Photo Responsive Electron and Proton Conductivity within a Hydrogen-Bonded Organic Framework

Rational design of crystalline porous materials with coupled proton-electron transfer has not yet been reported to date. Herein, we report a donor-acceptor (D-A) π-π stacking hydrogen-bonded organic framework (HOF; HOF-FJU-36 ) with zwitterionic 1,1′-bis(3-carboxybenzyl)-4,4′-bipyridinium (H₂L²⁺) as acceptor and 2,7-naphthalene disulfonate (NDS²⁻) as donor to form a two-dimensional (2D) layer. Three water molecules were situated in the channels to connect with acidic species through hydrogen bonding interactions to give a 3D framework. The continuous π-π interactions along the a axis and the smooth H-bonding chain along the b axis provide the electron and proton transfer pathways, respectively. After 405 nm light irradiation, the photogenerated radicals could simultaneously endow HOF-FJU-36 with photoswitchable electron and proton conductivity due to coupled electron-proton transfer. By single-crystal X-ray diffraction (SCXRD) analyses, X-ray photoelectron spectroscopy (XPS), transient absorption spectra and density functional theory (DFT) calculations, the mechanism of the switchable conductivity upon irradiation has been demonstrated.     

Inverse CO2/C2H2 Separation with MFU-4 and Selectivity Reversal via Postsynthetic Ligand Exchange

Although many porous materials, including metal–organic frameworks (MOFs), have been reported to selectively adsorb C₂H₂ in C₂H₂/CO₂ separation processes, CO₂-selective sorbents are much less common. Here, we report the remarkable performance of MFU-4 (Zn₅Cl₄(bbta)₃, bbta=benzo-1,2,4,5-bistriazolate) toward inverse CO₂/C₂H₂ separation. The MOF facilitates kinetic separation of CO₂ from C₂H₂, enabling the generation of high purity C₂H₂ (>98 %) with good productivity in dynamic breakthrough experiments. Adsorption kinetics measurements and computational studies show C₂H₂ is excluded from MFU-4 by narrow pore windows formed by Zn−Cl groups. Postsynthetic F⁻/Cl⁻ ligand exchange was used to synthesize an analogue ( MFU-4-F ) with expanded pore apertures, resulting in equilibrium C₂H₂/CO₂ separation with reversed selectivity compared to MFU-4 . MFU-4-F also exhibits a remarkably high C₂H₂ adsorption capacity (6.7 mmol g⁻¹), allowing fuel grade C₂H₂ (98 % purity) to be harvested from C₂H₂/CO₂ mixtures by room temperature desorption.     

Tetranuclear CuII Cluster as the Ten Node Building Unit for the Construction of a Metal–Organic Framework for Efficient C2H2/CO2 Separation

Rational design of high nuclear copper cluster-based metal–organic frameworks has not been established yet. Herein, we report a novel MOF ( FJU-112 ) with the ten-connected tetranuclear copper cluster [Cu₄(PO₃)₂(μ₂-H₂O)₂(CO₂)₄] as the node which was capped by the deprotonated organic ligand of H₄L (3,5-Dicarboxyphenylphosphonic acid). With BPE (1,2-Bis(4-pyridyl)ethane) as the pore partitioner, the pore spaces in the structure of FJU-112 were divided into several smaller cages and smaller windows for efficient gas adsorption and separation. FJU-112 exhibits a high separation performance for the C₂H₂/CO₂ separation, which were established by the temperature-dependent sorption isotherms and further confirmed by the lab-scale dynamic breakthrough experiments. The grand canonical Monte Carlo simulations (GCMC) studies show that its high C₂H₂/CO₂ separation performance is contributed to the strong π-complexation interactions between the C₂H₂ molecules and framework pore surfaces, leading to its more C₂H₂ uptakes over CO₂ molecules.     

Overcoming the Trade-Off between C2H2 Sorption and Separation Performance by Regulating Metal-Alkyne Chemical Interaction in Metal-Organic Frameworks

Designing porous materials for C₂H₂ purification and safe storage is essential research for industrial utilization. We emphatically regulate the metal-alkyne interaction of Pd^II and Pt^II on C₂H₂ sorption and C₂H₂/CO₂ separation in two isostructural NbO metal–organic frameworks (MOFs), Pd/Cu-PDA and Pt/Cu-PDA . The experimental investigations and systematic theoretical calculations reveal that Pd^II in Pd/Cu-PDA undergoes spontaneous chemical reaction with C₂H₂, leading to irreversible structural collapse and loss of C₂H₂/CO₂ sorption and separation. Contrarily, Pt^II in Pt/Cu-PDA shows strong di-σ bond interaction with C₂H₂ to form specific π-complexation, contributing to high C₂H₂ capture (28.7 cm³ g⁻¹ at 0.01 bar and 153 cm³ g⁻¹ at 1 bar). The reusable Pt/Cu-PDA efficiently separates C₂H₂ from C₂H₂/CO₂ mixtures with satisfying selectivity and C₂H₂ capacity (37 min g⁻¹). This research provides valuable insight into designing high-performance MOFs for gas sorption and separation.     

A Microporous Metal-Organic Framework with Unique Aromatic Pore Surfaces for High Performance C2H6/C2H4 Separation

Developing adsorptive separation processes based on C₂H₆-selective sorbents to replace energy-intensive cryogenic distillation is a promising alternative for C₂H₄ purification from C₂H₄/C₂H₆ mixtures, which however remains challenging. During our studies on two isostructural metal–organic frameworks ( Ni-MOF 1 and Ni-MOF 2 ), we found that Ni-MOF 2 exhibited significantly higher performance for C₂H₆/C₂H₄ separation than Ni-MOF-1 , as clearly established by gas sorption isotherms and breakthrough experiments. Density-Functional Theory (DFT) studies showed that the unblocked unique aromatic pore surfaces within Ni-MOF 2 induce more and stronger C−H⋅⋅⋅π with C₂H₆ over C₂H₄ while the suitable pore spaces enforce its high C₂H₆ uptake capacity, featuring Ni-MOF 2 as one of the best porous materials for this very important gas separation. It generates 12 L kg⁻¹ of polymer-grade C₂H₄ product from equimolar C₂H₆/C₂H₄ mixtures at ambient conditions.     

Hydrogen-Bonded Organic Framework to Upgrade Cycling Stability and Rate Capability of Li-CO2 Batteries

Elaborately designed multifunctional electrocatalysts capable of promoting Li⁺ and CO₂ transport are essential for upgrading the cycling stability and rate capability of Li-CO₂ batteries. Hydrogen-bonded organic frameworks (HOFs) with open channels and easily functionalized surfaces hold great potential for applications in efficient cathodes of Li-CO₂ batteries. Herein, a robust HOF_S (HOF-FJU-1) is introduced for the first time as a co-catalyst in the cathode material of Li-CO₂ batteries. HOF-FJU-1 with cyano groups located periodically in the pore can induce homogeneous deposition of discharge products and accommodate volumetric expansion of discharge products during cycling. Besides, HOF-FJU-1 enables effective interaction between Ru⁰ nanoparticles and cyano groups, thus forming efficient and uniform catalytic sites for CRR/CER. Moreover, HOF-FJU-1 with regularly arranged open channels are beneficial for CO₂ and Li⁺ transport, enabling rapid redox kinetic conversion of CO₂. Therefore, the HOF-based Li-CO₂ batteries are capable of stable operation at 400 mA g⁻¹ for 1800 h and maintain a low overpotential of 1.96 V even at high current densities up to 5 A g⁻¹. This work provides valuable guidance for developing multifunctional HOF-based catalysts to upgrade the longevity and rate capability of Li-CO₂ batteries.     

A Microporous Hydrogen-Bonded Organic Framework Based on Hydrogen-Bonding Tetramers for Efficient Xe/Kr Separation

Hydrogen-bonded organic frameworks (HOFs) have been emerging as a new type of very promising microporous materials for gas separation and purification, but few HOFs structures constructed through hydrogen-bonding tetramers have been explored in this field. Herein, we report the first microporous HOF (termed as HOF-FJU-46) afforded by hydrogen-bonding tetramers with 4-fold interpenetrated diamond networks, which shows excellent chemical and thermal stability. What's more, activated HOF-FJU-46 exhibits the highest xenon (Xe) uptake of 2.51 mmol g⁻¹ and xenon/krypton (Kr) selectivity of 19.9 at the ambient condition among the reported HOFs up to date. Dynamic breakthrough tests confirmed the excellent Xe/Kr separation of HOF-FJU-46a, showing high Kr productivity (110 mL g⁻¹) and Xe uptake (1.29 mmol g⁻¹), as well as good recyclability. The single crystal X-ray diffraction and the molecular simulations revealed that the abundant accessible aromatic and pyrazole rings in the pore channels of HOF-FJU-46a can provide the multiple strong C−H⋅⋅⋅Xe interactions with Xe atoms.     

Construction of a Stable Crystalline Polyimide Porous Organic Framework for C2H2/C2H4 and CO2/N2 Separation

Utilization of porous materials for gas capture and separation is a hot research topic. Removal of acetylene (C₂H₂) from ethylene (C₂H₄) is important in the oil refining and petrochemical industries, since C₂H₂ impurities deactivate the catalysts and terminate the polymerization of C₂H₄. Carbon dioxide (CO₂) emission from power plants contributes to global climate change and threatens the survival of life on this planet. Herein, 2D crystalline polyimide porous organic framework PAF-120, which was constructed by imidization of linear naphthalene-1,4,5,8-tetracarboxylic dianhydride and triangular 1,3,5-tris(4-aminophenyl)benzene, showed significant thermal and chemical stability. Low-pressure gas adsorption isotherms revealed that PAF-120 exhibits good selective adsorption of C₂H₂ over C₂H₄ and CO₂ over N₂. At 298 K and 1 bar, its C₂H₂ and CO₂ selectivities were predicted to be 4.1 and 68.7, respectively. More importantly, PAF-120 exhibits the highest selectivity for C₂H₂/C₂H₄ separation among porous organic frameworks. Thus PAF-120 could be a suitable candidate for selective separation of C₂H₂ over C₂H₄ and CO₂ over N₂.     

Highly Robust Microporous Metal-Organic Frameworks for Efficient Ethylene Purification under Dry and Humid Conditions

Two C₂H₆-selective metal-organic framework (MOF) adsorbents with ultrahigh stability, high surface areas, and suitable pore size have been designed and synthesized for one-step separation of ethane/ethylene (C₂H₆/C₂H₄) under humid conditions to produce polymer-grade pure C₂H₄. Experimental results reveal that these two MOFs not only adsorb a high amount of C₂H₆ but also display good C₂H₆/C₂H₄ selectivity verified by fixed bed column breakthrough experiments. Most importantly, the good water stability and hydrophobic pore environments make these two MOFs capable of efficiently separating C₂H₆/C₂H₄ under humid conditions, exhibiting the benchmark performance among all reported adsorbents for separation of C₂H₆/C₂H₄ under humid conditions. Moreover, the affinity sites and their static adsorption energies were successfully revealed by single crystal data and computation studies. Adsorbents described in this work can be used to address major chemical industrial challenges.     

Bioinspired Design of a Giant [Mn86] Nanocage-Based Metal-Organic Framework with Specific CO2 Binding Pockets for Highly Selective CO2 Separation

Adsorption-based removal of carbon dioxide (CO₂) from gas mixtures has demonstrated great potential for solving energy security and environmental sustainability challenges. However, due to similar physicochemical properties between CO₂ and other gases as well as the co-adsorption behavior, the selectivity of CO₂ is severely limited in currently reported CO₂-selective sorbents. To address the challenge, we create a bioinspired design strategy and report a robust, microporous metal–organic framework (MOF) with unprecedented [Mn₈₆] nanocages. Attributed to the existence of unique enzyme-like confined pockets, strong coordination interactions and dipole-dipole interactions are generated for CO₂ molecules, resulting in only CO₂ molecules fitting in the pocket while other gas molecules are prohibited. Thus, this MOF can selectively remove CO₂ from various gas mixtures and show record-high selectivities of CO₂/CH₄ and CO₂/N₂ mixtures. Highly efficient CO₂/C₂H₂, CO₂/CH₄, and CO₂/N₂ separations are achieved, as verified by experimental breakthrough tests. This work paves a new avenue for the fabrication of adsorbents with high CO₂ selectivity and provides important guidance for designing highly effective adsorbents for gas separation.     

Ultramicroporous Building Units as a Path to Bi‐microporous Metal–Organic Frameworks with High Acetylene Storage and Separation Performance

A strategy called ultramicroporous building unit (UBU) is introduced. It allows the creation of hierarchical bi‐porous features that work in tandem to enhance gas uptake capacity and separation. Smaller pores from UBUs promote selectivity, while larger inter‐UBU packing pores increase uptake capacity. The effectiveness of this UBU strategy is shown with a cobalt MOF (denoted SNNU‐45) in which octahedral cages with 4.5 Å pore size serve as UBUs. The C₂H₂ uptake capacity at 1 atm reaches 193.0 cm³ g^?1 (8.6 mmol g^?1) at 273 K and 134.0 cm³ g^?1 (6.0 mmol g^?1) at 298 K. Such high uptake capacity is accompanied by a high C₂H₂/CO₂ selectivity of up to 8.5 at 298 K. Dynamic breakthrough studies at room temperature and 1 atm show a C₂H₂/CO₂ breakthrough time up to 79 min g^?1, among top‐performing MOFs. Grand canonical Monte Carlo simulations agree that ultrahigh C₂H₂/CO₂ selectivity is mainly from UBU ultramicropores, while packing pores promote C₂H₂ uptake capacity.     

Mixed Metal–Organic Framework with Multiple Binding Sites for Efficient C2H2/CO2 Separation

The separation of C₂H₂/CO₂ is particularly challenging owing to their similarities in physical properties and molecular sizes. Reported here is a mixed metal–organic framework (M′MOF), [Fe(pyz)Ni(CN)₄] ( FeNi‐M′MOF , pyz=pyrazine), with multiple functional sites and compact one‐dimensional channels of about 4.0 Å for C₂H₂/CO₂ separation. This MOF shows not only a remarkable volumetric C₂H₂ uptake of 133 cm³ cm^?3, but also an excellent C₂H₂/CO₂ selectivity of 24 under ambient conditions, resulting in the second highest C₂H₂‐capture amount of 4.54 mol L^?1, thus outperforming most previous benchmark materials. The separation performance of this material is driven by π–π stacking and multiple intermolecular interactions between C₂H₂ molecules and the binding sites of FeNi‐M′MOF . This material can be facilely synthesized at room temperature and is water stable, highlighting FeNi‐M′MOF as a promising material for C₂H₂/CO₂ separation.     

Mixed Metal–Organic Framework with Multiple Binding Sites for Efficient C2H2/CO2 Separation

The separation of C₂H₂/CO₂ is particularly challenging owing to their similarities in physical properties and molecular sizes. Reported here is a mixed metal–organic framework (M′MOF), [Fe(pyz)Ni(CN)₄] ( FeNi-M′MOF , pyz=pyrazine), with multiple functional sites and compact one-dimensional channels of about 4.0 Å for C₂H₂/CO₂ separation. This MOF shows not only a remarkable volumetric C₂H₂ uptake of 133 cm³ cm⁻³, but also an excellent C₂H₂/CO₂ selectivity of 24 under ambient conditions, resulting in the second highest C₂H₂-capture amount of 4.54 mol L⁻¹, thus outperforming most previous benchmark materials. The separation performance of this material is driven by π–π stacking and multiple intermolecular interactions between C₂H₂ molecules and the binding sites of FeNi-M′MOF . This material can be facilely synthesized at room temperature and is water stable, highlighting FeNi-M′MOF as a promising material for C₂H₂/CO₂ separation.     

Two –COOH Decorated Anionic Metal‐organic Frameworks with Open Cu2+ Sites Afforded Highly C2H2/CO2 and C2H2/CH4 Separation and Removal of Organic Dyes

An anionic multifunctional porous metal organic framework (MOF), [Cu₂THBA(H₂O)₂] · (C₃H₇NO)₁₂ · (H₂O)₁₀ ( 1 ) (H₄THBA = p‐terphenyl‐3,2′′,3′′,5,5′′,5′′′‐ hexcarboxylic acid) with NbO‐type topology was synthesized and characterized. Due to multiple functional sites and suitable pore size, the desolvated compound 1a exhibits high separation selectivity for C₂H₂/CO₂ of 30 and C₂H₂/CH₄ of 131 at 1 kPa at room temperature. Compound 1 can also efficiently and completely separate methylene blue (MB⁺) molecules of low concentrations from aqueous solution in 12 h.     

Rational Design of Microporous MOFs with Anionic Boron Cluster Functionality and Cooperative Dihydrogen Binding Sites for Highly Selective Capture of Acetylene

Separation of acetylene (C₂H₂) from carbon dioxide (CO₂) or ethylene (C₂H₄) is important in industry but limited by the low capacity and selectivity owing to their similar molecular sizes and physical properties. Herein, we report two novel dodecaborate‐hybrid metal–organic frameworks, MB₁₂H₁₂(dpb)₂ (termed as BSF‐3 and BSF‐3‐Co for M=Cu and Co), for highly selective capture of C₂H₂. The high C₂H₂ capacity and remarkable C₂H₂/CO₂ selectivity resulted from the unique anionic boron cluster functionality as well as the suitable pore size with cooperative proton‐hydride dihydrogen bonding sites (B?H^δ????H^δ+?C≡C?H^δ+???H^δ??B). This new type of C₂H₂‐specific functional sites represents a fresh paradigm distinct from those in previous leading materials based on open metal sites, strong electrostatics, or hydrogen bonding.     

Ortho-Alkoxy-benzamide Directed Formation of a Single Crystalline Hydrogen-bonded Crosslinked Organic Framework and Its Boron Trifluoride Uptake and Catalysis

Boron trifluoride (BF₃) is a highly corrosive gas widely used in industry. Confining BF₃ in porous materials ensures safe and convenient handling and prevents its degradation. Hence, it is highly desired to develop porous materials with high adsorption capacity, high stability, and resistance to BF₃ corrosion. Herein, we designed and synthesized a Lewis basic single-crystalline hydrogen-bond crosslinked organic framework (H_COF-50) for BF₃ storage and its application in catalysis. Specifically, we introduced self-complementary ortho-alkoxy-benzamide hydrogen-bonding moieties to direct the formation of highly organized hydrogen-bonded networks, which were subsequently photo-crosslinked to generate H_COFs. The H_COF-50 features Lewis basic thioether linkages and electron-rich pore surfaces for BF₃ uptake. As a result, H_COF-50 shows a record-high 14.2 mmol/g BF₃ uptake capacity. The BF₃ uptake in H_COF-50 is reversible, leading to the slow release of BF₃. We leveraged this property to reduce the undesirable chain transfer and termination in the cationic polymerization of vinyl ethers. Polymers with higher molecular weights and lower polydispersity were generated compared to those synthesized using BF₃ ⋅ Et₂O. The elucidation of the structure–property relationship, as provided by the single-crystal X-ray structures, combined with the high BF₃ uptake capacity and controlled sorption, highlights the molecular understanding of framework-guest interactions in addressing contemporary challenges.     

A Porphyrin‐Based Porous rtl Metal–Organic Framework as an Efficient Catalyst for the Cycloaddition of CO2 to Epoxides

A porous rtl metal–organic framework (MOF) [Mn₅L(H₂O)₆?(DMA)₂]?5DMA?4C₂H₅OH ( 1? Mn) (H₁₀L=5,10,15,20‐tetra(4‐(3,5‐dicarboxylphenoxy)phenyl)porphyrin; DMA=N,N′‐dimethylacetamide) was synthesized by employing a new porphyrin‐based octacarboxylic acid ligand. 1? Mn exhibits high Mn^II density in the porous framework, providing it great Lewis‐acid heterogeneous catalytic capability for the cycloaddition of CO₂ with epoxides. Strikingly, 1? Mn features excellent catalytic activity to the cycloaddition of CO₂ to epoxides, with a remarkable initial turnover frequency 400 per mole of catalyst per hour at 20 atm. As‐synthesized 1? Mn also exhibits size selectivity to different epoxide substrates on account of their steric hindrance. The high catalytic activity, size selectivity, and stability toward the epoxides on catalytic cycloaddition of CO₂ make 1? Mn a promising heterogeneous catalyst for fixation and utilization of CO₂.     

Structure Regulation of MOF Nanosheet Membrane for Accurate H2/CO2 Separation

High-purity H₂ production accompanied with a precise decarbonization opens an avenue to approach a carbon-neutral society. Metal–organic framework nanosheet membranes provide great opportunities for an accurate and fast H₂/CO₂ separation, CO₂ leakage through the membrane interlayer galleries decided the ultimate separation accuracy. Here we introduce low dose amino side groups into the Zn₂(benzimidazolate)₄ conformation. Physisorbed CO₂ served as interlayer linkers, gently regulated and stabilized the interlayer spacing. These evoked a synergistic effect of CO₂ adsorption-assisted molecular sieving and steric hinderance, whilst exquisitely preserving apertures for high-speed H₂ transport. The optimized amino membranes set a new record for ultrathin nanosheet membranes in H₂/CO₂ separation (mixture separation factor: 1158, H₂ permeance: 1417 gas permeation unit). This strategy provides an effective way to customize ultrathin nanosheet membranes with desirable molecular sieving ability.     

Topological Design of Unprecedented Metal-Organic Frameworks Featuring Multiple Anion Functionalities and Hierarchical Porosity for Benchmark Acetylene Separation

Separation of acetylene (C₂H₂) from carbon dioxide (CO₂) or ethylene (C₂H₄) is industrially important but still challenging so far. Herein, we developed two novel robust metal organic frameworks AlFSIX-Cu-TPBDA (ZNU-8) with znv topology and SIFSIX-Cu-TPBDA (ZNU-9) with wly topology for efficient capture of C₂H₂ from CO₂ and C₂H₄. Both ZNU-8 and ZNU-9 feature multiple anion functionalities and hierarchical porosity. Notably, ZNU-9 with more anionic binding sites and three distinct cages displays both an extremely large C₂H₂ capacity (7.94 mmol/g) and a high C₂H₂/CO₂ (10.3) or C₂H₂/C₂H₄ (11.6) selectivity. The calculated capacity of C₂H₂ per anion (4.94 mol/mol at 1 bar) is the highest among all the anion pillared metal organic frameworks. Theoretical calculation indicated that the strong cooperative hydrogen bonds exist between acetylene and the pillared SiF₆²⁻ anions in the confined cavity, which is further confirmed by in situ IR spectra. The practical separation performance was explicitly demonstrated by dynamic breakthrough experiments with equimolar C₂H₂/CO₂ mixtures and 1/99 C₂H₂/C₂H₄ mixtures under various conditions with excellent recyclability and benchmark productivity of pure C₂H₂ (5.13 mmol/g) or C₂H₄ (48.57 mmol/g).     

Ultramicropore Engineering by Dehydration to Enable Molecular Sieving of H2 by Calcium Trimesate

The high energy footprint of commodity gas purification and increasing demand for gases require new approaches to gas separation. Kinetic separation of gas mixtures through molecular sieving can enable separation by molecular size or shape exclusion. Physisorbents must exhibit the right pore diameter to enable separation, but the 0.3–0.4 nm range relevant to small gas molecules is hard to control. Herein, dehydration of the ultramicroporous metal–organic framework Ca‐trimesate, Ca(HBTC)?H₂O (H₃BTC=trimesic acid), bnn‐1‐Ca‐H₂O, affords a narrow pore variant, Ca(HBTC), bnn‐1‐Ca. Whereas bnn‐1‐Ca‐H₂O (pore diameter 0.34 nm) exhibits ultra‐high CO₂/N₂, CO₂/CH₄, and C₂H₂/C₂H₄ binary selectivity, bnn‐1‐Ca (pore diameter 0.31 nm) offers ideal selectivity for H₂/CO₂ and H₂/N₂ under cryogenic conditions. Ca‐trimesate, the first physisorbent to exhibit H₂ sieving under cryogenic conditions, could be a prototype for a general approach to exert precise control over pore diameter in physisorbents.