Highly Boosted Reaction Kinetics in Carbon Dioxide Electroreduction by Surface-Introduced Electronegative Dopants

Effectively improving the selectivity while reducing the overpotential over the electroreduction of CO₂ (CO₂ER) has been challenging. Herein, electronegative N atoms and coordinatively unsaturated Ni N₃ moieties co-anchored carbon nanofiber (Ni N₃ NCNFs) catalyst via an integrated electrospinning and carbonization strategy are reported. The catalyst exhibits a maximum CO Faradaic efficiency (F.E.) of 96.6%, an onset potential of −0.3 V, and a low Tafel slope of 71 mV dec⁻¹ along with high stability over 100 h. Aberration corrected scanning transmission electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy identify the atomically dispersed Ni N₃ sites with Ni atom bonded by three pyridinic N atoms. The existence of abundant electronegative N dopants adjoin the Ni N₃ centers in Ni N₃ NCNFs. Theoretical calculations reveal that both, the undercoordinated Ni N₃ centers and their first neighboring C atoms modified by extra N dopants, display the positive effect on boosting CO₂ adsorption and water dissociation processes, thus accelerating the CO₂ER kinetics process. Furthermore, a designed Zn CO₂ battery with the cathode of Ni N₃ NCNFs delivers a maximum power density of 1.05 mW cm⁻² and CO F.E. of 96% during the discharge process, thus providing a promising approach to electric energy output and chemical conversion.     

New-Generation Anion-Pillared Metal–Organic Frameworks with Customized Cages for Highly Efficient CO2 Capture

The rational design of porous materials for CO₂ capture under realistic process conditions is highly desirable. However, trade-offs exist among a nanopore's capacity, selectivity, adsorption heat, and stability. In this study, a new generation of anion-pillared metal-organic frameworks (MOFs) are reported with customizable cages for benchmark CO₂ capture from flue gas. The optimally designed TIFSIX-Cu-TPA exhibits a high CO₂ capacity, excellent CO₂/N₂ selectivity, high thermal stability, and chemical stability in acid solution and acidic atmosphere, as well as modest adsorption heat for facile regeneration. Additionally, the practical separation performance of the synthesized MOFs is demonstrated by breakthrough experiments under various process conditions. A highly selective separation is achieved at 298–348 K with the impressive CO₂ capacity of 2.1–1.4 mmol g⁻¹. Importantly, the outstanding performance is sustained under high humidity and over ten repeat process cycles. The molecular mechanism of MOF's CO₂ adsorption is further investigated in situ by CO₂ dosed single crystal structure and theoretical calculations, highlighting two separate binding sites for CO₂ in small and large cages featured with high CO₂ selectivity and loading, respectively. The simultaneous adsorption of CO₂ inside these two types of interconnected cages accounts for the high performance of these newly designed anionic pillar-caged MOFs.     

A New Strategy for Accelerating Dynamic Proton Transfer of Electrochemical CO2 Reduction at High Current Densities

Developing single-atom electrocatalysts with high activity and superior selectivity at a wide potential window for CO₂ reduction reaction (CO₂RR) still remains a great challenge. Herein, a porous Ni N C catalyst containing atomically dispersed Ni N₄ sites and nanostructured zirconium oxide (ZrO₂@Ni-NC) synthesized via a post-synthetic coordination coupling carbonization strategy is reported. The as-prepared ZrO₂@Ni-NC exhibits an initial potential of −0.3 V, maximum CO Faradaic efficiency (F.E.) of 98.6% ± 1.3, and a low Tafel slope of 71.7 mV dec⁻¹ in electrochemical CO₂RR. In particular, a wide potential window from −0.7 to −1.4 V with CO F.E. of above 90% on ZrO₂@Ni-NC far exceeds those of recently developed state-of-the-art CO₂RR electrocatalysts based on Ni N moieties anchored carbon. In a flow cell, ZrO₂@Ni-NC delivers a current density of 200 mA cm⁻² with a superior CO selectivity of 96.8% at −1.58 V in a practical scale. A series of designed experiments and structural analyses identify that the isolated Ni N₄ species act as real active sites to drive the CO₂RR reaction and that the nanostructured ZrO₂ largely accelerates the protonation process of *CO₂⁻ to *COOH intermediate, thus significantly reducing the energy barrier of this rate-determining step and boosting whole catalytic performance.     

Visible Light Triggered CO2 Liberation from Silver Nanocrystals Incorporated Metal–Organic Frameworks

Widespread deployment of metal–organic frameworks (MOFs) for CO₂ capture remains challenging due to the great energy‐penalty associated with their regeneration. To overcome this challenge, a new type of photodynamic carbon capture material synthesized by incorporating Ag nanocrystals with UiO‐66 (Ag/UiO‐66) framework is presented. Upon the irradiation of visible light, Ag nanocrystals within the composites serve as “nanoheaters” to convert photon energy into thermal energy locally. Driven by such light‐induced localized heat (LLH), the adsorbed CO₂ within MOFs is remotely released. The CO₂ desorption capacity of such Ag/UiO‐66 composites can be readily regulated by control over their Ag contents and the applied light intensity. Up to 90.5% of CO₂ desorption is achieved under the investigated conditions. Distinct from the traditional light‐responsive MOFs for gas trigger release, currently developed LLH‐driven CO₂ release method not only offers a promising solution to the heat‐insulating nature of MOFs, but also demonstrates a potentially low energy method to remotely regenerate MOF adsorbents given the utilization of naturally abundant visible light as efficient stimulus.     

Mechanochemical Post-Synthesis of Metal–Organic Framework-Based Pre-Electrocatalysts with Surface Fe?O?Ni/Co Bonding for Highly Efficient Oxygen Evolution

Rational surface engineering of metal–organic frameworks (MOFs) provide potential opportunities to address the sluggish kinetics of oxygen evolution reaction (OER). However, the development of MOF-based materials with low overpotentials remains a great challenge. Herein, a post-synthesis strategy to prepare highly efficient MOF-based pre-electrocatalysts via all-solid-phase mechanochemistry is demonstrated. The surface of a Fe-based MOF (MIL-53) can be reconstructed and anchored with atomically dispersed Ni/Co sites. As expected, the optimized M-NiA-CoN exhibits a very low overpotential of 180 mV at 10 mA cm⁻² and a small Tafel slope of 41 mV dec⁻¹ in 1 m KOH electrolyte. The superior electrocatalytic OER activity is mainly due to the formation of surface Fe O Ni/Co bonding. Furthermore, density functional theory calculations reveal that the transformation from ^*OH to ^*O is the rate-determining step and the electrocatalytic OER activity trend at different metal sites is Co > Ni≈Fe.     

Hydrogen Adsorption in Metal–Organic Frameworks: Cu‐MOFs and Zn‐MOFs Compared

Hydrogen adsorption in two different metal–organic frameworks (MOFs), MOF‐5 and Cu‐BTC (BTC: benzene‐1,3,5‐tricarboxylate), with Zn²⁺ and Cu²⁺ as central metal ions, respectively, is investigated at temperatures ranging from 77 K to room temperature. The process responsible for hydrogen storage in these MOFs is pure physical adsorption with a heat of adsorption of approximately –4 kJ mol^–1. With a saturation value of 5.1 wt.‐% for the hydrogen uptake at high pressures and 77 K, MOF‐5 shows the highest storage capacity ever reported for crystalline microporous materials. However, at low pressures Cu‐BTC shows a higher hydrogen uptake than MOF‐5, making Cu‐based MOFs more promising candidates for potential storage materials. Furthermore, the hydrogen uptake is correlated with the specific surface area for crystalline microporous materials, as shown for MOFs and zeolites.     

Disclosing the Role of Defect-Engineered Metal–Organic Frameworks in Mixed Matrix Membranes for Efficient CO2 Separation: A Joint Experimental-Computational Exploration

Incorporation of defects in metal–organic frameworks (MOFs) offers new opportunities for manipulating their microporosity and functionalities. The so-called “defect engineering” has great potential to tailor the mass transport properties in MOF/polymer mixed matrix membranes (MMMs) for challenging separation applications, for example, CO₂ capture. This study first investigates the impact of MOF defects on the membrane properties of the resultant MOF/polymer MMMs for CO₂ separation. Highly porous defect-engineered UiO-66 nanoparticles are successfully synthesized and incorporated into a CO₂-philic crosslinked poly(ethylene glycol) diacrylate (PEGDA) matrix. A thorough joint experimental/simulation characterization reveals that defect-engineered UiO-66/PEGDA MMMs exhibit nearly identical filler–matrix interfacial properties regardless of the defect concentrations of their parental UiO-66 filler. In addition, non-equilibrium molecular dynamics simulations in tandem with gas transport studies disclose that the defects in MOFs provide the MMMs with ultrafast transport pathways mainly governed by diffusivity selectivity. Ultimately, MMMs containing the most defective UiO-66 show the most enhanced CO₂/N₂ separation performance—CO₂ permeability = 470 Barrer (four times higher than pure PEGDA) and maintains CO₂/N₂ selectivity = 41—which overcomes the trade-off limitation in pure polymers. The results emphasize that defect engineering in MOFs would mark a new milestone for the future development of optimized MMMs.     

Hybrid 2D Dual‐Metal–Organic Frameworks for Enhanced Water Oxidation Catalysis

Metal–organic frameworks (MOFs) and MOF‐derived nanostructures are recently emerging as promising catalysts for electrocatalysis applications. Herein, 2D MOFs nanosheets decorated with Fe‐MOF nanoparticles are synthesized and evaluated as the catalysts for water oxidation catalysis in alkaline medium. A dramatic enhancement of the catalytic activity is demonstrated by introduction of electrochemically inert Fe‐MOF nanoparticles onto active 2D MOFs nanosheets. In the case of active Ni‐MOF nanosheets (Ni‐MOF@Fe‐MOF), the overpotential is 265 mV to reach a current density of 10 mA cm^?2 in 1 m KOH, which is lowered by ≈100 mV after hybridization due to the 2D nanosheet morphology and the synergistic effect between Ni active centers and Fe species. Similar performance improvement is also successfully demonstrated in the active NiCo‐MOF nanosheets. More importantly, the real catalytic active species in the hybrid Ni‐MOF@Fe‐MOF catalyst are unraveled. It is found that, NiO nanograins (≈5 nm) are formed in situ during oxygen evolution reaction (OER) process and act as OER active centers as well as building blocks of the porous nanosheet catalysts. These findings provide new insights into understanding MOF‐based catalysts for water oxidation catalysis, and also shed light on designing highly efficient MOF‐derived nanostructures for electrocatalysis.     

Highly Dispersed NiO Clusters Induced Electron Delocalization of Ni?N?C Catalysts for Enhanced CO2 Electroreduction

Oxygen-regulated Ni-based single-atom catalysts (SACs) show great potential in accelerating the kinetics of electrocatalytic CO₂ reduction reaction (CO₂RR). However, it remains a challenge to precisely control the coordination environment of Ni O moieties and achieve high activity at high overpotentials. Herein, a facile carbonization coupled oxidation strategy is developed to mass produce NiO clusters-decorated Ni N C SACs that exhibit a high Faradaic efficiency of CO (maximum of 96.5%) over a wide potential range (−0.9 to −1.3 V versus reversible hydrogen electrode) and a high turnover frequency for CO production of 10 120 h⁻¹ even at the high overpotential of 1.19 V. Density functional theory calculations reveal that the highly dispersed NiO clusters induce electron delocalization of active sites and reduce the energy barriers for *COOH intermediates formation from CO₂, leading to an enhanced reaction kinetics for CO production. This study opens a new universal pathway for the construction of oxygen-regulated metal-based SACs for various catalytic applications.     

Molecular Storage of Mg Ions with Vanadium Oxide Nanoclusters

Mg batteries have potential advantages in terms of safety, cost, and reliability over existing battery technologies, but their practical implementations are hindered by the lack of amenable high‐voltage cathode materials. The development of cathode materials is complicated by limited understandings of the unique divalent Mg²⁺ ion electrochemistry and the interaction/transportation of Mg²⁺ ions with host materials. Here, it is shown that highly dispersed vanadium oxide (V₂O₅) nanoclusters supported on porous carbon frameworks are able to react with Mg²⁺ ions reversibly in electrolytes that are compatible with Mg metal, and exhibit high capacities and good reaction kinetics. They are able to deliver initial capacities exceeding 300 mAh g^?1 at 40 mA g^?1 in the voltage window of 0.5 to 2.8 V. The combined electron microscope, spectroscopy, and electrochemistry characterizations suggest a surface‐controlled pseudocapacitive electrochemical reaction, and may be best described as a molecular energy storage mechanism. This work can provide a new approach of using the molecular mechanism for pseudocapacitive storage of Mg²⁺ for Mg batteries cathode materials.     

Self‐Directed Localization of ZIF‐8 Thin Film Formation by Conversion of ZnO Nanolayers

Control of localized metal–organic framework (MOF) thin film formation is a challenge. Zeolitic imidazolate frameworks (ZIFs) are an important sub‐class of MOFs based on transition metals and imidazolate linkers. Continuous coatings of intergrown ZIF crystals require high rates of heterogeneous nucleation. In this work, substrates coated with zinc oxide layers are used, obtained by atomic layer deposition (ALD) or by magnetron sputtering, to provide the Zn²⁺ ions required for nucleation and localized growth of ZIF‐8 films ([Zn(mim)₂]; Hmim = 2‐methylimidazolate). The obtained ZIF‐8 films reveal the expected microporosity, as deduced from methanol adsorption studies using an environmentally controlled quartz crystal microbalance (QCM) and comparison with bulk ZIF‐8 reference data. The concept is transferable to other MOFs, and is applied to the formation of [Al(OH)(1,4‐ndc)]_n (ndc = naphtalenedicarboxylate) thin films derived from Al₂O₃ nanolayers.     

Highly CO2 Selective Metal–Organic Framework Membranes with Favorable Coulombic Effect

The topology and chemical functionality of metal–organic frameworks (MOFs) make them promising candidates for membrane gas separation; however, few meet the criteria for industrial applications, that is, selectivity of >30 for CO₂/CH₄ and CO₂/N₂. This paper reports on a dense CAU-10-H MOF membrane that is exceptionally CO₂-selective (ideal selectivity of 42 for CO₂/N₂ and 95 for CO₂/CH₄). The proposed membrane also achieves the highest CO₂ permeability (approximately 500 Barrer) among existing pure MOF membranes with CO₂/CH₄ selectivity exceeding 30. State-of-the-art atomistic simulations provide valuable insights into the outstanding separation performance of CAU-10-H at the molecular level. Adsorbent–adsorbate Coulombic interactions are identified as a crucial factor in the design of CO₂-selective MOF membranes.     

Hierarchical Cross-Linked Carbon Aerogels with Transition Metal-Nitrogen Sites for Highly Efficient Industrial-Level CO2 Electroreduction

Developing highly efficient carbon aerogels (CA) electrocatalysts based on transition metal-nitrogen sites is critical for the CO₂ electroreduction reaction (CO₂RR). However, simultaneously achieving a high current density and high Faradaic efficiency (FE) still remains a big challenge. Herein, a series of unique 3D hierarchical cross-linked nanostructured CA with metal-nitrogen sites (M N, M = Ni, Fe, Co, Mn, Cu) is developed for efficient CO₂RR. An optimal CA/N-Ni aerogel, featured with unique hierarchical porous structure and highly exposed M-N sites, exhibits an unusual CO₂RR activity with a CO FE of 98% at −0.8 V. Notably, an industrial current density of 300 mA cm⁻² with a high FE of 91% is achieved on CA/N-Ni aerogel in a flow-cell reactor, which outperforms almost all previously reported M-N/carbon based catalysts. The CO₂RR activity of different CA/N-M aerogels can be arranged as Ni, Fe, Co, Mn, and Cu from high to low. In situ spectroelectrochemistry analyses validate that the rate-determining step in the CO₂RR is the formation of *COOH intermediate. A Zn CO₂ battery is further assembled with CA/N-Ni as the cathode, which shows a maximum power density of 0.5 mW cm⁻² and a superior rechargeable stability.     

A New Type of Efficient CO2 Adsorbent with Improved Thermal Stability: Self‐Assembled Nanohybrids with Optimized Microporosity and Gas Adsorption Functions

A new type of efficient CO₂ absorbent with improved thermal stability is synthesized via self‐assembly between 2D inorganic nanosheets and two kinds of 0D inorganic nanoclusters. In these self‐assembled nanohybrids, the nanoclusters of CdO and Cr₂O₃ are commonly interstratified with layered titanate nanosheets, leading to the formation of highly microporous pillared structure with increased basicity of pore wall. The co‐pillaring of basic CdO with Cr₂O₃ is fairly effective at increasing a proportion of micropores and reactivity for CO₂ molecules and at improving the thermal stability of the resulting porous structure. Of prime importance is that the present inorganic‐pillared nanohybrids show highly efficient CO₂ adsorption capacity, which is much superior to those of many other absorbents and compatible to those of CO₂ adsorbing metal?organic framework (MOF) compounds. Taking into account an excellent thermal stability of the present nanohybrids, these materials are very promising CO₂ adsorbents usable at elevated temperature. This is the first example of efficient CO₂ adsorbent from pillared materials. The co‐pillaring of basic metal oxide nanoclusters employed in this study can provide a very powerful way of developing thermally stable CO₂ adsorbents from many known pillared systems.     

Metal‐Organic Frameworks Derived Nanotube of Nickel–Cobalt Bimetal Phosphides as Highly Efficient Electrocatalysts for Overall Water Splitting

The design of highly efficient, stable, and noble‐metal‐free bifunctional electrocatalysts for overall water splitting is critical but challenging. Herein, a facile and controllable synthesis strategy for nickel–cobalt bimetal phosphide nanotubes as highly efficient electrocatalysts for overall water splitting via low‐temperature phosphorization from a bimetallic metal‐organic framework (MOF‐74) precursor is reported. By optimizing the molar ratio of Co/Ni atoms in MOF‐74, a series of Cox Niy P catalysts are synthesized, and the obtained Co4Ni1P has a rare form of nanotubes that possess similar morphology to the MOF precursor and exhibit perfect dispersal of the active sites. The nanotubes show remarkable hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalytic performance in an alkaline electrolyte, affording a current density of 10 mA cm^?2 at overpotentials of 129 mV for HER and 245 mV for OER, respectively. An electrolyzer with Co4Ni1P nanotubes as both the cathode and anode catalyst in alkaline solutions achieves a current density of 10 mA cm^?2 at a voltage of 1.59 V, which is comparable to the integrated Pt/C and RuO₂ counterparts and ranks among the best of the metal‐phosphide electrocatalysts reported to date.     

Magnetic Cores with Porous Coatings: Growth of Metal‐Organic Frameworks on Particles Using Liquid Phase Epitaxy

A novel method for the homogeneous coating of magnetic nanoparticles with metal organic frameworks (MOFs) is reported. Using a liquid phase epitaxy process, a well‐defined number of [Cu₃(btc)₂]nH₂O, HKUST‐1, layers are grown on COOH terminated silica magnetic beads. The structure and porosity of the deposited MOF coatings are studied using X‐ray diffraction and BET analysis. In addition, size and shape of the fabricated composites are analyzed by transmission electron microscopy. Potential applications of particle based MOF films include catalytic coatings and chromatographic media.     

Disrupting Intracellular Iron Homeostasis by Engineered Metal-Organic Framework for Nanocatalytic Tumor Therapy in Synergy with Autophagy Amplification-Promoted Ferroptosis

Metal-organic frameworks (MOFs) featuring good biocompatibility and tunable microstructures are developed to generate reactive oxygen species (ROS) for nanocatalytic therapy. However, the relatively low catalytic activity of MOF and intracellular ion homeostasis, a self-protective mechanism to resist the intracellular accumulation of metal ions, results in the undesirable efficacy of tumor therapy. Herein, a therapeutic strategy is introduced of breaking intracellular iron homeostasis for nanocatalytic therapy in synergy with autophagy amplification-promoted ferroptosis, based on etched MOF nanocatalyst (denoted COS@MOF), which is self-etched by thiamine pyrophosphate (TPP) and further modified with autophagy agonist chitosan oligosaccharides (COS). Such self-etched MOF exhibit an open cavity structure that is more conducive to adsorbing reactive molecules and producing more active sites, and an enhanced Fe(II)/Fe(III) ratio, reinforcing catalytic activity for ROS generation. The catalytic process of COS@MOF can be accelerated by overexpressed endogenous hydrogen sulfide (H₂S) within colorectal tumors which reduces Fe³⁺ into more active Fe²⁺. In vitro and in vivo results demonstrate that COS@MOF amplifies autophagy to break iron homeostasis for facilitating ROS production to promote ferroptosis, achieving synergetic nanocatalytic/ferroptosis tumor therapy. This study provides a promising paradigm to elevate MOF-based catalytic performance in synergy with autophagy amplification-promoted ferroptosis for enhanced therapeutic efficacy.     

A Polymetallic Metal‐Organic Framework‐Derived Strategy toward Synergistically Multidoped Metal Oxide Electrodes with Ultralong Cycle Life and High Volumetric Capacity

Metal‐organic frameworks (MOFs) are very convenient self‐templated precursors toward functional materials with tunable functionalities. Although a huge family of MOFs has been discovered, conventional MOF‐derived strategies are largely limited to the sole MOF source based on a handful of the metal elements. The limitation in structure and functionalities greatly restrains the maximum performance of MOF‐based materials for fulfilling the practical potential. This study reports a polymetallic MOF‐derived strategy for easy synthesis of metal‐oxide‐based nanohybrids with precisely tailored multicomponent active dopants. A variety of MoO₂‐based nanohybrids with synergistical co‐doping of W, Cu, and P are yielded by controlled pyrolysis of tailor‐made polymetallic MOFs. The W doping induces the formation of Mo_x W_1?x O₂ solid solution with better activity. The homogeneous dispersion of Cu nanocrystallites in robust P‐doped carbon skeleton creates a conductive network for fast charge transfer. Boosting by synergistically multidoping effect, the Mo_0.8W_0.2O₂‐Cu@P‐doped carbon nanohybrids with optimized composition exhibit exceptionally long cycle life of 2000 cycles with high capacities but very slow capacity loss (0.043% per cycle), as well as high power output for lithium storage. Remarkably, the co‐doping of heavy W and Cu elements in MoO₂ with high density makes them particularly suitable for high volumetric lithium storage.     

Tailored Persistent Radical-containing Heterotrimetal-Organic Framework for Boosting Efficiency of Visible/NIR Light-driven Photocatalytic CO2 Reduction

Promoting light absorption range of photocatalysts is of great significance to improve solar light-driven photocatalytic CO₂ reduction efficiency. Herein, a new viologen-based multicomponent heterotrimetallic metal–organic framework (MOF) [Cu₃Th₆(µ₃-O)₄(µ₃-OH)₄(cpb)₁₂][Fe^III(CN)₆]₆ (IHEP-14) with an unprecedented (6, 18)-connected she-d topology is presented. Upon UV irradiation, this MOF undergoes ligand and iron photoreduction, and a single-crystal-to-single-crystal transformation to generate persistent radical-containing MOF [Cu₃Th₆(µ₃-O)₄(µ₃-OH)₄(cpb^•)₁₂][Fe^II(CN)₆]₆ (IHEP-15). This radical-containing MOF shows excellent stability without fading after at least 2 months in air. Besides extending the photoabsorption to a wider wavelength range covering from 200 to 2,500 nm, the generation of persistent radical in IHEP-15 also largely enhances its CO₂ adsorption capacity by a factor of three due to the strong affinity between π orbital of the radical and the π system of CO₂. These attributes endow IHEP-15 with excellent visible/NIR light-driven CO₂ photoreduction activity, with CO production rates under visible and NIR irradiation of 570.3 and 209.3 µmol h⁻¹ g⁻¹, respectively. Notably, the latter is a record high for NIR-induced CO production among all MOFs reported so far.     

N-Containing Carbons Derived from Microporous Coordination Polymers for Use in Post-Combustion Flue Gas Capture

Herein, novel carbons that, owing to a high density of micropores (up to 79%) and N-content (up to 14.9%), offering exciting potential for post-combustion CO₂ capture are reported. Given that little is known about how starting materials impact the structure and performance of carbons, three different microporous materials are pyrolyzed. These include a Co-(metal-organic framework) (MOF), a Co-MOF-polymer composite, and a coordination polymer derived from the same monomer and cobalt ions. Notably, the cobalt, which is required to drive the polymerization, is subsequently leached from the carbons via acid for its reuse in MOF synthesis. Next, various metrics including CO₂ capacity, selectivity, isosteric heat of adsorption, breakthrough time and cyclability are assessed. The acid treated carbons adsorb 0.21, 0.99, and 1.11 mmol CO₂ g⁻¹, respectively, (313 K, 0.15 bar) with CO₂/N₂ selectivity ranging from 37 to 52. Due to superior capacity, the polymer-derived carbons also reveal impressive breakthrough times in simulated flue gas mixtures (15% CO₂/85% N₂, 80% RH, 313 K) ranging from 33 to 40 min g⁻¹. Similar performance is also observed under dry conditions and after pre-saturation with water for 1.5 h. Remarkably, no loss in working capacity is observed after 100 CO₂ TSA cycles (313 K/393 K).