The separation of gas molecules with similar physicochemical properties is of high importance but practically entails a substantial energy penalty in chemical industry. Meanwhile, clean energy gases such as H_2 and CH...The separation of gas molecules with similar physicochemical properties is of high importance but practically entails a substantial energy penalty in chemical industry. Meanwhile, clean energy gases such as H_2 and CH_4 are considered as promising candidates for the replacement of traditional fossil fuels. However, the technologies for the storage of these gases are still immature. In addition, the release of anthropogenic toxic gases into the atmosphere is a worldwide threat of growing concern. Both in academia and industry, considerable research efforts have been devoted to developing advanced porous materials for the effective and energy-efficient separation, storage, or capture of the related gases. In contrast to conventional inorganic porous materials such as zeolites and activated carbons, metal–organic frameworks(MOFs) are considered as a type of promising materials for gas separation and storage. In this contribution, we review the recent research advance of MOFs in some relevant applications, including CO_2 capture, O_2 purification, separation of light hydrocarbons, separation of noble gases, storage of gases(CH_4,H_2, and C_2 H_2) for energy, and removal of some gaseous air pollutants(NH_3, NO_2, and SO_2). Finally, an outlook regarding the challenges of the future research of MOFs in these directions is given.展开更多
Short-chain perfluorocarboxylic acids(PFCAs) are a class of persistent organic pollutants that are widely used as substitutes for long-chain PFCAs. However, they also pose a non-negligible risk to ecosystems. In this ...Short-chain perfluorocarboxylic acids(PFCAs) are a class of persistent organic pollutants that are widely used as substitutes for long-chain PFCAs. However, they also pose a non-negligible risk to ecosystems. In this study, we demonstrated that a fluorescent metal–organic framework(MOF)(named V-101) constructed from In^(3+)and an aromatic-rich tetratopic carboxylate ligand 5-[2,6-bis(4-carboxyphenyl) pyridin-4-yl] isophthalic acid(H4BCPIA) exhibited highly efficient turn-off and turn-on fluorescence responses toward five short-chain PFCAs in water and methanol, respectively. The limits of detection of V-101 toward five short-chain PFCAs are down to μg/L level, and it showed good anti-interference abilities toward short-chain PFCAs in the presence of common metal ions. The major mechanisms associated with fluorescence responses were molecular collisions and interactions between V-101 and short-chain PFCAs. This work demonstrates that the structure variety of MOFs imparts them with the potential of MOFs in the detection of short-chain PFCAs for pollution control.展开更多
Under the context of carbon neutrality of China,it is urgent to shift our energy supply towards cleaner fuels as well as to reduce the greenhouse gas emission.Currently,coal is the main fossil fuel energy source of Ch...Under the context of carbon neutrality of China,it is urgent to shift our energy supply towards cleaner fuels as well as to reduce the greenhouse gas emission.Currently,coal is the main fossil fuel energy source of China.The country is striving hard to replace it with methane,a cleaner fossil fuel.Although China has rich geological resources of methane as coal bed methane(CBM)reserves,it is quite challenging to utilize them due to low concentration.The CBM is however mainly emitted directly to atmosphere during coal mining,causing waste of the resource and huge contribution to greenhouse effect.The recent work by Yang et al.demonstrated a potential solution to extract low concentration methane selectively from CBM through using MOF materials as sorbents.Such kind of materials and associated separation technology are promising to reduce greenhouse gas emission and promote the methane production capability,which would contribute to carbon neutrality in dual pathways.展开更多
The separation of aromatic/aliphatic hydrocarbon mixtures is a significant process in chemical industry, but challenged in some cases. Compared with conventional separation technologies, pervaporation is quite promisi...The separation of aromatic/aliphatic hydrocarbon mixtures is a significant process in chemical industry, but challenged in some cases. Compared with conventional separation technologies, pervaporation is quite promising in terms of its economical, energy-saving, and eco-friendly advantages. However, this technique has not been used in industry for separating aromatic/aliphatic mixtures yet. One of the main reasons is that the separation performance of existed pervaporation membranes is unsatisfactory. Membrane material is an important factor that affects the separation performance. This review provides an overview on the advances in studying membrane materials for the pervaporation separation of aromatic/aliphatic mixtures over the past decade. Explored pristine polymers and their hybrid materials(as hybrid membranes) are summarized to highlight their nature and separation performance. We anticipate that this review could provide some guidance in the development of new materials for the aromatic/aliphatic pervaporation separation.展开更多
Two new metal-organic frameworks（MOFs）,[Cu2（H_2O）_2（BCPIA）]（BUT-20）and（Me_2NH_2）[In（BCPIA）]（BUT-21）were designed and synthesized through the solvothermal reaction between a newly created desymmetric 4-co...Two new metal-organic frameworks（MOFs）,[Cu2（H_2O）_2（BCPIA）]（BUT-20）and（Me_2NH_2）[In（BCPIA）]（BUT-21）were designed and synthesized through the solvothermal reaction between a newly created desymmetric 4-connected ligand,5-（2,6-bis（4-carboxyphenyl）pyridin-4-yl）isophthalic acid（H_4BCPIA）and Cu（NO_3）2 2.5H_2O or In（NO_3）_3·5H_2O,respectively,and characterized by single-crystal and powder Xray diffraction,thermogravimetric analysis,infrared spectroscopy,and elemental analysis.The two MOFs have three-dimensional structures,in which both the BCPIA 4 ligand and metal-containing entities,Cu_2（COO）_4（H_2O）_2 and In（COO）_4 act as 4-connected nodes.However,different linkage configurations of the two metal-containing nodes,quadrilateral Cu_2_TD_2（COO）_4（H_2O）_2and tetrahedral In（COO）_4,lead to distinct structural networks of BUT-20 and 21,with Nbo and Unc topologies,respectively.展开更多
Exploring nonprecious electrocatalysts for water splitting with high efficiency and durability is critically important.Herein,bimetallic phosphides are encapsulated into graphitized carbon to construct a C@NiCoP compo...Exploring nonprecious electrocatalysts for water splitting with high efficiency and durability is critically important.Herein,bimetallic phosphides are encapsulated into graphitized carbon to construct a C@NiCoP composite nanoarray using bimetallic metal-organic framework(MOF) as a self-sacrificial template.The resulting C@NiCoP exhibits superior performance for pH-universal electrocatalytic hydrogen evolution reaction(HER),particularly representing a low overpotential of 46.3 mV at 10 mA cm^(-2) and Tafel slope of 44.1 mV dec^(-1) in alkaline media.The structural characterizations combined with theoretical calculation demonstrate that tailored electronic structure from bimetal atoms and the synergistic effect with graphitized carbon layer could jointly optimize the adsorption ability of hydrogen on active sites in HER process,and enhance the electrical conductivity as well.In addition,the carbon layer served as a protecting shell also prevents highly dispersed NiCoP components from agglomeration and/or loss in harsh media,finally improving the durability.This work thus provides a new insight into optimizing activity and stability of pH-universal electrocatalysts by the nanostructural design and electronic structure modulation.展开更多
Two primitive metal-organic frameworks(MOFs),Ni L1 and Ni L2,based on Ni_(8)O_(6)-cluster and ditopic pyrazolate linkers,L1(with rigid alkyne arms)and L2(with flexible alkyne chains),were prepared.The proton conductiv...Two primitive metal-organic frameworks(MOFs),Ni L1 and Ni L2,based on Ni_(8)O_(6)-cluster and ditopic pyrazolate linkers,L1(with rigid alkyne arms)and L2(with flexible alkyne chains),were prepared.The proton conductivities of these MOFs in pristine form and imidazole-encapsulated forms,Im@Ni L1 and Im@Ni L2,were measured and compared.Upon introduction of imidazole molecules,the proton conductivity could be increased by 3 to 5 orders of magnitude and reached as high as 1.72×10^(-2)S/cm(at 98%RH and 80℃).Also,whether imidazole molecules were introduced or not,Ni_(8)O_(6)-based MOFs with L2 in general gave better proton conductivity than those with L1 signifying that flexible side arms indeed assist proton conduction probably via establishment of efficient proton-conducting channels along with formation of highly ordered domains of water/imidazole molecules within the network cavities.Beyond the active Ni_(8)O_(6)-cluster,tuning flexibility of linker pendants serves as an alternative approach to regulate/modulate the proton conductivity of MOFs.展开更多
Large-scale deployment of carbon dioxide(CO_(2))removal technology is an essential step to cope with global warming and achieve carbon neutrality.Direct air capture(DAC)has recently received increasing attention given...Large-scale deployment of carbon dioxide(CO_(2))removal technology is an essential step to cope with global warming and achieve carbon neutrality.Direct air capture(DAC)has recently received increasing attention given the high flexibility to remove CO_(2)from discrete sources.Porous materials with adjustable pore characteristics are promising sorbents with low or no latent heat of vaporization.This review article has summarized the recent development of porous sorbents for DAC,with a focus of pore engineering strategy and adsorption mechanism.Physisorbents such as zeolites,porous carbons,metal-organic frameworks(MOFs),and amine-modified chemisorbents have been discussed and their challenges in practical application have been analyzed.At last,future directions have been proposed,and it is expected to inspire collaborations from chemistry,environment,material science and engineering communities.展开更多
The high porosity and tunable chemical functionality of metal-organic frameworks(MOFs)make it a promising catalyst design platform.High-throughput screening of catalytic performance is feasible since the large MOF str...The high porosity and tunable chemical functionality of metal-organic frameworks(MOFs)make it a promising catalyst design platform.High-throughput screening of catalytic performance is feasible since the large MOF structure database is available.In this study,we report a machine learning model for high-throughput screening of MOF catalysts for the CO_(2) cycloaddition reaction.The descriptors for model training were judiciously chosen according to the reaction mechanism,which leads to high accuracy up to 97%for the 75%quantile of the training set as the classification criterion.The feature contribution was further evaluated with SHAP and PDP analysis to provide a certain physical understanding.12,415 hypothetical MOF structures and 100 reported MOFs were evaluated under 100℃ and 1 bar within one day using the model,and 239 potentially efficient catalysts were discovered.Among them,MOF-76(Y)achieved the top performance experimentally among reported MOFs,in good agreement with the prediction.展开更多
CO_(2) valorization has been recognized as a pivotal process in reducing carbon sequestration costs.While metal-organic frameworks(MOFs)exhibit remarkable CO_(2) capture performance,their photocatalytic CO_(2) reducti...CO_(2) valorization has been recognized as a pivotal process in reducing carbon sequestration costs.While metal-organic frameworks(MOFs)exhibit remarkable CO_(2) capture performance,their photocatalytic CO_(2) reduction activity is often constrained by factors,such as insufficient active sites and frequent charge carrier recombination.In this work,an innovative strategy tailoring MOF surface architecture was developed.By tuning the concentration of highly supersaturated synthesis solutions,nonclassical secondary crystallization was facilitated,constructing abundant surface protrusions on the classic UiO-66 for the first time.These ultrasmall crystalline structures featuring high-index facets and missing-linker defects markedly increased both the amount and Lewis acid strength of exposed Zr sites,enhancing CO_(2) adsorption capacity and kinetics.Concurrently,the surface architecture induced an interfacial homojunction with a supporting built-in electric field,precisely delivering the photogenerated electrons to adsorbed CO_(2).Collectively,these upgrades synergistically boosted the critical surface reactions of the engineered catalyst,resulting in a sixfold increase in its CO yield relative to the pristine seeds.With its versatility,this strategy enriches the methodologies for addressing the intrinsic limitations of MOFs and enables the a priori design of efficient photocatalysts for low-concentration CO_(2).展开更多
Given the current global energy and environmental issues resulting from the fast pace of industrialization,the discovery of new functional materials has become increasingly imperative in order to advance science and t...Given the current global energy and environmental issues resulting from the fast pace of industrialization,the discovery of new functional materials has become increasingly imperative in order to advance science and technology and address the associated challenges.The boom in metal–organic frameworks(MOFs)and MOF-derived materials in recent years has stimulated profound interest in exploring their structures and applications.The preparation,characterization,and processing of MOF materials are the basis of their full engagement in industrial implementation.With intensive research in these topics,it is time to promote the practical utilization of MOFs on an industrial scale,such as for green chemical engineering,by taking advantage of their superior functions.Many famous MOFs have already demonstrated superiority over traditional materials in solving real-world problems.This review starts with the basic concept of MOF chemistry and ends with a discussion of the industrial production and exploitation of MOFs in several fields.Its goal is to provide a general scope of application to inspire MOF researchers to convert their focus on academic research to one on practical applications.After the obstacles of cost,scale-up preparation,processability,and stability have been overcome,MOFs and MOF-based devices will gradually enter the factory,become a part of our daily lives,and help to create a future based on green production and green living.展开更多
AIM： To investigate the features of various blood- borne virus infections and co-infection in intravenous drug users （IDUs）, and to examine the correlation of T lymphocyte subsets with virus co-infection. METHODS：...AIM： To investigate the features of various blood- borne virus infections and co-infection in intravenous drug users （IDUs）, and to examine the correlation of T lymphocyte subsets with virus co-infection. METHODS： Four hundred and six IDUs without any clinical manifestation of hepatitis and 102 healthy persons were enrolled in this study. HBV-DNA and HCV-RNA were detected by fluorescence quantitative PCR. HBsAg, HBeAg, anti-HBc, anti-HCV, HDV-Ag, anti-HGV, anti-HIV, and HCMV-IgM were assayed by enzyme-linked immunosorbent assay （ELISA） and immunochromatographic tests. The levels of Th1 and Th2 cytokines were measured by ELISA and radioactive immune assay （RIA）. The T lymphocyte subpopulation was detected by using fluorescence immunoassay. The similar indices taken from the healthy persons served as controls. RESULTS： The viral infection rate among IDUs was 36.45% for HBV, 69.7% for HCV, 47.3% for HIV, 2.22% for HDV, 1.97% for HGV, and 3.45% for HCMV. The co- infection rate of blood-borne virus was detected in 255 of 406 （62.81%） IDUs. More than 80% （161/192） of subjects infected with HIV were co-infected with the other viruses, such as HBV, HCV. In contrast, among the controls, the infection rate was 17.65% for HBV and 0% for the other viruses. Our investigation showed that there was a profound decrease in the proportion of CD4/CD8 and the percentage of CD3 and CD4, but not in the percentage of CD8. The levels of PHA-induced cytokines （IFN-γ and IL-4） and serum IL-2 were obviously decreased in IDUs. On the other hand, the level of serum IL-4 was increased. The level of IFN-γ and the percentage of CD4 were continuously decreased when the IDUs were infected with HIV or HIV co-infection. IDUs with HIV and HBV co-infection was 15.1% （29/192）. Of those 29 IDU with HIV and HBV co-infection, 51.72% （15/29） and 37.93% （11/29） were HBV-DNA-positive and HBeAg-positive, respectively. But, among IDUs without HIV infection, only 1.68% （2/119） of cases were HBV- DNA-positive.CONCLUSION： HCV, HBV and HIV infections are common in this population of IDU, leading to a high incidence of impaired Thl cytokine levels and CD4 lymphocyte. IDUs with HIV and HBV/HCV co-infection have lower expression of Th1 cytokine with enhancement of the Th2 response. HIV may be causing HBV replication by decreasing Thl function.展开更多
The separation of C2H4from C_(2)H_(6)/C_(2)H_(4)mixture is of great importance but difficult and energy intensive. Adsorptive separation provides an alternative approach to ameliorate this situation. Here, we report a...The separation of C2H4from C_(2)H_(6)/C_(2)H_(4)mixture is of great importance but difficult and energy intensive. Adsorptive separation provides an alternative approach to ameliorate this situation. Here, we report a microporous metal–organic framework(MOF) BUT-315-a as a C_(2)H_(6)-selective adsorbent for the separation of C2H6/C2H4gas mixture. BUT-315-a combines good IAST selectivity of 2.35 with high C_(2)H_(6)uptake of 97.5 cm^(3)g^(-1), giving superior high separation potential ΔQ(2226 mmol L^(-1)) for equimolar C_(2)H_(6)/C_(2)H_(4) at 298 K. Impressively, such excellent performance can be preserved at higher temperatures of 313 and 323 K to accommodate industrial conditions. Efficient dynamic separation performance of BUT-315-a has been demonstrated by column breakthrough experiments under varied temperatures and gas ratios. Theoretical calculations further reveal multiple synergistic interactions between C_(2)H_(6) and the framework. This work highlights a new benchmark material for C_(2)H_(6)/C_(2)H_(4)separation and provides guidance for designing adsorbent for separation applications.展开更多
Through an event-related potential(ERP)study,we examined the processing mechanisms of four types of Chinese(Mandarin)relative clauses(RCs),namely subject subject-extracted relative clause(SSR),subject object-extracted...Through an event-related potential(ERP)study,we examined the processing mechanisms of four types of Chinese(Mandarin)relative clauses(RCs),namely subject subject-extracted relative clause(SSR),subject object-extracted relative clause(SOR),object subject-extracted relative clause(OSR),and object object-extracted relative clause(OOR)to test the universality and language specificity of RC comprehension processes.The results of this study support a preference for object-extracted RCs modifying both the subject and object of a sentence,i.e.,SORs and OORs.In particular,ERP results showed stronger P600 effects in the RC region for SSRs compared with SORs,which we argue reflects a canonical word order theory.Stronger N400 effects were observed for verbs compared with nouns,reflecting easier understanding for nouns.ERP results from the matrix clause object and the relativizer“de”showed stronger P600 effects in SSRs compared with SORs,suggesting thematic structure effects on syntactic construction and the processing preference of the whole sentence.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
Framework materials(FMs)have been extensively investigated with a plethora of literature documenting their unique properties and potential applications.Despite this,a comprehensive knowledge graph for this emerging fi...Framework materials(FMs)have been extensively investigated with a plethora of literature documenting their unique properties and potential applications.Despite this,a comprehensive knowledge graph for this emerging field has not yet been constructed.In this study,by utilizing the natural language processing capabilities of large language models(LLMs),we have established a comprehensive knowledge graph(KG-FM).It covers synthesis,properties,applications,and other aspects of FMs including metal-organic frameworks(MOFs),covalent-organic frameworks(COFs),and hydrogen-bonded organic frameworks(HOFs).The knowledge graph was constructed through the analysis of over 100,000 articles,resulting in 2.53 million nodes and 4.01 million relationships.Subsequently,its application has been explored for enhancing data retrieval,mining,and the development of sophisticated question-answering systems.Especially when integrating the KGs with LLMs,resulted Qwen2-KG not only achieves a higher accuracy rate of 91.67%in question-answering than existing models but also provides precise information sources.展开更多
A facile strategy was designed to prepare magnetically layered chalcogenide Fe_(3)O_(4)/KMS-1(FK)composite adsorbents combining the advantages of rapid magnetic separation and satisfactory adsorption performance under...A facile strategy was designed to prepare magnetically layered chalcogenide Fe_(3)O_(4)/KMS-1(FK)composite adsorbents combining the advantages of rapid magnetic separation and satisfactory adsorption performance under vigorous stirring in ethanol solution at room temperature.The dispersion degree of Fe_(3)O_(4)in ethanol was superior to that in water,which gave a better result with the preparation in ethanol.Characterization by SEM-EDS,XRD,magnetic test,N_(2)physical-adsorption and TG-DTG demonstrated formation of FK and its adsorption performance.展开更多
Low-dimensional hybrid organic-inorganic metal halides(OIMHs)have been extensively investigated for their structural tunability and unique optoelectronic properties.However,the synthesis of highly photoluminescent lea...Low-dimensional hybrid organic-inorganic metal halides(OIMHs)have been extensively investigated for their structural tunability and unique optoelectronic properties.However,the synthesis of highly photoluminescent lead-free OIMHs remains challenging.To address this issue,we synthesized a series of hybrid OIMHs(DETA)_(3)InCl_(6):xSb^(3+)(DETA=diethylenetriamine,x=0-15%).With Sb^(3+)doping,the photoluminescence quantum yield(PLQY)is greatly improved from 4.84%to nearly 100%.Moreover,(DETA)_(3)InCl_(6):10%Sb^(3+)single crystals exhibit strong yellow broadband emission originating from selftrapped exciton(STE)radiative recombination.Interestingly,when Sb^(3+)doping is 0.005%,the single crystal doped Sb emits white light at an excitation wavelength of 365 nm with CIE coordinates of(0.35,0.36).We also explored the effect of Sb^(3+)dopants and STE state formation by DFT calculations and ultrafast transient absorption techniques.This research provides new insights into the design of high-performance photoluminescent materials based on hybrid metal halides.展开更多
Due to the unique photophysical and electrochemical properties of porphyrins,porphyrin-based metal-organic frameworks(PMOFs)offer an excellent platform for heterogeneous catalysis applications and the fundamental stud...Due to the unique photophysical and electrochemical properties of porphyrins,porphyrin-based metal-organic frameworks(PMOFs)offer an excellent platform for heterogeneous catalysis applications and the fundamental study of structure-property relationships based on their crystalline nature.In this study,we investigate the impact of porphyrin ligands with different substituents on the structural diversity of derived Zr(IV)-based PMOFs(Zr-PMOFs),with a particular emphasis on the advantage of a bifunctional pyridylcarboxylate porphyrinic ligand in tuning the structure and catalysis performance of resultant PMOFs.Two highly stable and porous Zr-PMOFs(BUT-229 and-230)prepared from the bifunctional porphyrinic ligand have similar constituents but different structural topology due to their ligands adopting different conformations.Noteworthily,the catalytic performance of Zr-PMOFs could be profoundly affected by the conformation of their porphyrinic ligands,which determines not only the topology,porosity,and catalytically active center density of the PMOFs,but also their photoelectric properties,including visible-light absorption,bandgap,electron transfer and charge separation efficiency.As a rare example of PMOFs with the flu topology,BUT-229 afforded obviously higher catalytic activity than BUT-230 as well as some benchmark PMOFs in the photo-oxidation reaction of benzyl alcohol.Moreover,with Lewis base sites(free pyridyl N atoms)on pore surfaces,BUT-229 could efficiently catalyze the tandem reactions between aromatic alcohols and active methylene compounds under mild conditions.Its catalytic activity was further enhanced by partially appending covalently the cocatalyst TEMPO(TEMPO=2,2,6,6-tetramethylpiperidinooxy)to the free pyridyl groups via the Zincke reaction.These results provide insights into the development of high-performance porphyrin-based catalysts for tandem organic reactions.展开更多
Separating/capturing SF_(6),having the strongest global warming potential,from exhaust gas with low concentration(1%–10%)in the power industry is significant for both greenhouse gas emission control and SF_(6) recycl...Separating/capturing SF_(6),having the strongest global warming potential,from exhaust gas with low concentration(1%–10%)in the power industry is significant for both greenhouse gas emission control and SF_(6) recycling and reutilization.In this study,we achieved highly efficient SF_(6)/N_(2) separation under different SF_(6) concentrations(1% and 10%)using two homologous metal-organic frameworks,Ni-bpz and Zn-bpz.This outcome underscores the effectiveness of rational nano-traps distribution engineering for targeted separation applications.The molecular simulation suggests that an SF_(6) molecule interacts with a single nano-trap in Zn-bpz.At the same time,it is efficiently confined by two adjacent nano-traps in the parallel distribution of Ni-bpz.Consequently,exceptional SF_(6)/N_(2) selectivity for 1/99 and 10/90 mixtures have been respectively achieved in Ni-bpz(516,SF_(6)/N_(2)=1/99)and Zn-bpz(608,SF_(6)/N_(2)=10/90)at 298 K and 1 bar.In dynamic breakthrough experiments,Ni-bpz exhibits a record pure N_(2)(≥99.99%)productivity(1496 mL/g)for an SF_(6)/N_(2)(1/99)gas mixture.Moreover,both MOFs demonstrate excellent water resistance across multiple cycles,suggesting their high promise for practical application.展开更多
基金supported from the Natural Science Foundation of China (Grant Nos. 21771012, 21601008 and 21576006)the National Natural Science Fund for Innovative Research Groups (Grant No. 51621003)the China Postdoctoral Science Foundation (Grant No. 2016M600879)
文摘The separation of gas molecules with similar physicochemical properties is of high importance but practically entails a substantial energy penalty in chemical industry. Meanwhile, clean energy gases such as H_2 and CH_4 are considered as promising candidates for the replacement of traditional fossil fuels. However, the technologies for the storage of these gases are still immature. In addition, the release of anthropogenic toxic gases into the atmosphere is a worldwide threat of growing concern. Both in academia and industry, considerable research efforts have been devoted to developing advanced porous materials for the effective and energy-efficient separation, storage, or capture of the related gases. In contrast to conventional inorganic porous materials such as zeolites and activated carbons, metal–organic frameworks(MOFs) are considered as a type of promising materials for gas separation and storage. In this contribution, we review the recent research advance of MOFs in some relevant applications, including CO_2 capture, O_2 purification, separation of light hydrocarbons, separation of noble gases, storage of gases(CH_4,H_2, and C_2 H_2) for energy, and removal of some gaseous air pollutants(NH_3, NO_2, and SO_2). Finally, an outlook regarding the challenges of the future research of MOFs in these directions is given.
基金the financial support from the National Natural Science Foundation of China (Nos.22225803 and 22038001)。
文摘Short-chain perfluorocarboxylic acids(PFCAs) are a class of persistent organic pollutants that are widely used as substitutes for long-chain PFCAs. However, they also pose a non-negligible risk to ecosystems. In this study, we demonstrated that a fluorescent metal–organic framework(MOF)(named V-101) constructed from In^(3+)and an aromatic-rich tetratopic carboxylate ligand 5-[2,6-bis(4-carboxyphenyl) pyridin-4-yl] isophthalic acid(H4BCPIA) exhibited highly efficient turn-off and turn-on fluorescence responses toward five short-chain PFCAs in water and methanol, respectively. The limits of detection of V-101 toward five short-chain PFCAs are down to μg/L level, and it showed good anti-interference abilities toward short-chain PFCAs in the presence of common metal ions. The major mechanisms associated with fluorescence responses were molecular collisions and interactions between V-101 and short-chain PFCAs. This work demonstrates that the structure variety of MOFs imparts them with the potential of MOFs in the detection of short-chain PFCAs for pollution control.
基金financial support from the National Natural Science Foundation of China(No.22038001,51621003,22108007)。
文摘Under the context of carbon neutrality of China,it is urgent to shift our energy supply towards cleaner fuels as well as to reduce the greenhouse gas emission.Currently,coal is the main fossil fuel energy source of China.The country is striving hard to replace it with methane,a cleaner fossil fuel.Although China has rich geological resources of methane as coal bed methane(CBM)reserves,it is quite challenging to utilize them due to low concentration.The CBM is however mainly emitted directly to atmosphere during coal mining,causing waste of the resource and huge contribution to greenhouse effect.The recent work by Yang et al.demonstrated a potential solution to extract low concentration methane selectively from CBM through using MOF materials as sorbents.Such kind of materials and associated separation technology are promising to reduce greenhouse gas emission and promote the methane production capability,which would contribute to carbon neutrality in dual pathways.
基金Supported by the National Natural Science Foundation of China(21406006,21576003)the Science and Technology Program of Beijing Municipal Education Commission(KM201510005010)+1 种基金the Importation and Development of High-Caliber Talents Project of Beijing Municipal Institutions(CIT&TCD20150309)the China Postdoctoral Science Foundation funded project(2015M580954)
文摘The separation of aromatic/aliphatic hydrocarbon mixtures is a significant process in chemical industry, but challenged in some cases. Compared with conventional separation technologies, pervaporation is quite promising in terms of its economical, energy-saving, and eco-friendly advantages. However, this technique has not been used in industry for separating aromatic/aliphatic mixtures yet. One of the main reasons is that the separation performance of existed pervaporation membranes is unsatisfactory. Membrane material is an important factor that affects the separation performance. This review provides an overview on the advances in studying membrane materials for the pervaporation separation of aromatic/aliphatic mixtures over the past decade. Explored pristine polymers and their hybrid materials(as hybrid membranes) are summarized to highlight their nature and separation performance. We anticipate that this review could provide some guidance in the development of new materials for the aromatic/aliphatic pervaporation separation.
基金financially supported by the NSFC (Nos. 21322601, 21271015, 21406006, and U1407119)Program for New Century Excellent Talents in University (No. NCET-13-0647)
文摘Two new metal-organic frameworks（MOFs）,[Cu2（H_2O）_2（BCPIA）]（BUT-20）and（Me_2NH_2）[In（BCPIA）]（BUT-21）were designed and synthesized through the solvothermal reaction between a newly created desymmetric 4-connected ligand,5-（2,6-bis（4-carboxyphenyl）pyridin-4-yl）isophthalic acid（H_4BCPIA）and Cu（NO_3）2 2.5H_2O or In（NO_3）_3·5H_2O,respectively,and characterized by single-crystal and powder Xray diffraction,thermogravimetric analysis,infrared spectroscopy,and elemental analysis.The two MOFs have three-dimensional structures,in which both the BCPIA 4 ligand and metal-containing entities,Cu_2（COO）_4（H_2O）_2 and In（COO）_4 act as 4-connected nodes.However,different linkage configurations of the two metal-containing nodes,quadrilateral Cu_2_TD_2（COO）_4（H_2O）_2and tetrahedral In（COO）_4,lead to distinct structural networks of BUT-20 and 21,with Nbo and Unc topologies,respectively.
基金supported by the National Natural Science Foundation of China (nos. 21771012, 22038001, 51621003)。
文摘Exploring nonprecious electrocatalysts for water splitting with high efficiency and durability is critically important.Herein,bimetallic phosphides are encapsulated into graphitized carbon to construct a C@NiCoP composite nanoarray using bimetallic metal-organic framework(MOF) as a self-sacrificial template.The resulting C@NiCoP exhibits superior performance for pH-universal electrocatalytic hydrogen evolution reaction(HER),particularly representing a low overpotential of 46.3 mV at 10 mA cm^(-2) and Tafel slope of 44.1 mV dec^(-1) in alkaline media.The structural characterizations combined with theoretical calculation demonstrate that tailored electronic structure from bimetal atoms and the synergistic effect with graphitized carbon layer could jointly optimize the adsorption ability of hydrogen on active sites in HER process,and enhance the electrical conductivity as well.In addition,the carbon layer served as a protecting shell also prevents highly dispersed NiCoP components from agglomeration and/or loss in harsh media,finally improving the durability.This work thus provides a new insight into optimizing activity and stability of pH-universal electrocatalysts by the nanostructural design and electronic structure modulation.
基金the National Natural Science Foundation of China(No.21871061)the Foundation of Basic and Applied Basic Research of Guangdong Province(No.2021A1515010274)+2 种基金the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(No.2017BT01Z032)the Science and Technology Planning Project of Guangdong Province(No.2021A0505030066)the Science and Technology Program of Guangzhou(No.201807010026)。
文摘Two primitive metal-organic frameworks(MOFs),Ni L1 and Ni L2,based on Ni_(8)O_(6)-cluster and ditopic pyrazolate linkers,L1(with rigid alkyne arms)and L2(with flexible alkyne chains),were prepared.The proton conductivities of these MOFs in pristine form and imidazole-encapsulated forms,Im@Ni L1 and Im@Ni L2,were measured and compared.Upon introduction of imidazole molecules,the proton conductivity could be increased by 3 to 5 orders of magnitude and reached as high as 1.72×10^(-2)S/cm(at 98%RH and 80℃).Also,whether imidazole molecules were introduced or not,Ni_(8)O_(6)-based MOFs with L2 in general gave better proton conductivity than those with L1 signifying that flexible side arms indeed assist proton conduction probably via establishment of efficient proton-conducting channels along with formation of highly ordered domains of water/imidazole molecules within the network cavities.Beyond the active Ni_(8)O_(6)-cluster,tuning flexibility of linker pendants serves as an alternative approach to regulate/modulate the proton conductivity of MOFs.
基金financial support from the National Natural Science Foundation of China(Nos.22278011,22225803,22038001 and 22108007)Beijing Natural Science Foundation(No.Z230023)+1 种基金The Science&Technology Project of Beijing Municipal Education Committee(No.KZ201810005004)Beijing Nova Program(No.Z211100002121094)。
文摘Large-scale deployment of carbon dioxide(CO_(2))removal technology is an essential step to cope with global warming and achieve carbon neutrality.Direct air capture(DAC)has recently received increasing attention given the high flexibility to remove CO_(2)from discrete sources.Porous materials with adjustable pore characteristics are promising sorbents with low or no latent heat of vaporization.This review article has summarized the recent development of porous sorbents for DAC,with a focus of pore engineering strategy and adsorption mechanism.Physisorbents such as zeolites,porous carbons,metal-organic frameworks(MOFs),and amine-modified chemisorbents have been discussed and their challenges in practical application have been analyzed.At last,future directions have been proposed,and it is expected to inspire collaborations from chemistry,environment,material science and engineering communities.
基金financial support from the National Key Research and Development Program of China(2021YFB 3501501)the National Natural Science Foundation of China(No.22225803,22038001,22108007 and 22278011)+1 种基金Beijing Natural Science Foundation(No.Z230023)Beijing Science and Technology Commission(No.Z211100004321001).
文摘The high porosity and tunable chemical functionality of metal-organic frameworks(MOFs)make it a promising catalyst design platform.High-throughput screening of catalytic performance is feasible since the large MOF structure database is available.In this study,we report a machine learning model for high-throughput screening of MOF catalysts for the CO_(2) cycloaddition reaction.The descriptors for model training were judiciously chosen according to the reaction mechanism,which leads to high accuracy up to 97%for the 75%quantile of the training set as the classification criterion.The feature contribution was further evaluated with SHAP and PDP analysis to provide a certain physical understanding.12,415 hypothetical MOF structures and 100 reported MOFs were evaluated under 100℃ and 1 bar within one day using the model,and 239 potentially efficient catalysts were discovered.Among them,MOF-76(Y)achieved the top performance experimentally among reported MOFs,in good agreement with the prediction.
基金support from the National Natural Science Foundation of China(No.22378007)the Beijing Natural Science Foundation(No.Z230023)a collaborative project from Beijing Energy Holding Co.,Ltd.(No.40053002202405).
文摘CO_(2) valorization has been recognized as a pivotal process in reducing carbon sequestration costs.While metal-organic frameworks(MOFs)exhibit remarkable CO_(2) capture performance,their photocatalytic CO_(2) reduction activity is often constrained by factors,such as insufficient active sites and frequent charge carrier recombination.In this work,an innovative strategy tailoring MOF surface architecture was developed.By tuning the concentration of highly supersaturated synthesis solutions,nonclassical secondary crystallization was facilitated,constructing abundant surface protrusions on the classic UiO-66 for the first time.These ultrasmall crystalline structures featuring high-index facets and missing-linker defects markedly increased both the amount and Lewis acid strength of exposed Zr sites,enhancing CO_(2) adsorption capacity and kinetics.Concurrently,the surface architecture induced an interfacial homojunction with a supporting built-in electric field,precisely delivering the photogenerated electrons to adsorbed CO_(2).Collectively,these upgrades synergistically boosted the critical surface reactions of the engineered catalyst,resulting in a sixfold increase in its CO yield relative to the pristine seeds.With its versatility,this strategy enriches the methodologies for addressing the intrinsic limitations of MOFs and enables the a priori design of efficient photocatalysts for low-concentration CO_(2).
基金We acknowledge financial support from the National Natural Science Foundation of China(51621003,21771012,and 22038001)the Science&Technology Project of Beijing Municipal Education Committee(KZ201810005004).
文摘Given the current global energy and environmental issues resulting from the fast pace of industrialization,the discovery of new functional materials has become increasingly imperative in order to advance science and technology and address the associated challenges.The boom in metal–organic frameworks(MOFs)and MOF-derived materials in recent years has stimulated profound interest in exploring their structures and applications.The preparation,characterization,and processing of MOF materials are the basis of their full engagement in industrial implementation.With intensive research in these topics,it is time to promote the practical utilization of MOFs on an industrial scale,such as for green chemical engineering,by taking advantage of their superior functions.Many famous MOFs have already demonstrated superiority over traditional materials in solving real-world problems.This review starts with the basic concept of MOF chemistry and ends with a discussion of the industrial production and exploitation of MOFs in several fields.Its goal is to provide a general scope of application to inspire MOF researchers to convert their focus on academic research to one on practical applications.After the obstacles of cost,scale-up preparation,processability,and stability have been overcome,MOFs and MOF-based devices will gradually enter the factory,become a part of our daily lives,and help to create a future based on green production and green living.
基金Supported by the National Natural Sciences Foundation of China, No. 30160083
文摘AIM： To investigate the features of various blood- borne virus infections and co-infection in intravenous drug users （IDUs）, and to examine the correlation of T lymphocyte subsets with virus co-infection. METHODS： Four hundred and six IDUs without any clinical manifestation of hepatitis and 102 healthy persons were enrolled in this study. HBV-DNA and HCV-RNA were detected by fluorescence quantitative PCR. HBsAg, HBeAg, anti-HBc, anti-HCV, HDV-Ag, anti-HGV, anti-HIV, and HCMV-IgM were assayed by enzyme-linked immunosorbent assay （ELISA） and immunochromatographic tests. The levels of Th1 and Th2 cytokines were measured by ELISA and radioactive immune assay （RIA）. The T lymphocyte subpopulation was detected by using fluorescence immunoassay. The similar indices taken from the healthy persons served as controls. RESULTS： The viral infection rate among IDUs was 36.45% for HBV, 69.7% for HCV, 47.3% for HIV, 2.22% for HDV, 1.97% for HGV, and 3.45% for HCMV. The co- infection rate of blood-borne virus was detected in 255 of 406 （62.81%） IDUs. More than 80% （161/192） of subjects infected with HIV were co-infected with the other viruses, such as HBV, HCV. In contrast, among the controls, the infection rate was 17.65% for HBV and 0% for the other viruses. Our investigation showed that there was a profound decrease in the proportion of CD4/CD8 and the percentage of CD3 and CD4, but not in the percentage of CD8. The levels of PHA-induced cytokines （IFN-γ and IL-4） and serum IL-2 were obviously decreased in IDUs. On the other hand, the level of serum IL-4 was increased. The level of IFN-γ and the percentage of CD4 were continuously decreased when the IDUs were infected with HIV or HIV co-infection. IDUs with HIV and HBV co-infection was 15.1% （29/192）. Of those 29 IDU with HIV and HBV co-infection, 51.72% （15/29） and 37.93% （11/29） were HBV-DNA-positive and HBeAg-positive, respectively. But, among IDUs without HIV infection, only 1.68% （2/119） of cases were HBV- DNA-positive.CONCLUSION： HCV, HBV and HIV infections are common in this population of IDU, leading to a high incidence of impaired Thl cytokine levels and CD4 lymphocyte. IDUs with HIV and HBV/HCV co-infection have lower expression of Th1 cytokine with enhancement of the Th2 response. HIV may be causing HBV replication by decreasing Thl function.
基金the financial support of the National Natural Science Foundation of China (No. 22038001)。
文摘The separation of C2H4from C_(2)H_(6)/C_(2)H_(4)mixture is of great importance but difficult and energy intensive. Adsorptive separation provides an alternative approach to ameliorate this situation. Here, we report a microporous metal–organic framework(MOF) BUT-315-a as a C_(2)H_(6)-selective adsorbent for the separation of C2H6/C2H4gas mixture. BUT-315-a combines good IAST selectivity of 2.35 with high C_(2)H_(6)uptake of 97.5 cm^(3)g^(-1), giving superior high separation potential ΔQ(2226 mmol L^(-1)) for equimolar C_(2)H_(6)/C_(2)H_(4) at 298 K. Impressively, such excellent performance can be preserved at higher temperatures of 313 and 323 K to accommodate industrial conditions. Efficient dynamic separation performance of BUT-315-a has been demonstrated by column breakthrough experiments under varied temperatures and gas ratios. Theoretical calculations further reveal multiple synergistic interactions between C_(2)H_(6) and the framework. This work highlights a new benchmark material for C_(2)H_(6)/C_(2)H_(4)separation and provides guidance for designing adsorbent for separation applications.
基金supported by the National Social Science Foundation of China under Grant No.13BYY072
文摘Through an event-related potential(ERP)study,we examined the processing mechanisms of four types of Chinese(Mandarin)relative clauses(RCs),namely subject subject-extracted relative clause(SSR),subject object-extracted relative clause(SOR),object subject-extracted relative clause(OSR),and object object-extracted relative clause(OOR)to test the universality and language specificity of RC comprehension processes.The results of this study support a preference for object-extracted RCs modifying both the subject and object of a sentence,i.e.,SORs and OORs.In particular,ERP results showed stronger P600 effects in the RC region for SSRs compared with SORs,which we argue reflects a canonical word order theory.Stronger N400 effects were observed for verbs compared with nouns,reflecting easier understanding for nouns.ERP results from the matrix clause object and the relativizer“de”showed stronger P600 effects in SSRs compared with SORs,suggesting thematic structure effects on syntactic construction and the processing preference of the whole sentence.
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the financial support from the National Key Research and Development Program of China(2021YFB3501501)the National Natural Science Foundation of China(Nos.22225803,22038001,22278011,and 22108007)Beijing Natural Science Foundation(No.Z230023).
文摘Framework materials(FMs)have been extensively investigated with a plethora of literature documenting their unique properties and potential applications.Despite this,a comprehensive knowledge graph for this emerging field has not yet been constructed.In this study,by utilizing the natural language processing capabilities of large language models(LLMs),we have established a comprehensive knowledge graph(KG-FM).It covers synthesis,properties,applications,and other aspects of FMs including metal-organic frameworks(MOFs),covalent-organic frameworks(COFs),and hydrogen-bonded organic frameworks(HOFs).The knowledge graph was constructed through the analysis of over 100,000 articles,resulting in 2.53 million nodes and 4.01 million relationships.Subsequently,its application has been explored for enhancing data retrieval,mining,and the development of sophisticated question-answering systems.Especially when integrating the KGs with LLMs,resulted Qwen2-KG not only achieves a higher accuracy rate of 91.67%in question-answering than existing models but also provides precise information sources.
基金supported by the National Natural Science Foundation of China[No.51708535 and 51278481]the Science and Technique Plan Project of Ningbo City[No.2016C51032]the Industry guide(key)project of Fujian province[No.2016H0041].
文摘A facile strategy was designed to prepare magnetically layered chalcogenide Fe_(3)O_(4)/KMS-1(FK)composite adsorbents combining the advantages of rapid magnetic separation and satisfactory adsorption performance under vigorous stirring in ethanol solution at room temperature.The dispersion degree of Fe_(3)O_(4)in ethanol was superior to that in water,which gave a better result with the preparation in ethanol.Characterization by SEM-EDS,XRD,magnetic test,N_(2)physical-adsorption and TG-DTG demonstrated formation of FK and its adsorption performance.
基金supported by the National Natural Science Foundation of China(22275075)the Natural Science Foundation of Jiangxi Province(20204BCJ22015 and 20202ACBL203001)the Jiangxi Provincial Key Laboratory of Functional Molecular Materials Chemistry(20212BCD42018).
文摘Low-dimensional hybrid organic-inorganic metal halides(OIMHs)have been extensively investigated for their structural tunability and unique optoelectronic properties.However,the synthesis of highly photoluminescent lead-free OIMHs remains challenging.To address this issue,we synthesized a series of hybrid OIMHs(DETA)_(3)InCl_(6):xSb^(3+)(DETA=diethylenetriamine,x=0-15%).With Sb^(3+)doping,the photoluminescence quantum yield(PLQY)is greatly improved from 4.84%to nearly 100%.Moreover,(DETA)_(3)InCl_(6):10%Sb^(3+)single crystals exhibit strong yellow broadband emission originating from selftrapped exciton(STE)radiative recombination.Interestingly,when Sb^(3+)doping is 0.005%,the single crystal doped Sb emits white light at an excitation wavelength of 365 nm with CIE coordinates of(0.35,0.36).We also explored the effect of Sb^(3+)dopants and STE state formation by DFT calculations and ultrafast transient absorption techniques.This research provides new insights into the design of high-performance photoluminescent materials based on hybrid metal halides.
基金support from the National Natural Science Foundation of China(No.22225803 and 22038001)the Beijing Natural Science Foundation(No.Z230023).
文摘Due to the unique photophysical and electrochemical properties of porphyrins,porphyrin-based metal-organic frameworks(PMOFs)offer an excellent platform for heterogeneous catalysis applications and the fundamental study of structure-property relationships based on their crystalline nature.In this study,we investigate the impact of porphyrin ligands with different substituents on the structural diversity of derived Zr(IV)-based PMOFs(Zr-PMOFs),with a particular emphasis on the advantage of a bifunctional pyridylcarboxylate porphyrinic ligand in tuning the structure and catalysis performance of resultant PMOFs.Two highly stable and porous Zr-PMOFs(BUT-229 and-230)prepared from the bifunctional porphyrinic ligand have similar constituents but different structural topology due to their ligands adopting different conformations.Noteworthily,the catalytic performance of Zr-PMOFs could be profoundly affected by the conformation of their porphyrinic ligands,which determines not only the topology,porosity,and catalytically active center density of the PMOFs,but also their photoelectric properties,including visible-light absorption,bandgap,electron transfer and charge separation efficiency.As a rare example of PMOFs with the flu topology,BUT-229 afforded obviously higher catalytic activity than BUT-230 as well as some benchmark PMOFs in the photo-oxidation reaction of benzyl alcohol.Moreover,with Lewis base sites(free pyridyl N atoms)on pore surfaces,BUT-229 could efficiently catalyze the tandem reactions between aromatic alcohols and active methylene compounds under mild conditions.Its catalytic activity was further enhanced by partially appending covalently the cocatalyst TEMPO(TEMPO=2,2,6,6-tetramethylpiperidinooxy)to the free pyridyl groups via the Zincke reaction.These results provide insights into the development of high-performance porphyrin-based catalysts for tandem organic reactions.
基金the financial support from the National Natural Science Foundation of China(Nos.22225803,22038001,22278011,and 22108007)the Beijing Natural Science Foundation(No.Z230023)the Beijing Nova Program(No.Z211100002121094).
文摘Separating/capturing SF_(6),having the strongest global warming potential,from exhaust gas with low concentration(1%–10%)in the power industry is significant for both greenhouse gas emission control and SF_(6) recycling and reutilization.In this study,we achieved highly efficient SF_(6)/N_(2) separation under different SF_(6) concentrations(1% and 10%)using two homologous metal-organic frameworks,Ni-bpz and Zn-bpz.This outcome underscores the effectiveness of rational nano-traps distribution engineering for targeted separation applications.The molecular simulation suggests that an SF_(6) molecule interacts with a single nano-trap in Zn-bpz.At the same time,it is efficiently confined by two adjacent nano-traps in the parallel distribution of Ni-bpz.Consequently,exceptional SF_(6)/N_(2) selectivity for 1/99 and 10/90 mixtures have been respectively achieved in Ni-bpz(516,SF_(6)/N_(2)=1/99)and Zn-bpz(608,SF_(6)/N_(2)=10/90)at 298 K and 1 bar.In dynamic breakthrough experiments,Ni-bpz exhibits a record pure N_(2)(≥99.99%)productivity(1496 mL/g)for an SF_(6)/N_(2)(1/99)gas mixture.Moreover,both MOFs demonstrate excellent water resistance across multiple cycles,suggesting their high promise for practical application.
