Data-driven design of metal-organic frameworks for wet flue gas CO2 capture.

Limiting the increase of CO2 in the atmosphere is one of the largest challenges of our generation1. Because carbon capture and storage is one of the few viable technologies that can mitigate current CO2 emissions2, much effort is focused on developing solid adsorbents that can efficiently capture CO2 from flue gases emitted from anthropogenic sources3. One class of materials that has attracted considerable interest in this context is metal-organic frameworks (MOFs), in which the careful combination of organic ligands with metal-ion nodes can, in principle, give rise to innumerable structurally and chemically distinct nanoporous MOFs. However, many MOFs that are optimized for the separation of CO2 from nitrogen4-7 do not perform well when using realistic flue gas that contains water, because water competes with CO2 for the same adsorption sites and thereby causes the materials to lose their selectivity. Although flue gases can be dried, this renders the capture process prohibitively expensive8,9. Here we show that data mining of a computational screening library of over 300,000 MOFs can identify different classes of strong CO2-binding sites-which we term 'adsorbaphores'-that endow MOFs with CO2/N2 selectivity that persists in wet flue gases. We subsequently synthesized two water-stable MOFs containing the most hydrophobic adsorbaphore, and found that their carbon-capture performance is not affected by water and outperforms that of some commercial materials. Testing the performance of these MOFs in an industrial setting and consideration of the full capture process-including the targeted CO2 sink, such as geological storage or serving as a carbon source for the chemical industry-will be necessary to identify the optimal separation material.

Biomimetic Photodegradation of Glyphosate in Carborane-Functionalized Nanoconfined Spaces.

The removal of organophosphorus (OP) herbicides from water has been studied using adsorptive removal, chemical oxidation, electrooxidation, enzymatic degradation, and photodegradation. The OP herbicide glyphosate (GP) is one of the most used herbicides worldwide, leading to excess GP in wastewater and soil. GP is commonly broken down in environmental conditions to compounds such as aminomethylphosphonic acid (AMPA) or sarcosine, with AMPA having a longer half-life and similar toxicity to GP. Metal-organic frameworks (MOFs) are excellent materials for purifying OP herbicides from water due to their ability to combine adsorption and photoactivity within one material. Herein, we report the use of a robust Zr-based MOF with a meta-carborane carboxylate ligand (mCB-MOF-2) to examine the adsorption and photodegradation of GP. The maximum adsorption capacity of mCB-MOF-2 for GP was determined to be 11.4 mmol/g. Non-covalent intermolecular forces between the carborane-based ligand and GP within the micropores of mCB-MOF-2 are thought to be responsible for strong binding affinity and capture of GP. After 24 h of irradiation with ultraviolet-visible (UV-vis) light, mCB-MOF-2 selectively converts 69% of GP to sarcosine and orthophosphate, following the C-P lyase enzymatic pathway and biomimetically photodegrading GP. Circumventing the production of AMPA is desirable, as it has a longer half-life and similar toxicity to GP. The exceptional adsorption capacity of GP by mCB-MOF-2 and its biomimetic photodegradation to non-toxic sarcosine make it a promising material for removing OP herbicides from water.

Photoactive Organo-Sulfur Polymers for Hydrogen Generation.

Herein, we report the synthesis of photoactive polymeric organo-sulfur (POS) materials. These polymers absorb light in the ultraviolet/visible and near-infrared region of the solar spectrum, and upon irradiation, they reduce water to hydrogen (H2 ). The decoration of POS materials with nitrile (-CN) groups is found to be the critical factor for enhanced interactions with the co-catalyst, Ni2 P, leading to greater H2 evolution rates compared to the nitrile-free POS material.

Hypsochromically-shifted Emission of Metal-organic Frameworks Generated through Post-synthetic Ligand Reduction.

Luminescent materials with tunable emission are becoming increasingly desirable as we move towards needing efficient Light Emitting Diodes (LEDs) for displays. Key to developing better displays is the advancement of strategies for rationally designing emissive materials that are tunable and efficient. We report a series of emissive metal-organic frameworks (MOFs) generated using BUT-10 (BUT: Beijing University of Technology) that emits green light with λmax at 525 nm. Post-synthetic reduction of the ketone on the fluorenone ligand in BUT-10 generates new materials, BUT-10-M and BUT-10-R. The emission for BUT-10-R is hypsochromically-shifted by 113 nm. Multivariate BUT-10-M structures demonstrate emission with two maxima corresponding to the emission of both fluorenol and fluorenone moieties present in their structures. Our study represents a novel post-synthetic ligand reduction strategy for producing emissive MOFs with tunable emission ranging from green, white-blue to deep blue.

Strengthening Aqueous Electrolytes without Strengthening Water.

Aqueous electrolytes typically suffer from poor electrochemical stability; however, eutectic aqueous solutions-25 wt.% LiCl and 62 wt.% H3 PO4 -cooled to -78 °C exhibit a significantly widened stability window. Integrated experimental and simulation results reveal that, upon cooling, Li+ ions become less hydrated and pair up with Cl- , ice-like water clusters form, and H⋅⋅⋅Cl- bonding strengthens. Surprisingly, this low-temperature solvation structure does not strengthen water molecules' O-H bond, bucking the conventional wisdom that increasing water's stability requires stiffening the O-H covalent bond. We propose a more general mechanism for water's low temperature inertness in the electrolyte: less favorable solvation of OH- and H+ , the byproducts of hydrogen and oxygen evolution reactions. To showcase this stability, we demonstrate an aqueous Li-ion battery using LiMn2 O4 cathode and CuSe anode with a high energy density of 109 Wh/kg. These results highlight the potential of aqueous batteries for polar and extraterrestrial missions.

A Highly Water-Stable meta-Carborane-Based Copper Metal-Organic Framework for Efficient High-Temperature Butanol Separation.

Biofuels are considered sustainable and renewable alternatives to conventional fossil fuels. Biobutanol has recently emerged as an attractive option compared to bioethanol and biodiesel, but a significant challenge in its production lies in the separation stage. The current industrial process for the production of biobutanol includes the ABE (acetone-butanol-ethanol) fermentation process from biomass; the resulting fermentation broth has a butanol concentration of no more than 2 wt% (the rest is essentially water). Therefore, the development of a cost-effective process for separation of butanol from dilute aqueous solutions is highly desirable. The use of porous materials for the adsorptive separation of ABE mixtures is considered a highly promising route, as these materials can potentially have high affinities for alcohols and low affinities for water. To date, zeolites have been tested toward this separation, but their hydrophilic nature makes them highly incompetent for this application. The use of metal-organic frameworks (MOFs) is an apparent solution; however, their low hydrolytic stabilities hinder their implementation in this application. So far, a few nanoporous zeolitic imidazolate frameworks (ZIFs) have shown excellent potential for butanol separation due to their good hydrolytic and thermal stabilities. Herein, we present a novel, porous, and hydrophobic MOF based on copper ions and carborane-carboxylate ligands, mCB-MOF-1, for butanol recovery. mCB-MOF-1 exhibits excellent stability when immersed in organic solvents, water at 90 °C for at least two months, and acidic and basic aqueous solutions. We found that, like ZIF-8, mCB-MOF-1 is non-porous to water (type II isotherm), but it has higher affinity for ethanol, butanol, and acetone compared to ZIF-8, as suggested by the shape of the vapor isotherms at the crucial low-pressure region. This is reflected in the separation of a realistic ABE mixture in which mCB-MOF-1 recovers butanol more efficiently compared to ZIF-8 at 333 K.

Sustainable Capture of Aromatic Volatile Organic Compounds by a Pyrene-Based Metal-Organic Framework under Humid Conditions.

The threat posed by the presence of artificial volatile organic compounds (VOCs) in the environment is a widely acknowledged fact, both for environmental issues and human health concerns. Ever-increasing production requires the continuous development of technologies toward the removal of these substances. In recent years, metal-organic frameworks (MOFs) have shown a great promise toward the capture of VOCs, but their stability in humid conditions still remains a major challenge, thus hindering their widespread development. To tackle this obstacle, we designed a 3-dimensional and porous MOF, named SION-82, for the capture of small aromatic VOCs, relying solely on π-π interactions. SION-82 captures benzene efficiently (107 mg/g) in dry conditions, and no uptake decrease was observed in the presence of high relative humidity for at least six cycles. Unlike HKUST-1 and MOF-74(Co), SION-82 possesses two vital characteristics toward sustainable benzene capture under humid conditions: moisture stability and reusability. In addition, SION-82 captures benzene under humid conditions more efficiently compared to the hydrolytically stable UiO-66, highlighting the impact of having an active site for benzene capture that is not affected by water. SION-82 can additionally capture other aromatic VOCs, showing pyridine and thiophene uptake capacities of 140 and 160 mg/g, respectively.

CO2 Methanation via Amino Alcohol Relay Molecules Employing a Ruthenium Nanoparticle/Metal Organic Framework Catalyst.

Methanation of carbon dioxide (CO2 ) is attractive within the context of a renewable energy refinery. Herein, we report an indirect methanation method that harnesses amino alcohols as relay molecules in combination with a catalyst comprising ruthenium nanoparticles (NPs) immobilized on a Lewis acidic and robust metal-organic framework (MOF). The Ru NPs are well dispersed on the surface of the MOF crystals and have a narrow size distribution. The catalyst efficiently transforms amino alcohols to oxazolidinones (upon reaction with CO2 ) and then to methane (upon reaction with hydrogen), simultaneously regenerating the amino alcohol relay molecule. This protocol provides a sustainable, indirect way for CO2 methanation as the process can be repeated multiple times.

Selective, Fast-Response, and Regenerable Metal-Organic Framework for Sampling Excess Fluoride Levels in Drinking Water.

Prolonged consumption of water contaminated with fluoride ions (F-) at concentrations exceeding 1.5 ppm can lead to considerable health implications, particularly in children and developing embryos. With irreversible and potentially severe forms of fluoride (F-) toxicity such as skeletal fluorosis being endemic in at least 25 countries, constructing affordable, remote-access, reliable water-sampling methods for F- contamination is an important goal. In this work, we present a novel lanthanide-based luminescent metal-organic framework, named SION-105, with a boron (B) receptor site whose interactions with F- in aqueous solutions are simultaneously electrostatic and specific in nature because of its carefully designed structural environment. This allows the material to be easily regenerated and used over 10 cycles, setting it apart from most existing molecular and polymeric F- sensors. SION-105 has been combined with a portable prototype sampling device that was designed and built in-house to measure F- concentrations in natural groundwater samples taken from three different countries, with the results showing excellent agreement with ion chromatography analysis.

Incarceration of Iodine in a Pyrene-Based Metal-Organic Framework.

A pyrene-based metal-organic framework (MOF) SION-8 captured iodine (I2 ) vapor with a capacity of 460 and 250 mg g-1 MOF at room temperature and 75 °C, respectively. Single-crystal X-ray diffraction analysis and van-der-Waals-corrected density functional theory calculations confirmed the presence of I2 molecules within the pores of SION-8 and their interaction with the pyrene-based ligands. The I2 -pyrene interactions in the I2 -loaded SION-8 led to a 104 -fold increase of its electrical conductivity compared to the bare SION-8. Upon adsorption, ≥95 % of I2 molecules were incarcerated and could not be washed out, signifying the potential of SION-8 towards the permanent capture of radioactive I2 at room temperature.

In†Situ Formation of Frustrated Lewis Pairs in a Water-Tolerant Metal-Organic Framework for the Transformation of CO2.

Frustrated Lewis pairs (FLPs) consist of sterically hindered Lewis acids and Lewis bases, which provide high catalytic activity towards non-metal-mediated activation of "inert" small molecules, including CO2 among others. One critical issue of homogeneous FLPs, however, is their instability upon recycling, leading to catalytic deactivation. Herein, we provide a solution to this issue by incorporating a bulky Lewis acid-functionalized ligand into a water-tolerant metal-organic framework (MOF), named SION-105, and employing Lewis basic diamine substrates for the in situ formation of FLPs within the MOF. Using CO2 as a C1-feedstock, this combination allows for the efficient transformation of a variety of diamine substrates into benzimidazoles. SION-105 can be easily recycled by washing with MeOH and reused multiple times without losing its identity and catalytic activity, highlighting the advantage of the MOF approach in FLP chemistry.

Shedding Light on the Protonation States and Location of Protonated N Atoms of Adenine in Metal-Organic Frameworks.

We report the syntheses and structures of five metal-organic frameworks (MOFs) based on transition metals (NiII, CuII, and ZnII), adenine, and di-, tri-, and tetra-carboxylate ligands. Adenine, with multiple N donor sites, was found to coordinate to the metal centers in different binding modes including bidentate (through N7 and N9, or N3 and N9) and tridentate (through N3, N7, and N9). Systematic investigations of the protonation states of adenine in each MOF structure via X-ray photoelectron spectroscopy revealed that adenine can be selectively protonated through N1, N3, or N7. The positions of H atoms connected to the N atoms were found from the electron density maps, and further supported by the study of C-N-C bond angles compared to the literature reports. DFT calculations were performed to geometrically optimize and energetically assess the structures simulated with different protonation modes. The present study highlights the rich coordination chemistry of adenine and provides a method for the determination of its protonation states and the location of protonated N atoms of adenine within MOFs, a task that would be challenging in complicated adenine-based MOF structures.

A Recyclable Metal-Organic Framework as a Dual Detector and Adsorbent for Ammonia.

Recyclable materials for simultaneous detection and uptake of ammonia (NH3 ) are of great interest due to the hazardous nature of NH3 . The structural versatility and porous nature of metal-organic frameworks (MOFs) make them ideal candidates for NH3 capture. Herein, the synthesis of a water-stable and porous 3-dimensional CuII -based MOF (SION-10) displaying a ship-in-a-bottle structure is reported; the pores of the host SION-10 framework accommodate mononuclear CuII -complexes. SION-10 spontaneously uptakes NH3 as a result of two concurrent mechanisms: chemisorption due to the presence of active CuII sites and physisorption (bulk permanent porosity). The color of the material changes from green to blue upon NH3 capture, with the shifts of the UV/Vis absorption bands clearly seen at NH3 concentrations as low as 300 ppm. SION-10 can be recovered upon immersion of SION-10⊃NH3 in water and can be further reused for NH3 capture for at least three cycles.

Switchable Surface Hydrophobicity-Hydrophilicity of a Metal-Organic Framework.

Materials with surfaces that can be switched from high/superhydrophobicity to superhydrophilicity are useful for myriad applications. Herein, we report a metal-organic framework (MOF) assembled from ZnII ions, 1,4-benzenedicarboxylate, and a hydrophobic carborane-based linker. The MOF crystal-surface can be switched between hydrophobic and superhydrophilic through a chemical treatment to remove some of the building blocks.

Engineering Homochiral Metal-Organic Frameworks by Spatially Separating 1D Chiral Metal-Peptide Ladders: Tuning the Pore Size for Enantioselective Adsorption.

The reaction of the chiral dipeptide glycyl-L(S)-glutamate with Co(II) ions produces chiral ladders that can be used as rigid 1D building units. Spatial separation of these building units with linkers of different lengths allows the engineering of homochiral porous MOFs with enhanced pore sizes, pore volumes, and surface areas. This strategy enables the synthesis of a family of isoreticular MOFs, in which the pore size dictates the enantioselective adsorption of chiral molecules (in terms of their size and enantiomeric excess).

Direct On-Surface Patterning of a Crystalline Laminar Covalent Organic Framework Synthesized at Room Temperature.

We report herein an efficient, fast, and simple synthesis of an imine-based covalent organic framework (COF) at room temperature (hereafter, RT-COF-1). RT-COF-1 shows a layered hexagonal structure exhibiting channels, is robust, and is porous to N2 and CO2 . The room-temperature synthesis has enabled us to fabricate and position low-cost micro- and submicropatterns of RT-COF-1 on several surfaces, including solid SiO2 substrates and flexible acetate paper, by using lithographically controlled wetting and conventional ink-jet printing.

Recent Advances in Carbon Capture with Metal-Organic Frameworks.

The escalating level of CO(2) in the atmosphere is one of the most critical environmental issues of our age. The carbon capture and storage from pilot test plants represents an option for reducing CO(2) emissions, however, the energy cost associated with post-combustion carbon capture process alone is ∼30% of the total energy generated by the power plant. Thus, the generation of carbon capture adsorbents with high uptake capacities, great separation performance and low cost is of paramount importance. Metal-organic frameworks are infinite networks of metal-containing nodes bridged by organic ligands through coordination bonds into porous extended structures and several reports have revealed that they are ideal candidates for the selective capture of CO(2). In this review we summarize recent advances related to the synthesis of porous MOFs and the latest strategies to enhance the CO(2) adsorption enthalpies and capacities at low-pressures, increase hydrolytic and mechanical stabilities, and improve the ease of regeneration. Although they show great promise for post-combustion carbon capture, there are still major challenges that must be overcome before they can be used for such a large-scale application.

Metal-organic frameworks: from molecules/metal ions to crystals to superstructures.

Metal-organic frameworks (MOFs) are among the most attractive porous materials known today, exhibiting very high surface areas, tuneable pore sizes and shapes, adjustable surface functionality, and flexible structures. Advances in the formation of MOF crystals, and in their subsequent assembly into more complex and/or composite superstructures, should expand the scope of these materials in many applications (e.g., drug delivery, chemical sensors, selective reactors and removal devices, etc.) and facilitate their integration onto surfaces and into devices. This Concept article aims to showcase recently developed synthetic strategies to control the one-, two- and three-dimensional (1-, 2- and 3D) organisation of MOF crystals.

Selective Xenon Recovery Using Aluminum-Based Metal-Organic Frameworks with Conserved Pore Topology.

Xenon (Xe) is a commercially valuable element found in trace amounts in the off-gas from used nuclear fuel. Recovering Xe from these streams provides a cost-effective means to increase its supply. However, achieving high-purity Xe recovery is challenging due to the need for separation from nearly identical krypton (Kr). Metal-organic frameworks (MOFs), a class of crystalline porous materials, show potential to separate Xe and Kr by utilizing differences in their kinetic diameters, allowing for selective separation. In this work, we study the impact of pore aperture and volume on selective Xe recovery using four robust aluminum MOFs: Al-PMOF, Al-PyrMOF, Al-BMOF and MIL-120, all with conserved structural topology. The pore topology in each MOF is dictated by the dimensions of the tetracarboxylate ligand employed, with larger ligands leading to MOFs with increased pore size and volume. Our experimental and computational investigations revealed that MIL-120 exhibits the highest affinity (21.94 kH(Xe) = 21.94 mmol g-1 bar-1) for Xe among all MOFs, while Al-BMOF demonstrates the highest Xe/Kr selectivity of 14.34. We evaluated the potential of both MIL-120 and Al-BMOF for Xe recovery through breakthrough analysis using a mixture of 400 ppm Xe:40 ppm Kr. Our results indicate that due to its larger pore volume, Al-BMOF captured more Xe than MIL-120, demonstrating superior Xe/Kr separation efficiency.

Elucidation of the role of metals in the adsorption and photodegradation of herbicides by metal-organic frameworks.

Here, four MOFs, namely Sc-TBAPy, Al-TBAPy, Y-TBAPy, and Fe-TBAPy (TBAPy: 1,3,6,8-tetrakis(p-benzoic acid)pyrene), were characterized and evaluated for their ability to remediate glyphosate (GP) from water. Among these materials, Sc-TBAPy demonstrates superior performance in both the adsorption and degradation of GP. Upon light irradiation for 5 min, Sc-TBAPy completely degrades 100% of GP in a 1.5 mM aqueous solution. Femtosecond transient absorption spectroscopy reveals that Sc-TBAPy exhibits enhanced charge transfer character compared to the other MOFs, as well as suppressed formation of emissive excimers that could impede photocatalysis. This finding was further supported by hydrogen evolution half-reaction (HER) experiments, which demonstrated Sc-TBAPy's superior catalytic activity for water splitting. In addition to its faster adsorption and more efficient photodegradation of GP, Sc-TBAPy also followed a selective pathway towards the oxidation of GP, avoiding the formation of toxic aminomethylphosphonic acid observed with the other M3+-TBAPy MOFs. To investigate the selectivity observed with Sc-TBAPy, electron spin resonance, depleted oxygen conditions, and solvent exchange with D2O were employed to elucidate the role of different reactive oxygen species on GP photodegradation. The findings indicate that singlet oxygen (1O2) plays a critical role in the selective photodegradation pathway achieved by Sc-TBAPy.