Enhanced Catalytic Activity of Crystalline Phosphorus Nanosheets Fabricated via Solvothermal Phase Transformation.

The newly reported crystalline phosphorus nanosheets (cryst-P NSs) exhibit promising features for industrial applications, including outstanding air-water stability and facile large-scale production. However, their complex crystallization impedes a priori tailoring. Herein, the temporal evolution of cryst-P NSs was investigated with the optimized synthesis parameters. The occurrence of self-assembly and solid-state rearrangement unveiled the existence of an intermediate phase as the bulk crystalline precursor and the predominance of nonclassical crystallization pathway(s). With the upgraded synthesis protocol simultaneously strengthening the merits of cryst-P NSs, their catalytic performances were evaluated in various electro- and/or photocatalytic reactions spanning hydrogen and oxygen evolution, full water splitting, CO2 reduction, and organic pollutant decomposition. Superior catalytic activities and orders of magnitude longer lifetimes were consistently discerned compared with the widely employed black phosphorus nanosheets with similar size and thickness. The exciting discoveries in both fundamental crystallization and catalytic applications drastically thrust the comprehension of elemental phosphorus, shedding light on the encouraging capabilities of solvothermal synthesis strategies in the design and systematic tailoring of phosphorus materials.

Rare-Earth Metal-Organic Framework with Nonplanar Porphyrin Groups for High-Efficiency Photocatalysis.

Nonplanar porphyrins play crucial roles in many biological processes and chemical reactions as catalysts. However, the preparation of artificial nonplanar porphyrins suffers from complicated organic syntheses. Herein, we present a new rare-earth porphyrinic metal-organic framework (RE-PMOF), BUT-233, which is a three-dimensional (3D) framework structure with the flu topology consisting of 4-connected BBCPPP-Ph ligands H4BBCPPP-Ph = 5',5⁗-(10,20-diphenylporphyrin-5,15-diyl)bis([1,1':3',1″-terphenyl]-4,4'' dicarboxylic acid) and 8-connected Eu6 clusters. Noteworthily, the porphyrin cores of the BBCPPP-Ph ligands in BUT-233 are nonplanar with a ruffle-like conformation. In contrast, the porphyrin core in the free ligand H4BBCPPP-Ph is in a nearly ideally planar conformation, as confirmed by its single-crystal structure. BUT-233 is microporous with 6-8 Špores and a Brunauer-Emmett-Teller (BET) surface area of 649 m2/g, as well as high stability in common solvents. The MOF was used as a photocatalyst for the oxidation degradation of a chemical warfare agent model molecule CEES (CEES = 2-chloroethyl ethyl sulfide) under the light-emitting diode (LED) irradiation and an O2 atmosphere at room temperature. CEES was almost completely converted into its nontoxic light-oxidized product CEESO (CEESO = 2-chloroethyl ethyl sulfoxide) in only 5 min with t1/2 = 2 min (t1/2: half-life). Moreover, the toxic deep-oxidized product 2-chloroethyl ethyl sulfone (CEESO2) was not detected. The catalytic activity of BUT-233 was high in comparison with those of some previously reported MOF catalysts. The results of photo/electrochemical property studies suggested that the high catalytic activity of BUT-233 was benefited from the presence of nonplanar porphyrin rings on its pore surface.

Evaluation of Open-Source Large Language Models for Metal-Organic Frameworks Research.

Along with the development of machine learning, deep learning, and large language models (LLMs) such as GPT-4 (GPT: Generative Pre-Trained Transformer), artificial intelligence (AI) tools have been playing an increasingly important role in chemical and material research to facilitate the material screening and design. Despite the exciting progress of GPT-4 based AI research assistance, open-source LLMs have not gained much attention from the scientific community. This work primarily focused on metal-organic frameworks (MOFs) as a subdomain of chemistry and evaluated six top-rated open-source LLMs with a comprehensive set of tasks including MOFs knowledge, basic chemistry knowledge, in-depth chemistry knowledge, knowledge extraction, database reading, predicting material property, experiment design, computational scripts generation, guiding experiment, data analysis, and paper polishing, which covers the basic units of MOFs research. In general, these LLMs were capable of most of the tasks. Especially, Llama2-7B and ChatGLM2-6B were found to perform particularly well with moderate computational resources. Additionally, the performance of different parameter versions of the same model was compared, which revealed the superior performance of higher parameter versions.

Expanding the Structural Topologies of Rare-Earth Porphyrinic Metal-Organic Frameworks through Ligand Modulation.

Expanding the structural diversity of porphyrinic metal-organic frameworks (PMOFs) is essential to develop functional materials with novel properties or enhanced performance in different applications. Herein, we establish a strategy to construct rare-earth (RE) PMOFs with unprecedented topology via rational functionalization of porphyrinic ligands. By introducing phenyl/pyridyl groups to the meso-positions of the porphyrin core, the symmetries and connectivities of the ligands are tuned, and three RE-PMOFs (BUT-224/-225/-226) with new topologies are successfully obtained. In addition, BUT-225(Co), with both the Lewis basic and acidic sites, exhibits enhanced CO2 uptake and higher catalytic activity for the cycloaddition of CO2 and epoxides under mild conditions. This work reveals that the RE-PMOFs with novel topologies can be rationally designed and constructed through ligand functionalization, which provides insights into the construction of tailored PMOFs for various applications.

Enhancing Ethane/Ethylene Separation Performance in Two Dynamic MOFs by Regulating Temperature-Controlled Structural Interpenetration.

The separation of ethane from ethylene is an important but challenging process in the chemical industry because of their similar physicochemical properties. Generally, the adsorbents for C2H6/C2H4 separation require an appropriate and relatively small aperture. Herein, we report two dynamic pillar-layered metal-organic frameworks (MOFs) BUT-111 and BUT-112 with isomorphic frameworks but different degrees of interpenetration for efficient C2H4 purification. The dynamic behavior makes both the activated MOFs exhibit ultramicropores and reversed order adsorption behavior for C2H6 and C2H4, which could obtain highly purified C2H4 in one step from the C2H6/C2H4 mixture. BUT-111 and BUT-112 could work in a wide temperature range, and with the decrease in temperature, the C2H6/C2H4 selectivity would increase. Moreover, the degree of interpenetration could be well controlled by the synthetic temperature, and the increase in the interpenetration degree of BUT-112 enhanced the C2H4 purification effectively.

UiO-66 Selective Enrichment Integrated with Thermal Desorption GC-MS for Detection of Benzene Homologues in Ambient Air.

In this study, UiO-66 was selected as sorbent media packed in the tube to selectively enrich trace levels of benzene homologues such as benzene, toluene, and xylene (BTX) in ambient air prior to thermal desorption (TD)-GC-MS determination. A series of experiments were conducted to obtain the optimal TD conditions. The results indicated that the optimal TD parameters were as follows: desorption temperature of 180°C, desorption flow rate of 50 mL min-1, and desorption time of 30 min. Furthermore, the method based on UiO-66 enrichment integrated with TD-GC-MS for trace levels of BTX was successfully developed. It exhibited a good linearity (R 2 > 0.99) in the range of 50-1000 ng, except for p, m-xylene in the range of 100-2000 ng, and achieved the recovery of 69.4-101.3%, and the relative standard deviation of 3.8-6.4%. The detection limits of BTX were 1.6-4.0 ng; according to 10 L of sampling volume, the method detection limits would be in the range of 0.16-0.40 µg m-3. Additionally, the method was successfully applied to determine BTX in indoor air and showed good selectivity and sensitivity. In summary, the findings in this work revealed that UiO-66 was an attractive adsorbent for selective enrichment trace levels of BTX compounds in ambient air, which was favorable for the subsequent detection by TD-GC-MS.

Effective Removal of Clenbuterol and Ractopamine from Water with a Stable Al(III)-Based Metal-Organic Framework.

Clenbuterol (CLE) and ractopamine (RAC) are two kinds of typical ß2-adrenergic agonists which pose a serious threat to the health of human beings. In this work, 10 kinds of metal-organic frameworks (MOFs) with high stability and various pore features are screened to assess adsorption performance for CLE and RAC. An Al(III)-MOF (BUT-19) with abundant ethyl groups exhibits exceptional performance in removing CLE and RAC from water. The maximum adsorption capacity for CLE and RAC are up to 294.1 and 366.3 mg/g under the optimum adsorption conditions, respectively. Meanwhile, the adsorption mechanism effects of pH, temperature, and coexisted ions are investigated systematically. It is found that the MOF pore size and weak hydrogen-bond interactions between CLE/RAC molecules and the MOF are the main causes leading to the extraordinary adsorption. This study provides a new idea for the purposeful design and synthesis of MOFs for removing environmental pollutants and sheds light on the depuration of contaminated water.

Partial Sulfurization of a 2D MOF Array for Highly Efficient Oxygen Evolution Reaction.

A feasible strategy for the in situ growth of two-dimensional (2D) [Ni3(OH)2(1,4-BDC)2-(H2O)4]·2H2O (Ni-BDC; 1,4-BDC = 1,4-benzenedicarboxylate) and the subsequent partial sulfurization treatment for the decoration of nickle sulfide (NiS) is developed. The fabricated hierarchically structured Ni-BDC@NiS as a synergistic electrocatalyst shows extremely high activity toward the oxygen evolution reaction (OER). The optimal Ni-BDC@NiS catalyst acquires a current density of 20 mA cm-2 at a lower overpotential of 330 mV and low Tafel slope of 62 mV dec-1, outperforming most previously reported Ni-based sulfide catalysts. Clearly, the combination of the NiS and Ni-BDC array contributed to the improvement of electron transfer, promotion of water adsorption, and increase of rich active species. In addition, the in situ created hierarchical structure not only affords feasible access for mass transport but also strengthens structural integrity, contributing to efficient and stable OER performance. This general and effective strategy anchoring conductive active species on a porous metal-organic framework (MOF) thus provides an efficient way to fabricate synergistic electrocatalysts for the OER.

A Copper(II)-Paddlewheel Metal-Organic Framework with Exceptional Hydrolytic Stability and Selective Adsorption and Detection Ability of Aniline in Water.

Copper(II)-paddlewheel-based metal-organic frameworks (CP-MOFs) represent a unique subclass of MOFs with highly predictable porous structures, facile syntheses, and functional open metal sites. However, the lack of high hydrolytic stability is an obstacle for CP-MOFs in many practical applications. In this work, we report a new CP-MOF, [Cu4(tdhb)] (BUT-155), which is constructed from a judiciously designed carboxylate ligand with high coordination connectivity (octatopic), abundant hydrophobic substituents (six methyl groups), and substituent constrained geometry (tetrahedral backbone), tdhb8- [H8tdhb = 3,3',5,5'-tetrakis(3,5-dicarboxyphenyl)-2,2',4,4',6,6'-hexamethylbiphenyl)]. BUT-155 shows high porosity with a Brunauer-Emmett-Teller surface area of 2070 m2/g. Quite interestingly, this CP-MOF retains its structural integrity after being treated in water for 10 days at room temperature or in boiling water for 24 h. To the best of our knowledge, BUT-155 represents the first CP-MOF that is demonstrated to retain its structural integrity in boiling water. The high hydrolytic stability of BUT-155 allowed us to carry out adsorption studies of water vapor and aqueous organic pollutants on it. Water-vapor adsorption reveals a sigmoidal isotherm and a high uptake (46.7 wt %), which is highly reversible and regenerable. In addition, because of the availability of soft-acid-type open Cu(II) sites, BUT-155 shows a high performance for selective adsorption of soft-base-type aniline over water or phenol, and a naked-eye detectable color change for the MOF sample accompanies this. The adsorption selectivity and high adsorption capacity of aniline in BUT-155 are also well-interpreted by single-crystal structures of the water- and aniline-included phases of BUT-155.

Preparation, characterization, and performance evaluation of UiO-66 analogues as stationary phase in HPLC for the separation of substituted benzenes and polycyclic aromatic hydrocarbons.

UiO-66 analogues are good candidates as stationary phase in HPLC because of their chemical/thermal stability, large surface area, and two cage structures. Here, two UiO-66 analogues, UiO-66-NH2 and UiO-67, were synthesized and used as stationary phase in HPLC to evaluate their performance in the separation of substituted benzenes (SBs) and polycyclic aromatic hydrocarbons (PAHs). The results showed that SBs could be well separated on UiO-66-NH2 column but not on UiO-67 column. Nonetheless, PAHs could be well separated on UiO-67 column. The separation mechanisms of SBs and PAHs on UiO-66 analogues may be involved in the pore size and functional group in the frameworks of UiO-66 analogues. Introduction of the-NH2 into UiO-66 significantly reduced its adsorption capacity for SB congeners, which resulted in less separation of SBs on UiO-66-NH2. As for the separation of PAHs on UiO-67 column, the π-π stacking effect was supposed to play a vital role.

A Base-Resistant Metalloporphyrin Metal-Organic Framework for C-H Bond Halogenation.

A base-resistant porphyrin metal-organic framework (MOF), namely PCN-602 has been constructed with 12-connected [Ni8(OH)4(H2O)2Pz12] (Pz = pyrazolate) cluster and a newly designed pyrazolate-based porphyrin ligand, 5,10,15,20-tetrakis(4-(pyrazolate-4-yl)phenyl)porphyrin under the guidance of the reticular synthesis strategy. Besides its robustness in hydroxide solution, PCN-602 also shows excellent stability in aqueous solutions of F-, CO32-, and PO43- ions. Interestingly, the Mn3+-porphyrinic PCN-602, as a recyclable MOF catalyst, presents high catalytic activity for the C-H bond halogenation reaction in a basic system, significantly outperforming its homogeneous counterpart. For the first time, a porphyrinic MOF was thus used as an efficient catalyst in a basic solution with coordinating anions, to the best of our knowledge.

Highly Stable Zr(IV)-Based Metal-Organic Frameworks for the Detection and Removal of Antibiotics and Organic Explosives in Water.

Antibiotics and organic explosives are among the main organic pollutants in wastewater; their detection and removal are quite important but challenging. As a new class of porous materials, metal-organic frameworks (MOFs) are considered as a promising platform for the sensing and adsorption applications. In this work, guided by a topological design approach, two stable isostructural Zr(IV)-based MOFs, Zr6O4(OH)8(H2O)4(CTTA)8/3 (BUT-12, H3CTTA = 5'-(4-carboxyphenyl)-2',4',6'-trimethyl-[1,1':3',1″-terphenyl]-4,4″-dicarboxylic acid) and Zr6O4(OH)8(H2O)4(TTNA)8/3 (BUT-13, H3TTNA = 6,6',6″-(2,4,6-trimethylbenzene-1,3,5-triyl)tris(2-naphthoic acid)) with the the-a topological structure constructed by D4h 8-connected Zr6 clusters and D3h 3-connected linkers were designed and synthesized. The two MOFs are highly porous with the Brunauer-Emmett-Teller surface area of 3387 and 3948 m(2) g(-1), respectively. Particularly, BUT-13 features one of the most porous water-stable MOFs reported so far. Interestingly, these MOFs represent excellent fluorescent properties, which can be efficiently quenched by trace amounts of nitrofurazone (NZF) and nitrofurantoin (NFT) antibiotics as well as 2,4,6-trinitrophenol (TNP) and 4-nitrophenol (4-NP) organic explosives in water solution. They are responsive to NZF and TNP at parts per billion (ppb) levels, which are among the best performing luminescent MOF-based sensing materials. Simultaneously, both MOFs also display high adsorption abilities toward these organic molecules. It was demonstrated that the adsorption plays an important role in the preconcentration of analytes, which can further increase the fluorescent quenching efficiency. These results indicate that BUT-12 and -13 are favorable materials for the simultaneous selective detection and removal of specific antibiotics and organic explosives from water, being potentially useful in monitoring water quality and treating wastewater.

Pyrazolate-Based Porphyrinic Metal-Organic Framework with Extraordinary Base-Resistance.

Guided by a top-down topological analysis, a metal-organic framework (MOF) constructed by pyrazolate-based porphyrinic ligand, namely, PCN-601, has been rationally designed and synthesized, and it exhibits excellent stability in alkali solutions. It is, to the best of our knowledge, the first identified MOF that can retain its crystallinity and porosity in saturated sodium hydroxide solution (∼ 20 mol/L) at room temperature and 100 °C. This almost pushes base-resistance of porphyrinic MOFs (even if MOFs) to the limit in aqueous media and greatly extends the range of their potential applications. In this work, we also tried to interpret the stability of PCN-601 from both thermodynamic and kinetic perspectives.

Structural and magnetic modulations of copper(II) azido complexes: unexpected in situ reactions of mono-N-donor pyridine-based co-ligands.

Low-temperature hydrothermal reactions of copper salts with NaN3 and structurally related pyridine-based ligands, 1-(4-pyridyl)pyridinium, 3-chloromethylpyridine, 4-benzylpyridine, and quinoline (L(4)), respectively, led to the formation of four new magnetic complexes, [Cu3(L(1))2(N3)6]n (), [Cu3(L(2))2(N3)6]n (), [Cu(L(3))2(N3)2] (), and [Cu(L(4))(N3)2]n (). In these complexes, L(1), L(2), and L(3) are pyridine, 3-azidomethylpyridine, and 4-benzoylpyridine, being generated in situ by the decomposition, azido substitution, and oxidation reaction of the 1-(4-pyridyl)pyridinium, 3-chloromethylpyridine, and 4-benzylpyridine, respectively. and have similar structures being composed of double end-on azido-bridging planar [Cu3(L)2(N3)6] trinuclear units, which are further linked into a two-dimensional layer by the end-to-end azido bridges of themselves, along with their weak end-on coordination. It is interesting that the only slight differences of geometrical parameters in and have led to distinct magnetic interactions between the trinuclear units, where the former is antiferromagnetic but the latter is ferromagnetic, whereas has a mono-nuclear core structure, which is further extended to a one-dimensional (1D) chain by weakly coordinated end-on azido bridges. consists of unique 1D chains with double end-on azido bridge bonding distorted five-coordinated Cu(ii) centers, and exhibits ferromagnetic intrachain interactions. In the structures of these complexes there also exist weak inter-layer or inter-chain hydrogen bonds, which should also be responsible for some magnetic behavior at low temperature. In addition, primary structural and magnetic comparisons and discussions have also been performed by combining other reported azido-Cu(ii) systems with related pyridyl-based co-ligands. These results show that the selection of synthesis conditions and slight decoration of co-ligands (or geometric differences of them) have important influences on the structures and magnetic properties of resulting metal azido complexes.

An in situ self-assembly template strategy for the preparation of hierarchical-pore metal-organic frameworks.

Metal-organic frameworks (MOFs) have recently emerged as a new type of nanoporous materials with tailorable structures and functions. Usually, MOFs have uniform pores smaller than 2 nm in size, limiting their practical applications in some cases. Although a few approaches have been adopted to prepare MOFs with larger pores, it is still challenging to synthesize hierarchical-pore MOFs (H-MOFs) with high structural controllability and good stability. Here we demonstrate a facile and versatile method, an in situ self-assembly template strategy for fabricating stable H-MOFs, in which multi-scale soluble and/or acid-sensitive metal-organic assembly (MOA) fragments form during the reactions between metal ions and organic ligands (to construct MOFs), and act as removable dynamic chemical templates. This general strategy was successfully used to prepare various H-MOFs that show rich porous properties and potential applications, such as in large molecule adsorption. Notably, the mesopore sizes of the H-MOFs can be tuned by varying the amount of templates.

4-Substituent pyridine directed cobalt(II) azides: solvothermal synthesis, structure, and magnetic properties.

The structure and magnetism of three cobalt(ii)-azide complexes, [Co(N3)2(bepy)2]n (), [Co2(N3)4(vipy)4]n (), and [Co(N3)2(bipy)]n () were tuned by three structurally related 4-substituent pyridines, 4-benzylpyridine (bepy), 4-vinyl pyridine (vipy), and 4,4'-bipyridine (bipy) as co-ligands in solvothermal reactions. With flexible benzyl as a substituent group of the pyridine co-ligand, a one-dimensional (1D) complex with double end-to-end (EE) azide-bridging Co(ii) chain is formed. While using a rigid but small vinyl group as the substituent, a distinct Co(ii)-azide chain with alternate double end-on (EO) and double EE azide bridges was obtained. Finally, when another pyridine group was used instead of the substituent incapable of coordinating in and , a bipyridine, it gave rise to a chiral complex with a three-dimensional (3D) diamondoid Co(ii)-azide framework further reinforced by the bipy ligand. Magnetic studies indicate antiferromagnetic interactions between the Co(ii) ions in the three complexes, but interestingly, weak antiferromagnetism origin of spin canting exists in at low temperatures.

Embedment of Ag(I)-organic frameworks into silica gels for microextraction of polybrominated diphenyl ethers in soils.

Three Ag(I)-organic frameworks, [Ag5(pydc)2(CN)]n, {[Ag4(pydc)2]CH3CN}n, and [Ag(4,4'-bpy)NO3]n, were synthesized and embedded into silica gels to form metal-organic-framework (MOF)-embedded gels for the microextraction of polybrominated diphenyl ethers (PBDEs) in soils. Despite the great differences in the structures of the organic ligands, all three Ag(I)-organic frameworks were found to effectively accumulate and concentrate PBDEs from sample solutions prepared with contaminated soil and purified water, indicating the important roles of Ag centers in PBDE extraction. Under the optimal experimental conditions (MOF mass, water volume, temperature, extraction time, and back-extraction time) for PBDE extraction from sample solutions, the detection limits of seven PBDEs (BDE-28, 47, 99, 100, 153, 154, and 183) ranged from 0.01 to 2.6ngg(-1) for [Ag5(pydc)2(CN)]n, 0.20-0.64ngg(-1) for {[Ag4(pydc)2]CH3CN}n, and 0.60-3.08ngg(-1) for [Ag(4,4'-bpy)NO3]n. The reproducibilities of the three methods were all satisfactory with relative standard deviations (RSDs) in the range of 2.2-9.6%, 5.3-10.4%, and 6.9-9.4% for [Ag5(pydc)2(CN)]n, {[Ag4(pydc)2]CH3CN}n, and [Ag(4,4'-bpy)NO3]n, respectively. The use of Ag(I)-organic frameworks for the microextraction of PBDEs was validated using both certified reference soils and field-contaminated soils, and the proposed methods are recommended as rapid and environmentally friendly alternatives for the extraction and determination of PBDEs in soils.

Separations of substituted benzenes and polycyclic aromatic hydrocarbons using normal- and reverse-phase high performance liquid chromatography with UiO-66 as the stationary phase.

Metal-organic frameworks (MOFs) have great potential for applications in chromatography due to their highly tailorable porous structures and unique properties. In this work, the stable MOF UiO-66 was evaluated as both a normal-phase (NP-) and a reverse-phase (RP-) stationary phase in the high performance liquid chromatography (HPLC) to separate substituted benzenes (SBs) and polycyclic aromatic hydrocarbons (PAHs). It was found that the mobile phase composition has a significant effect on the HPLC separation. Baseline RP-HPLC separations of xylene isomers; naphthalene and anthracene; naphthalene and chrysene; and naphthalene, fluorene, and chrysene were achieved using MeOH/H2O ratios of 80:20, 75:25, 85:15, and 75:25, respectively, on the UiO-66 column. Similarly, baseline NP-HPLC separations of xylene isomers and ethylbenzene; ethylbenzene, styrene, o-xylene, and m-xylene; and several PAHs were also obtained on the UiO-66 column with different mobile phase compositions. The relative standard deviations (RSDs) of retention time, peak height, peak area, and half peak width for five replicate separations of the tested analytes were within the ranges 0.2-0.4%, 0.2-1.6%, 0.7-3.9%, 0.4-1.1%, respectively. We also evaluated other critical HPLC parameters, including injected sample mass, column temperature, and the thermodynamic characters of both the RP-HPLC and the NP-HPLC separation processes. It was confirmed that the separation of SBs on a UiO-66 column was an exothermic process, controlled by both enthalpy change (ΔH) and entropy change (ΔS). The reverse shape selectivity, size selectivity, stacking effect, and electrostatic force played vital roles in the separations of these analytes. To the best of our knowledge, this method is one of the very few examples of using MOFs as the stationary phase in both NP-HPLC and RP-HPLC. MOF-based stationary phases may thus be applied in the separations and analyses of SBs and PAHs in environmental samples.

Hybrid membranes of metal-organic molecule nanocages for aromatic/aliphatic hydrocarbon separation by pervaporation.

Hybrid membranes composed of porous metal-organic molecule nanocages as fillers embedded in a hyperbranched polymer (Boltorn W3000) were fabricated, which exhibit excellent pervaporation separation performances towards aromatic/aliphatic hydrocarbons. The unique nature of the molecule-based fillers and their good dispersion and compatibility in/with the polymer are responsible for the good membrane properties.

Tuning CO2 selective adsorption over N2 and CH4 in UiO-67 analogues through ligand functionalization.

Introducing functional groups into pores of metal-organic frameworks (MOFs) through ligand modification provides an efficacious approach for tuning gas adsorption and separation performances of this type of novel porous material. In this work, two UiO-67 analogues, [Zr6O4(OH)4(FDCA)6] (BUT-10) and [Zr6O4(OH)4(DTDAO)6] (BUT-11), with functionalized pore surfaces and high stability were synthesized from two functional ligands, 9-fluorenone-2,7-dicarboxylic acid (H2FDCA) and dibenzo[b,d]thiophene-3,7-dicarboxylic acid 5,5-dioxide (H2DTDAO), respectively, and structurally determined by single-crystal X-ray diffraction. Notwithstanding skeleton bend of the two ligands relative to the linear 4,4'-biphenyldicarboxylic acid in UiO-67, the two MOFs have structures similar to that of UiO-67, with only lowered symmetry in their frameworks. Attributed to these additional functional groups (carbonyl and sulfone, respectively) in the ligands, BUT-10 and -11 show enhanced CO2 adsorption and separation selectivities over N2 and CH4, in spite of decreased pore sizes and surface areas compared with UiO-67. At 298 K and 1 atm, the CO2 uptake is 22.9, 50.6, and 53.5 cm(3)/g, and the infinite dilution selectivities of CO2/CH4 are 2.7, 5.1, and 9.0 and those of CO2/N2 are 9.4, 18.6, and 31.5 for UiO-67, BUT-10, and BUT-11, respectively. The selectivities of CO2/CH4 and CO2/N2 are thus enhanced 1.9 and 2.0 times in BUT-10 and 3.3 and 3.4 times in BUT-11, respectively, on the basis of UiO-67. The adsorption mechanism of CO2 in BUT-11 has also been explored through computational simulations. The results show that CO2 molecules locate around the sulfone groups in pore surfaces of BUT-11, verifying at the molecular level that sulfone groups significantly increase the affinity toward CO2 molecules of the framework. This provides thus an efficient strategy for the design of CO2 capture materials.