatalytic hydrogen peroxide production with organic pollutants degradation has an expansive perspective in energy storage and environmental conservation.Herein,an S-scheme het-erojunction is constructed by hybridizing a 3D flower like Schiff-based covalent organic framework(COF)with a porous structure g-C_(3)N_(4),and a comprehensive strategy is proposed to achieve efficient H_(2)O_(2)pro-duction yield coupling highly Rhodamine B(RhB)degradation rate.The charge carrier transfer mechanism is validated by an in-situ X-ray photoelectron spectroscopy,the density functional theory calculation,and a femtosecond transient absorption spectroscopy.Interestingly,the COF/g-C_(3)N_(4)S-scheme heterojunction exhibits better charge separation efficiency compared to bare COF and pure g-C_(3)N_(4),resulting in ameliora-tive photocatalytic activity.In addition,RhB is employed to consume photogenerated holes.Remarkably,2307μmol g^(-1)h^(-1)H_(2)O_(2)achieved over 10%-COF/g-C_(3)N_(4)composite in RhB solution and O_(2)atmosphere,and 100%-RhB degradation rate obtained at 45 min.This work improves a facile strategy to ameliorate SchiffCOF-based S-scheme heterojunction for efficient H_(2)O_(2)production with full hole-electron utilization ability.
基金supported by the National Natural Science Foundation of China(22478007)the National Key Research and Development Program of China(2022YFB3805100)the Anhui Provincial Natural Science Foundation(2023AH050728)。
文摘One of the main challenges in oil-water separation of traditional Chinese medicines(TCM)is to obtain essential oils from the aromatic water of TCM.In this study,silicon dioxide/polyvinylidene fluoride(SiO_(2)/PVDF)membranes were prepared using nonsolvent induce phase separation.Then polydimethylsiloxane(PDMS)was coated to obtain PDMS/SiO_(2/)PVDF membranes.Separated essential oils and water from aromatic water in the gaseous state by vapor permeation membrane separation technology.The relationship between membrane structure and membrane separation effect was investigated.Response surface methodology was used to develop a quadratic model for the separation factor,membrane permeation separation index and membrane preparation process.The optimal process parameters for the membrane separation were 12.31%(mass)concentration of PVDF solution,9.6%(mass)of N,Ndimethylacetamide in the solidification bath,and 0.2 g hydrophobic nano-SiO_(2)incorporation,with a separation factor of 14.45,and a membrane flux of 1203.04 g·m^(-2)·h^(-1).Compared with the PDMS/PVDF membranes,the separation factor and membrane flux were increased by 68.59%and 3.46%,respectively.Compared with the SiO_(2)/PVDF membranes,the separation factor and membrane flux were increased by478%and 79.33%,respectively.Effectively mitigated the limitations of traditional polymer membrane material performance affected by the"trade-off"effect.Attenuated total internal reflection-Fourier transform infrared spectroscopy,contact angle,scanning electron microscopy and energy dispersive spectroscopy were used to characterize the PDMS/SiO_(2)/PVDF membranes,and gas chromatography was used to characterize the permeate.In addition,the contents of L-menthol,L-menthone,menthyl acetate and limonene in the permeate,conformed to the European Pharmacopoeia standards.This study provided an effective preparation strategy of a feasible hydrophobic powder polymer membrane for the separation of essential oils from gaseous peppermint aromatic water.
基金Project(52204363)supported by the National Natural Science Foundation of ChinaProject(2024JJ8042)supported by the Hunan Natural Science Foundation,ChinaProject(22C0220)supported by the Education Department of Hunan Province,China。
文摘The lime-Cu^(2+)-xanthate process is commonly used for the flotation separation of sphalerite from pyrite.In this process,lime is added to the pulp to inhibit the floatability of pyrite.However,the excessive use of lime can result in pipeline blockage and inadequate recovery of associated precious metals.Therefore,it is necessary to develop new flotation process that minimizes or eliminates the use of lime.In this paper,a novel Fe^(3+)-Cu^(2+)-butyl xanthate process was developed as an alternative to lime for separating of sphalerite from pyrite.The flotation results indicated that with the artificially-mixed minerals,the flotation recovery of pyrite was lower than 16%and that of sphalerite was higher than 47%at pH 5.0−10.0.The zeta potential measurements revealed that ferric ion preferred to adsorb on pyrite,and copper ion displaced with zinc ion from the lattice at the interface of sphalerite.The wettability analyses indicated that the hydrophobicity of sphalerite surface increased apparently after being treated with Fe^(3+)-Cu^(2+)-BX,while the hydrophobicity of pyrite surface remained nearly unchanged.With XPS analysis,Cu-S bond and hydrophilic ferric hydroxide were detected separately on the surface of sphalerite and pyrite after conditioning with Fe^(3+)-Cu^(2+)-BX,which facilitated the flotation separation of sphalerite from pyrite with butyl xanthate collector.
基金Babol Noshirvani University of Technology for financially support of this project(BNUT/393054/2023)。
文摘In this study,Pebax■2533 polymer was used as the continuous phase and UiO-67 was employed as the filler to prepare mixed matrix membranes.UiO-67 is usually synthesized using two ligands:biphenyl-4,4'-dicarboxylate(bpdc)and 2,2'-bipyridine-5,5'-dicarboxylic acid(bpy).In this research,UiO-67 was synthesized not only with these two ligands but also using a mixed ligand approach(50% bpdc and 50% bpy).The synthesized UiOs were incorporated into the polymer matrix at mass percentages ranging from 0% to 2% to form the mixed matrix membranes(MMMs).Membranes containing UiO-67 with mixed ligands exhibited a greater affinity for CO_(2) compared to other membranes.Various analytical techniques,including X-ray diffraction,thermogravimetric analyzer,Fourier transform infrared spectroscope(FTIR),field emission scanning electron micro scope(FESEM),and differential scanning calorimetry,were used to analyze the properties of the prepared membranes.The FTIR spectrum confirmed all desired bands of Pebax?2533 and UiO-67 in the MMMs.The FESEM images showed that the pure Pebax membrane has a uniform structure,and the developed membranes are uniformly incorporated with the synthesized UiO-67 nanoparticles.Gas permeation measurements indicated that CO_(2) permeability and CO_(2)/CH_4 selectivity increased from 402.7 Barrer(1 Barrer=1.33×10^(-14)m^(3)(STP)·m·m^(-2)·s^(-1)·kPa^(-1))and 9.32 for the pure Pebax membrane at 1.0 MPa to 770.1 Barrer and 16.96 in the modified membrane.Additionally,the gas permeation test results demonstrated that adding functionalized porous nanofillers increases the CO_(2)separation performance.Permeability tests at different temperatures revealed that as temperature was raised,at constant pressure,CO_(2) permeability for the membrane containing the mixed ligand increased from 682.2 Barrer to 733.5 Barrer,While CO_(2)/CH_(4) selectivity decreased from 15.46 to 13.43.
基金The authors sincerely appreciate funding from“Producing Hydrogen in Trentino-H2@TN”(PAT-Trento)through the research grant(SAP 40104237)Researchers Supporting Project number(RSP2025R399)King Saud University,Riyadh,Saudi Arabia.
文摘Simultaneously inducing dual built-in electric fields(EFs)both within a single component and at the heterojunction interface creates a dual-driving force that is crucial for promoting spatial charge separation.This is particularly significant in challenging coupled systems,such as CO_(2)photoreduction integrated with selective oxidation of toluene to benzaldehyde.However,developing such a system is quite challenging and often requires a precise design and engineering.Herein,we demonstrate a unique Ni-CdS@Ni(OH)_(2)heterojunction synthesized via an in-situ self-assembly method.Comprehensive mechanistic and theoretical investigations reveal that the NiCdS@Ni(OH)_(2)heterojunction induces dual electric fields(EFs):an intrinsic polarized electric-field within the CdS lattice from Ni doping and an interfacial electric-field from the growth of ultrathin nanosheets of Ni(OH)_(2)on NiCdS nanorods,enabling efficient spatial charge separation and enhanced redox potential.As proof of concept,the Ni-CdS@Ni(OH)_(2)heterojunction simultaneously exhibits outstanding bifunctional photocatalytic performance,producing CO at a rate of 427μmol g^(-1)h^(-1)and selectively oxidizing toluene to benzaldehyde at a rate of 1476μmol g^(-1)h^(-1)with a selectivity exceeding 85%.This work offers a promising strategy to optimize the utilization of photogenerated carriers in heterojunction photocatalysts,advancing synergistic photocatalytic redox systems.
基金supported by the National Natural Science Foundation of China(No.22271022,No 22378327).
文摘Covalent organic skeletons(COFs)have been widely used in gas separation due to their excellent pore structure,high crystallinity,and high specific surface area.In this work,Dha Tab-COF was synthesized by solvothermal method and filled in polyether block polyamide(PEBAX)to form mixed matrix membranes(MMMs).Various characterization methods such as Fourier transform infrared spectroscopy(FT-IR),Xray photoelectron spectroscopy(XPS),scanning electron microscopy(SEM)and X-ray diffractometry(XRD)were used to characterize the structure of Dha Tab-COF as well as the MMMs.The effects of operating pressure,operating temperature and the content of Dha Tab-COF particles on the CO_(2)/CH_(4)separation performance of the membranes were investigated.The best separation performance with a CO_(2)permeability of 295.8 barrer(1 barrer=7.52×10^(-18)m^(3)·(STP)·m^(-2)·m·s^(-1)·Pa^(-1))and a CO_(2)/CH_(4)selectivity of 21.6 was achieved when the Dha Tab-COF content is 2%(mass),which were 45.7%and 108.1%higher than that of the pure PEBAX membrane,respectively.
