High-Performance Porous Organic Polymers for Environmental Remediation of Toxic Gases.

Sulfur dioxide (SO2) is a harmful acidic gas generated from power plants and fossil fuel combustion and represents a significant health risk and threat to the environment. Benzimidazole-linked polymers (BILPs) have emerged as a promising class of porous solid adsorbents for toxic gases because of their chemical and thermal stability as well as the chemical nature of the imidazole moiety. The performance of BILPs in SO2 capture was examined by synergistic experimental and theoretical studies. BILPs exhibit a significantly high SO2 uptake of up to 8.5 mmol g-1 at 298 K and 1.0 bar. The density functional theory (DFT) calculations predict that this high SO2 uptake is due to the dipole-dipole interactions between SO2 and the functionalized polymer frames through O2S(δ+)···N(δ-)-imine and O═S═O(δ-)···H(δ+)-aryl and intermolecular attraction between SO2 molecules (O═S═O(δ-)···S(δ+)O2). Moderate isosteric heats of adsorption (Qst ≈ 38 kJ mol-1) obtained from experimental SO2 uptake studies are well supported by the DFT calculations (≈40 kJ mol-1), which suggests physisorption processes enabling rapid adsorbent regeneration for reuse. Repeated adsorption experiments with almost identical SO2 uptake confirm the easy regeneration and robustness of BILPs. Moreover, BILPs possess very high SO2 adsorption selectivity at low concentration over carbon dioxide (CO2), methane (CH4), and nitrogen (N2): SO2/CO2, 19-24; SO2/CH4, 118-113; SO2/N2, 600-674. This study highlights the potential of BILPs in the desulfurization of flue gas or other gas mixtures through capturing trace levels of SO2.

Biomimetic Mineralization of Large Enzymes Utilizing a Stable Zirconium-Based Metal-Organic Frameworks.

Enzymes are natural catalysts for a wide range of metabolic chemical transformations, including selective hydrolysis, oxidation, and phosphorylation. Herein, we demonstrate a strategy for the encapsulation of enzymes within a highly stable zirconium-based metal-organic framework. UiO-66-F4 was synthesized under mild conditions using an enzyme-compatible amino acid modulator, serine, at a modest temperature in an aqueous solution. Enzyme@UiO-66-F4 biocomposites were then formed by an in situ encapsulation route in which UiO-66-F4 grows around the enzymes and, consequently, provides protection for the enzymes. A range of enzymes, namely, lysozyme, horseradish peroxidase, and amano lipase, were successfully encapsulated within UiO-66-F4. We further demonstrate that the resulting biocomposites are stable under conditions that could denature many enzymes. Horseradish peroxidase encapsulated within UiO-66-F4 maintained its biological activity even after being treated with the proteolytic enzyme pepsin and heated at 60 °C. This strategy expands the toolbox of potential metal-organic frameworks with different topologies or functionalities that can be used as enzyme encapsulation hosts. We also demonstrate that this versatile process of in situ encapsulation of enzymes under mild conditions (i.e., submerged in water and at a modest temperature) can be generalized to encapsulate enzymes of various sizes within UiO-66-F4 while protecting them from harsh conditions (i.e., high temperatures, contact with denaturants or organic solvents).

Thermodynamic Insights into Phosphonate Binding in Metal-Azolate Frameworks.

Organophosphorus chemicals, including chemical warfare agents (CWAs) and insecticides, are acutely toxic materials that warrant capture and degradation. Metal-organic frameworks (MOFs) have emerged as a class of tunable, porous, crystalline materials capable of hydrolytically cleaving, and thus detoxifying, several organophosphorus nerve agents and their simulants. One such MOF is M-MFU-4l (M = metal), a bioinspired azolate framework whose metal node is composed of a variety of divalent first-row transition metals. While Cu-MFU-4l and Zn-MFU-4l are shown to rapidly degrade CWA simulants, Ni-MFU-4l and Co-MFU-4l display drastically lower activities. The lack of reactivity was hypothesized to arise from the strong binding of the phosphate product to the node, which deactivates the catalyst by preventing turnover. No such study has provided detailed insight into this mechanism. Here, we leverage isothermal titration calorimetry (ITC) to monitor the binding of an organophosphorus compound with the M-MFU-4l series to construct a complete thermodynamic profile (Ka, ΔH, ΔS, ΔG) of this interaction. This study further establishes ITC as a viable technique to probe small differences in thermodynamics that result in stark differences in material properties, which may allow for better design of first-row transition metal MOF catalysts for organophosphorus hydrolysis.

Tailoring Hydrophobicity and Pore Environment in Physisorbents for Improved Carbon Dioxide Capture under High Humidity.

CALF-20, a Zn-triazolate-based metal-organic framework (MOF), is one of the most promising adsorbent materials for CO2 capture. However, competitive adsorption of water severely limits its performance when the relative humidity (RH) exceeds 40%, limiting the potential implementation of CALF-20 in practical settings where CO2 is saturated with moisture, such as postcombustion flue gas. In this work, three newly designed MOFs related to CALF-20, denoted as NU-220, CALF-20M-w, and CALF-20M-e that feature hydrophobic methyltriazolate linkers, are presented. Inclusion of methyl groups in the linker is proposed as a strategy to improve the uptake of CO2 in the presence of water. Notably, both CALF-20M-w and CALF-20M-e retain over 20% of their initial CO2 capture efficiency at 70% RH─a threshold at which CALF-20 shows negligible CO2 uptake. Grand canonical Monte Carlo simulations reveal that the methyl group hinders water network formation in the pores of CALF-20M-w and CALF-20M-e and enhances their CO2 selectivity over N2 in the presence of a high moisture content. Moreover, calculated radial distribution functions indicate that introducing the methyl group into the triazolate linker increases the distance between water molecules and Zn coordination bonds, offering insights into the origin of the enhanced moisture stability observed for CALF-20M-w and CALF-20M-e relative to CALF-20. Overall, this straightforward design strategy has afforded more robust sorbents that can potentially meet the challenge of effectively capturing CO2 in practical industrial applications.

Effective Strategy toward Obtaining Reliable Breakthrough Curves of Solid Adsorbents.

Metal-organic frameworks (MOFs) have demonstrated their versatility in a wide range of applications, including chemical separation, gas capture, and storage. In industrial adsorption processes, MOFs are integral to the creation of selective gas adsorption fixed beds. In this context, the assessment of their separation performance under relevant conditions often relies on breakthrough experiments. One aspect frequently overlooked in these experiments is the shaping of MOF powders, which can significantly impact the accuracy of breakthrough results. In this study, we present an approach for immobilizing MOF particles on the surface of glass beads (GBs) utilizing trimethylolpropane triglycidyl ether (TMPTGE) as a binder, leading to the creation of MOF@GB materials. We successfully synthesized five targeted MOF composites, namely, SIFSIX-3-Ni@GB, CALF-20@GB, UiO-66@GB, HKUST-1@GB, and MOF-808@GB, each possessing distinct pore sizes and structural topologies. Characterization studies employing powder X-ray diffraction and adsorption isotherm analyses demonstrated that MOFs@GB retained their crystallinity and 73-90% of the Brunauer-Emmett-Teller area of their parent MOFs. Dynamic breakthrough experiments revealed that, in comparison to their parent MOFs, MOF@GB configurations enhanced the accuracy of breakthrough measurements by mitigating pressure buildup and minimizing reductions in the gas flow rate. This work underscores the significance of meticulous experimental design, specifically in shaping MOF powders, to optimize the efficacy of breakthrough experiments. Our proposed strategy aims to provide a versatile platform for MOF powder processing, thereby facilitating more reliable breakthrough experiments.

Robust Carborane-Based Metal-Organic Frameworks for Hexane Separation.

Hexane isomers play a vital role as feedstocks and fuel additives in the petrochemical industry. However, their similar physical and chemical properties lead to significant challenges in the separation process. Traditional thermal separation techniques are energy-intensive and lead to significant carbon footprint penalties. As such, there is a growing demand for the development of less energy-intensive nonthermal separation methods. Adsorption-based separation methods, such as using solid sorbents or membranes, have emerged as promising alternatives to distillation. Here, we report the successful synthesis of two novel metal-organic frameworks (MOFs), NU-2004 and NU-2005, by incorporating a carborane-based three-dimensional (3D) linker and using aluminum and vanadium nodes, respectively. These MOFs exhibit exceptional thermal stability and structural rigidity compared to other MIL-53 analogues, which is further corroborated using synchrotron studies. Furthermore, the inclusion of the quasi-spherical 3D linker in NU-2004 demonstrates significant advancements in the separation of hexane isomers compared to other MIL MOFs containing two-dimensional (2D) and aliphatic 3D linkers.

Air-Stable Cu(I) Metal-Organic Framework for Hydrogen Storage.

Metal-organic frameworks (MOFs) that contain open metal sites have the potential for storing hydrogen (H2) at ambient temperatures. In particular, Cu(I)-based MOFs demonstrate very high isosteric heats of adsorption for hydrogen relative to other reported MOFs with open metal sites. However, most of these Cu(I)-based MOFs are not stable in ambient conditions since the Cu(I) species display sensitivity toward moisture and can rapidly oxidize in air. As a result, researchers have focused on the synthesis of new air-stable Cu(I)-based materials for H2 storage. Here, we have developed a de novo synthetic strategy to generate a robust Cu(I)-based MOF, denoted as NU-2100, using a mixture of Cu/Zn precursors in which zinc acts as a catalyst to transform an intermediate MOF into NU-2100 without getting incorporated into the final MOF structure. NU-2100 is air-stable and displays one of the initial highest isosteric heats of adsorption (32 kJ/mol) with good hydrogen storage capability under ambient conditions (10.4 g/L, 233 K/100 bar to 296 K/5 bar). We further elucidated the H2 storage performance of NU-2100 using a combination of spectroscopic analysis and computational modeling studies. Overall, this new synthetic route may enable the design of additional stable Cu(I)-MOFs for next-generation hydrogen storage adsorbents at ambient temperatures.

Suitability of a diamine functionalized metal-organic framework for direct air capture.

The increase in the atmospheric carbon dioxide level is a significant threat to our planet, and therefore the selective removal of CO2 from the air is a global concern. Metal-organic frameworks (MOFs) are a class of porous materials that have shown exciting potential as adsorbents for CO2 capture due to their high surface area and tunable properties. Among several implemented technologies, direct air capture (DAC) using MOFs is a promising strategy for achieving climate targets as it has the potential to actively reduce the atmospheric CO2 concentration to a safer levels. In this study, we investigate the stability and regeneration conditions of N,N'-dimethylethylenediamine (mmen) appended Mg2(dobpdc), a MOF with exceptional CO2 adsorption capacity from atmospheric air. We employed a series of systematic experiments including thermogravimetric analysis (TGA) coupled with Fourier transformed infrared (FTIR) and gas chromatography mass spectrometer (GCMS) (known as TGA-FTIR-GCMS), regeneration cycles at different conditions, control and accelerated aging experiments. We also quantified CO2 and H2O adsorption under humid CO2 using a combination of data from TGA-GCMS and coulometric Karl-Fischer titration techniques. The quantification of CO2 and H2O adsorption under humid conditions provides vital information for the design of real-world DAC systems. Our results demonstrate the stability and regeneration conditions of mmen appended Mg2(dobpdc). It is stable up to 50% relative humidity when the adsorption temperature varies from 25-40 °C and the best regeneration condition can be achieved at 120 °C under dynamic vacuum and at 150 °C under N2.

Metal-Organic Frameworks with a Bioinspired Porous Polymer Coating for Sieving Separation.

Polymer/metal-organic framework (MOF) composites have been widely studied for their favorable combination of polymer flexibility and MOF crystallinity. While traditional polymer-coated MOFs maximize the polymer properties at the surface, the dramatic loss of MOF porosity due to blockage by the nonporous polymeric coating remains a problem. Herein, we introduce intrinsically microporous synthetic allomelanin (AM) as a porous coating on the zirconium-based MOF (Zr-MOF) UiO-66 via an in situ surface-constrained oxidative polymerization of the AM precursor, 1,8-dihydroxynaphthalene (1,8-DHN). Transmission electron microscopy images verify the formation of well-defined nanoparticles with a core-shell morphology (AM@UiO-66), and nitrogen sorption isotherms indicate the porosity of the UiO-66 core remains constant and is not disturbed by the AM coating. Notably, such a strategy could be adapted to MOFs with larger pores, such as MOF-808 by generating porous AM polymer coatings from bulkier DHN oligomers, highlighting the versatility of this method. Finally, we showed that by tuning the AM coating thickness on UiO-66, the hierarchically porous structures of these AM@UiO-66 composites engender excellent hexane isomer separation selectivity and storage capacity.

Fibrous Zr-MOF Nanozyme Aerogels with Macro-Nanoporous Structure for Enhanced Catalytic Hydrolysis of Organophosphate Toxins.

Metal-organic frameworks (MOFs) with Lewis acid catalytic sites, such as zirconium-based MOFs (Zr-MOFs), comprise a growing class of phosphatase-like nanozymes that can degrade toxic organophosphate pesticides and nerve agents. Rationally engineering and shaping MOFs from as-synthesized powders into hierarchically porous monoliths is essential for their use in emerging applications, such as filters for air and water purification and personal protection gear. However, several challenges still limit the production of practical MOF composites, including the need for sophisticated reaction conditions, low MOF catalyst loadings in the resulting composites, and poor accessibility to MOF-based active sites. To overcome these limitations, a rapid synthesis method is developed to introduce Zr-MOF nanozyme coating into cellulose nanofibers, resulting in the formation of processable monolithic aerogel composites with high MOF loadings. These composites contain Zr-MOF nanozymes embedded in the structure, and hierarchical macro-micro porosity enables excellent accessibility to catalytic active sites. This multifaceted rational design strategy, including the selection of a MOF with many catalytic sites, fine-tuning the coating morphology, and the fabrication of a hierarchically structured monolithic aerogel, renders synergistic effects toward the efficient continuous hydrolytic detoxification of organophosphorus-based nerve agent simulants and pesticides from contaminated water.

Unveiling Unexpected Modulator-CO2 Dynamics within a Zirconium Metal-Organic Framework.

Carbon capture, storage, and utilization (CCSU) represents an opportunity to mitigate carbon emissions that drive global anthropogenic climate change. Promising materials for CCSU through gas adsorption have been developed by leveraging the porosity, stability, and tunability of extended crystalline coordination polymers called metal-organic frameworks (MOFs). While the development of these frameworks has yielded highly effective CO2 sorbents, an in-depth understanding of the properties of MOF pores that lead to the most efficient uptake during sorption would benefit the rational design of more efficient CCSU materials. Though previous investigations of gas-pore interactions often assumed that the internal pore environment was static, discovery of more dynamic behavior represents an opportunity for precise sorbent engineering. Herein, we report a multifaceted in situ analysis following the adsorption of CO2 in MOF-808 variants with different capping agents (formate, acetate, and trifluoroacetate: FA, AA, and TFA, respectively). In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis paired with multivariate analysis tools and in situ powder X-ray diffraction revealed unexpected CO2 interactions at the node associated with dynamic behavior of node-capping modulators in the pores of MOF-808, which had previously been assumed to be static. MOF-808-TFA displays two binding modes, resulting in higher binding affinity for CO2. Computational analyses further support these dynamic observations. The beneficial role of these structural dynamics could play an essential role in building a deeper understanding of CO2 binding in MOFs.

Structure-Activity Relationship Insights for Organophosphonate Hydrolysis at Ti(IV) Active Sites in Metal-Organic Frameworks.

Organophosphorus nerve agents are among the most toxic chemicals known and remain threats to humans due to their continued use despite international bans. Metal-organic frameworks (MOFs) have emerged as a class of heterogeneous catalysts with tunable structures that are capable of rapidly detoxifying these chemicals via hydrolysis at Lewis acidic active sites on the metal nodes. To date, the majority of studies in this field have focused on zirconium-based MOFs (Zr-MOFs) that contain hexanuclear Zr(IV) clusters, despite the large toolbox of Lewis acidic transition metal ions that are available to construct MOFs with similar catalytic properties. In particular, very few reports have disclosed the use of a Ti-based MOF (Ti-MOF) as a catalyst for this transformation even though Ti(IV) is a stronger Lewis acid than Zr(IV). In this work, we explored five Ti-MOFs (Ti-MFU-4l, NU-1012-NDC, MIL-125, Ti-MIL-101, MIL-177(LT), and MIL-177(HT)) that each contains Ti(IV) ions in unique coordination environments, including monometallic, bimetallic, octanuclear, triangular clusters, and extended chains, as catalysts to explore how both different node structures and different linkers (e.g., azolate and carboxylate) influence the binding and subsequent hydrolysis of an organophosphorus nerve agent simulant at Ti(IV)-based active sites in basic aqueous solutions. Experimental and theoretical studies confirm that Ti-MFU-4l, which contains monometallic Ti(IV)-OH species, exhibits the best catalytic performance among this series with a half-life of roughly 2 min. This places Ti-MFU-4l as one of the best nerve agent hydrolysis catalysts of any MOF reported to date.

Engineering Metal-Organic Frameworks for Selective Separation of Hexane Isomers Using 3-Dimensional Linkers.

Metal-organic frameworks (MOFs) are highly tunable materials with potential for use as porous media in non-thermal adsorption or membrane-based separations. However, many separations target molecules with sub-angstrom differences in size, requiring precise control over the pore size. Herein, we demonstrate that this precise control can be achieved by installing a three-dimensional linker in an MOF with one-dimensional channels. Specifically, we synthesized single crystals and bulk powder of NU-2002, an isostructural framework to MIL-53 with bicyclo[1.1.1]pentane-1,3-dicarboxylic acid as the organic linker component. Using variable-temperature X-ray diffraction studies, we show that increasing linker dimensionality limits structural breathing relative to MIL-53. Furthermore, single-component adsorption isotherms demonstrate the efficacy of this material for separating hexane isomers based on the different sizes and shapes of these isomers.

Pore Aperture Control Toward Size-Exclusion-Based Hydrocarbon Separations.

Metal-organic frameworks (MOFs) have been proposed as a promising material for non-thermal chemical separations owing to their high structural diversity and tunability. Here, we report the synthesis of a zinc-based MOF containing a three-dimensional (3D) linker, bicyclo[2.2.2]octane-1,4-dicarboxylic acid, with high thermal stability towards the separation of hexane isomers. The incorporation of the 3D linker enhances the structural stability and provides well-defined pore apertures/channels with sub-Ångstrom precision. This precision allowed for the separation of similarly sized hexane isomers based on subtle differences in their kinetic diameters. Multi-component liquid phase batch experiments confirmed the separation of hexanes mixture into linear, monobranched, and dibranched isomers. This work represents a significant milestone in the construction of stable Zn-based MOFs and the incorporation of 3D linkers as a potential solution to challenging separations.

Tröger's Base Chemistry in Solution and in Zr(IV)-Based Metal-Organic Frameworks.

Tröger's base (TB) and its derivatives have been studied extensively due to their unique concave shape stemming from the endomethylene strap. However, the strap-clipped TB chemistry has been largely overlooked in metal-organic framework (MOF) solids, leading to a gap in our knowledge within this field. In this work, we report the in situ strap elimination of a carboxylate-carrying TB in the presence of formic acid, both in solution and in Zr(IV)-based MOFs. In the solution system, the methanodiazocine nucleus can be exclusively transformed into an N,N'-diformyl-decorated phenhomazine derivative, regardless of the solvent used (DMF, DMA, or DEF), as unambiguously uncovered by single crystal X-ray crystallography. In contrast, while in the MOF synthetic system, the degree of derivatization reaction can be effectively controlled to give either the secondary diamine or formyl-decorated diamine, depending on the solvent used (DMF or DEF), resulting in the formation of two Zr-MOFs with 8-connected bcu (NU-1900) and 12-connected fcu (NU-407) topologies, respectively. The derivatization mechanism is proposed to be topology-guided and dependent on the local acid concentration during the MOF formation processes. Moreover, we discovered a novel post-synthetically water-induced in situ linker formylation process in NU-1900 through sequential formic acid elimination, migration, and condensation processes, affording an isostructural framework with the same linker as in NU-407, which further corroborates our proposed mechanism. Additionally, the highly defective NU-1900 with abundant accessible Zr sites was demonstrated to be an outstanding catalyst for the detoxification of a nerve agent simulant with a half-life of less than 1 min.

Influence of Pore Size on Hydrocarbon Transport in Isostructural Metal-Organic Framework Crystallites.

Hydrocarbon separations using porous materials such as metal-organic frameworks (MOFs) have been proposed to reduce the energy demands associated with current distillation-based methods. Despite the potential of these materials to distinguish hydrocarbons through thermodynamic or kinetic mechanisms, experimental data quantifying hydrocarbon transport in MOFs is lacking. Such mass transfer measurements are vital to elucidate structure-property relationships and design future high-performing separation materials. In this work, we aim to isolate the influence of pore size on hydrocarbon diffusion by studying a pair of isoreticular MOFs, Co2Cl2BBTA and Co2Cl2BTDD. We use a volumetric method to extract mass transport coefficients for six hydrocarbon probe molecules of varying size and chemical functionality. From these nonequilibrium mass transport measurements, we determine the rate-limiting diffusion mechanism and identify trends in hydrocarbon surface permeabilities in the MOFs based on pore size, hydrocarbon chain length, and temperature.

Leveraging Isothermal Titration Calorimetry to Explore Structure-Property Relationships of Protein Immobilization in Metal-Organic Frameworks.

Proteins immobilized in metal-organic frameworks (MOFs) often show extraordinary stability. However, most efforts to immobilize proteins in MOFs have only been exploratory. Herein, we present the first systematic study on the thermodynamics of protein immobilization in MOFs. Using insulin as a probe, we leveraged isothermal titration calorimetry (ITC) to investigate how topology, pore size, and hydrophobicity of MOFs influence immobilization. ITC data obtained from the encapsulation of insulin in a series of Zr-MOFs reveals that MOFs provide proteins with a hydrophobic stabilizing microenvironment, making the encapsulation entropically driven. In particular, the pyrene-based NU-1000 tightly encapsulates insulin in its ideally sized mesopores and stabilizes insulin through π-π stacking interactions, resulting in the most enthalpically favored encapsulation process among this series. This study reveals critical insights into the structure-property relationships of protein immobilization.

Separation of Aromatic Hydrocarbons in Porous Materials.

Industrial-scale thermal separation processes have contributed greatly to the rise in carbon dioxide emissions. Porous materials, such as metal-organic frameworks (MOFs), can potentially reduce these emissions by achieving nonthermal chemical separations through the physical adsorption of targeted species with high selectivity. Here, we report the synthesis of the channel-based MOFs NU-2000 and NU-2001, which are constructed from three-dimensional (3D) linkers, to separate the industrially relevant xylene isomers under ambient conditions by leveraging sub-Ångstrom differences in the sizes of each isomer. While the rotation of two-dimensional (2D) linkers in MOFs often affords changes in pore apertures and pore sizes that are substantial enough to hinder separation efficiency, increasing the linker dimensionality from 2D to three-dimensional (3D) enables precise control of the MOF pore size and aperture regardless of the linker orientation, establishing this design principle as a broadly applicable strategy.

Interfacial Unit-Dependent Catalytic Activity for CO Oxidation over Cerium Oxysulfate Cluster Assemblies.

Atomically precise cerium oxo clusters offer a platform to investigate structure-property relationships that are much more complex in the ill-defined bulk material cerium dioxide. We investigated the activity of the MCe70 torus family (M = Cd, Ce, Co, Cu, Fe, Ni, and Zn), a family of discrete oxysulfate-based Ce70 rings linked by monomeric cation units, for CO oxidation. CuCe70 emerged as the best performing MCe70 catalyst among those tested, prompting our exploration of the role of the interfacial unit on catalytic activity. Temperature-programmed reduction (TPR) studies of the catalysts indicated a lower temperature reduction in CuCe70 as compared to CeCe70. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) indicated that CuCe70 exhibited a faster formation of Ce3+ and contained CO bridging sites absent in CeCe70. Isothermal CO adsorption measurements demonstrated a greater uptake of CO by CuCe70 as compared to CeCe70. The calculated energies for the formation of a single oxygen defect in the structure significantly decreased with the presence of Cu at the linkage site as opposed to Ce. This study revealed that atomic-level changes in the interfacial unit can change the reducibility, CO binding/uptake, and oxygen vacancy defect formation energetics in the MCe70 family to thus tune their catalytic activity.

Heteroatom-Doped Porous Carbons as Effective Adsorbers for Toxic Industrial Gasses.

Ammonia (NH3), often stored in large quantities before being used in the production of fertilizer, and sulfur dioxide (SO2), a byproduct of fossil fuel consumption, particularly the burning of coal, are highly toxic and corrosive gases that pose a significant danger to humans if accidentally released. Therefore, developing advanced materials to enable their effective capture and safe storage is highly desired. Herein, advanced benzimidazole-derived carbons (BIDCs) with an exceptional capacity for NH3 and SO2 have been designed and tested. These heteroatom-doped porous carbon adsorbents were synthesized by thermolysis of imidazolate-potassium salts affording high surface area and controlled heteroatom content to optimize for rapid NH3 and SO2 gas uptake and release under practical conditions. According to gas uptake measurements, these nitrogen-doped carbons exhibit exceptional gas adsorption capacity, with BIDC-3-800 adsorbing 21.42 mmol/g SO2 at 298 K and 1 bar, exceeding most reported porous materials and BIDC-2-700 adsorbing 14.26 mmol/g NH3 under the same conditions. The NH3 uptake of BIDC-2-700 surpassed reported activated carbons and is among the best adsorbents including metal organic frameworks (MOFs). Our synthetic method allows for control over both textural and chemical properties of the carbon and enables heteroatom functionality to be incorporated directly into the carbon framework without the need for postsynthetic modification. These materials were also tested for recyclability; all adsorbents showed almost complete retention of their initial gas uptake capacity during recyclability studies and maintained their structural integrity and their previous adsorption capacity of both NH3 and SO2, highlighting their potential for practical application.