Investigation on cost-effective composites for CO2 adsorption from post-gasification residue and metal organic framework.

Cost-effective CO2 adsorbents are gaining increasing attention as viable solutions for mitigating climate change. In this study, composites were synthesized by electrochemically combining the post-gasification residue of Macadamia nut shell with copper benzene-1,3,5-tricarboxylate (CuBTC). Among the different composites synthesized, the ratio of 1:1 between biochar and CuBTC (B 1:1) demonstrated the highest CO2 adsorption capacity. Under controlled laboratory conditions (0°C, 1 bar, without the influence of ambient moisture or CO2 diffusion limitations), B 1:1 achieved a CO2 adsorption capacity of 9.8 mmol/g, while under industrial-like conditions (25°C, 1 bar, taking into account the impact of ambient moisture and CO2 diffusion limitations within a bed of adsorbent), it reached 6.2 mmol/g. These values surpassed those reported for various advanced CO2 adsorbents investigated in previous studies. The superior performance of the B 1:1 composite can be attributed to the optimization of the number of active sites, porosity, and the preservation of the full physical and chemical surface properties of both parent materials. Furthermore, the composite exhibited a notable CO2/N2 selectivity and improved stability under moisture conditions. These favorable characteristics make B 1:1 a promising candidate for industrial applications.

Reversible Multi-Complexation of CO2 to Alkaline Earth Metal Ion-Pair at 400 ppm and 298 K.

The efficient capture of low-pressure CO2 remains a significant challenge due to the lack of established multi-complexation of CO2 to active sites in microporous materials. In this study, we introduce a novel concept of reversible multi-complexation of CO2 to alkaline earth metal (AEM) ion pairs, utilizing a host site in ferrierite-type zeolite (FER). This unique site constrains two AEM ions in proximity, thereby enhancing and isotopically spreading their electrostatic potentials within the zeolite cavity. This electrostatic potential-engineered micropore can trap up to four CO2 molecules, forming M2+-(CO2)n-M2+ (n = 0-4, M = Ca, Sr, Ba) complexes, where each CO2 molecule is stabilized by interactions between terminal oxygen (Ot) in CO2 and the AEM ions. Notably, the Ba2+ pair site exhibits higher thermodynamic stability for multiple adsorptions due to the optimal binding mode of Ba2+-Ot-Ba2+. Through high-accuracy energy calculations, we established the relationship among structure, CO2 uptake, and operating temperature/pressure, demonstrating that the Ba2+ pair site can reversibly capture four CO2 molecules even at concentrations as low as 400 ppm and at 298 K. The findings in the present study provide a new direction for developing efficient CO2 adsorbents.

Pore structure and mineral composition characteristics of coal slime before and after ashing and the effects on CO2 adsorption.

To realize the resource utilization of solid waste (coal slime) and further the dual carbon goals, utilizing coal slime and coal ash as adsorbates for CO2 capture is crucial. This study employed low-temperature N2 adsorption, low-pressure CO2 adsorption, X-ray diffraction, X-ray fluorescence, and isothermal adsorption tests to assess coal slime and coal ash's pore/mineral composition characteristics. Subsequently, the influence on CO2 adsorption was analyzed to reveal the CO2 adsorption mechanisms of pores and clay minerals, and CO2 molecule adsorption behavior. The results showed that: (1) ashing led to reductions in total pore volume, specific surface area, micropore volume, and micropore specific surface area, accompanied by substantial decreases in micropores and mesopores; (2) ashing generated high-temperature stable mineral species, including quartz, andalusite, hematite, and gypsum, while all calcite decomposed into CaO; (3) coal slime exhibited greater CO2 adsorption capacity than coal ash, influenced by pore structure and clay minerals; (4) the adsorption behavior of coal slime and coal ash likely aligns with micropore filling theory, suggesting CO2 is adsorbed within the 0.30-1.47 nm pore structure. This research contributes to optimizing coal by-product utilization in mining areas and exploring adsorbate materials for CO2 sequestration in abandoned goaf.

Integrated "Two-in-One" Strategy for High-Rate Electrocatalytic CO2 Reduction to Formate.

The electrochemical CO2 reduction reaction (ECR) is a promising pathway to producing valuable chemicals and fuels. Despite extensive studies reported, improving CO2 adsorption for local CO2 enrichment or water dissociation to generate sufficient H* is still not enough to achieve industrial-relevant current densities. Herein, we report a "two-in-one" catalyst, defective Bi nanosheets modified by CrOx (Bi-CrOx), to simultaneously promote CO2 adsorption and water dissociation, thereby enhancing the activity and selectivity of ECR to formate. The Bi-CrOx exhibits an excellent Faradic efficiency (≈ 100 %) in a wide potential range from ‒0.4 to ‒0.9 V. In addition, it achieves a remarkable formate partial current density of 687 mA cm‒2 at a moderate potential of ‒0.9 V without iR compensation, the highest value at ‒0.9 V reported so far. Control experiments and theoretical simulations revealed that the defective Bi facilitates CO2 adsorption/activation while the CrOx accounts for enhancing the protonation process via accelerating H2O dissociation. This work presents a pathway to boosting formate production through tuning CO2 and H2O species at the same time.

Activation of Bi2MoO6/Zn0.5Cd0.5S charge transfer through interface chemical bonds and surface defects for photothermal catalytic CO2 reduction.

The photocatalytic reduction of CO2 to high-value fuels has been proposed as a solution to the energy crisis caused by the depletion of energy resources. Despite significant advancements in photocatalytic CO2 reduction catalyst development, there are still limitations such as poor CO2 adsorption/activation and low charge transfer efficiency. In this study, we employed a defect-induced heterojunction strategy to construct atomic-level interface Cd-O bonds and form Bi2MoO6/Zn0.5Cd0.5S heterojunctions. The sulfur vacancies (VS) formed in Bi2MoO6/Zn0.5Cd0.5S acted as activation sites for CO2 adsorption. While the interfacial stability provided by the Cd-O bonds served as an electron transfer channel that facilitated the movement of electrons from the interface to the catalytic site. The VS and Cd-O bonds simultaneously influence the distribution of charge, inducing the creation of an interface electric field that facilitates the upward displacement of the center of the d-band. This enhances the adsorption of reaction intermediates. The optimized Bi2MoO6/Zn0.5Cd0.5S heterostructure exhibited high selectivity and stability of photoelectrochemical properties for CO, generating 42.97 µmol⋅g-1⋅h-1 of CO, which was 16.65-fold higher than Zn0.5Cd0.5S under visible light drive. This research provides valuable insights for designing photocatalyst interfaces with improved CO2 adsorption conversion efficiency.

Effects of pore characteristics on CO2 adsorption performance of coal slime with different metamorphic degrees.

With the rapid development of Carbon Capture, Utilization and Storage (CCUS) technology, it is necessary to explore the feasibility of coal slime as a porous carbon material for CO2 capture. In this paper, scanning electron microscopy (SEM) was used to observe the morphological characteristics of coal slime samples with different metamorphic degrees, and the pore structure of coal slime was explored by low temperature N2 adsorption and low-pressure CO2 adsorption experiments. The pore distribution characteristics were analyzed, and the adsorption law of different metamorphic degrees were summarized through CO2 isothermal adsorption experiments. The results showed that: The specific surface area (SSA) and pore volume (PV) of the mesopores of the coal slime exhibited a U-shaped distribution with coal rank, and are much smaller than that of its micropores. Micropores less than 2 nm are the main adsorption space of coal slime, its PV accounted for 59%, 60%, 71%, and SSA accounted for 92%, 93%, 95%, obviously, which are dominant at all stages. The linear correlation fitting coefficients R2 between the limiting adsorbed amount a of CO2 and the micropores PV and the SSA were up to 0.830 and 0.887, respectively. The coal slime has good adsorption performance for CO2. Based on the Langmuir model to fit the limit adsorption amount, a-value can reach 41.774 cm3 g-1, 32.072 cm3 g-1, 38.457 cm3 g-1 at 303 K with the increase of Rmax. Studying the impact of coal slime on CO2 adsorption performance provides a theoretical basis for the subsequent preparation of energy storage materials and is of great significance for the safe, efficient and economic capture and sequestration of CO2, to alleviate the serious situation of the environment and realizing the dual-carbon goal.

Unveiling the role of silicon in boosting electrochemical carbon dioxide reduction via carbon nanotubes@bismuth silicates.

Electrochemical CO2 reduction reaction (CO2RR) is one of the most attractive measures to achieve the carbon neutral goal by converting CO2 into high-value chemicals such as formate. Si in Bi silicates is promising to enhance CO2 adsorption and activation due to its strong oxygenophilicity. Whereas, its role in boosting CO2RR via the cheap Bi-based catalysts is still not clear. Herein, we design CNT@Bi silicates catalyst, demonstrating the highest FEHCOOH of 96.3 % at -0.9 V vs. reversible hydrogen electrode with good stability. Through X-ray photoelectron spectroscopy (XPS), in-situ Attenuated Total Reflectance-Fourier Transform Infrared (In-situ ATR-SEIRAS) experiments, and Density Functional Theory (DFT) calculations, the role of Si in Bi silicates was unveiled: tuning the electronic structure of Bi, weakening the Bi-O bond, and strengthening electron transfer from Bi to CO2, thereby promoting the generation of CO2*- and *OCHO intermediates. Additionally, carbon nanotubes (CNTs) promote not only the conductivity but also the generation of abundant oxygen vacancies in CNT@Bi silicates evidenced by the electron transfer from CNT to Bi silicates from XPS results. Further, the CNT@Bi silicates endows it with the highest electrochemical activation area. These findings suggest the effectiveness of Si in Bi silicates and structure tuning to design highly selective CO2RR catalyst for HCOOH production.

Activated Carbon for CO2 Adsorption from Avocado Seeds Activated with NaOH: The Significance of the Production Method.

The rise in atmospheric greenhouse gases like CO2 is a primary driver of global warming. Human actions are the primary factor behind the surge in CO2 levels, contributing to two-thirds of the greenhouse effect over the past decade. This study focuses on the chemical activation of avocado seeds with sodium hydroxide (NaOH). The influence of various preparation methods was studied under the same parameters: carbon precursor to NaOH mass ratio, carbonization temperature, and nitrogen flow. For two samples, preliminary thermal treatment was applied (500 °C). NaOH was used in the form of a saturated solution as well as dry NaOH. The same temperature of 850 °C of carbonization combined with chemical activation was applied for all samples. The applied modifications resulted in the following textural parameters: specific surface area from 696 to 1217 m2/g, total pore volume from 0.440 to 0.761 cm3/g, micropore volume from 0.159 to 0.418 cm3/g. The textural parameters were estimated based on nitrogen sorption at -196 °C. The XRD measurements and SEM pictures were also performed. CO2 adsorption was performed at temperatures of 0, 10, 20, and 30 °C and pressure up to 1 bar. In order to calculate the CO2 selectivity over N2 nitrogen adsorption at 20 °C was investigated. The highest CO2 adsorption (4.90 mmol/g) at 1 bar and 0 °C was achieved.

Computational and Machine Learning Methods for CO2 Capture Using Metal-Organic Frameworks.

Machine learning (ML) using data sets of atomic and molecular force fields (FFs) has made significant progress and provided benefits in the fields of chemistry and material science. This work examines the interactions between chemistry and materials computational science at the atomic and molecular scales for metal-organic framework (MOF) adsorbent development toward carbon dioxide (CO2) capture. Herein, a connection will be drawn between atomic forces predicted by ML algorithms and the structures of MOFs for CO2 adsorption. Our study also takes into account the successes of atomic computational screening in the field of materials science, especially quantum ML, and its relationship to ML algorithms that clarify advancements in the area of CO2 adsorption by MOFs. Additionally, we reviewed the processes for supplying data to ML algorithms for algorithm training, including text mining from scientific articles, and MOF's formula processing linked to the chemical properties of MOFs. To create ML algorithms for future research, we recommend that the digitization of scientific records can help efficiently synthesize advanced MOFs. Finally, a future vision for developing pioneer MOF synthesis routes for CO2 capture is presented in this review article.

Enhanced CO2 Capture Potential of Chitosan-Based Composite Beads by Adding Activated Carbon from Coffee Grounds and Crosslinking with Epichlorohydrin.

Carbon dioxide (CO2) capture has been identified as a potential technology for reducing the anthropic emissions of greenhouse gases, particularly in post-combustion processes. The development of adsorbents for carbon capture and storage is expanding at a rapid rate. This article presents a novel sustainable synthesis method for the production of chitosan/activated carbon CO2 adsorbents. Chitosan is a biopolymer that is naturally abundant and contains amino groups (-NH2), which are required for the selective adsorption of CO2. Spent coffee grounds have been considered as a potential feedstock for the synthesis of activated coffee grounds through carbonization and chemical activation. The chitosan/activated coffee ground composite microspheres were created using the emulsion cross-linking method with epichlorohydrin. The effects of the amount of chitosan (15, 20, and 25 g), activated coffee ground (10, 20, 30, and 40%w/w), and epichlorohydrin (2, 3, 4, 5, 6, 7 and 8 g) were examined. The CO2 capture potential of the composite beads is superior to that of the neat biopolymer beads. The CO2 adsorbed of synthesized materials at a standard temperature and pressure is improved by increasing the quantity of activated coffee ground and epichlorohydrin. These findings suggest that the novel composite bead has the potential to be applied in CO2 separation applications.

Hierarchical porous MOF-199 mediated cellulosic paper for selective CO2 capture.

MOF-199 is considered to be an excellent CO2 adsorbent owing to its substantial specific surface area, suitable pore structure and abundant sorption sites. However, powdered MOF-199 is prone to agglomeration and has poor recyclability. Herein, we proposed a MOF-199-based adsorbent by combining the MOF synthesis process with traditional papermaking process. Through such a design, MOF-199 particles are adhered on the surface of wood pulp fiber. The sufficient hydroxyl groups and electrostatic forces of cellulose facilitates the homogeneous and tight adhesion of MOF crystals. The optimal MP-4 sample demonstrated a high CO2 adsorption capacity (1.80 mmol·g--1 at 25 °C) and good CO2/N2 selectivity (30.06). Moreover, the composite sorbent can be easily regenerated. The adsorption mechanism was analyzed by the density functional theory approach. The simulation results showed that the carboxyl functional groups with a large number of oxygen atoms and active metal sites are the key to boost the CO2 adsorption performance.

Study of CO2 Adsorption Properties on the SrTiO3(001) Surface with Ambient Pressure XPS.

The adsorption properties of CO2 on the SrTiO3(001) surface were investigated using ambient pressure X-ray photoelectron spectroscopy under elevated pressure and temperature conditions. On the Nb-doped TiO2-enriched (1 × 1) SrTiO3 surface, CO2 adsorption, i.e., the formation of CO3 surface species, occurs first at the oxygen lattice site under 10-6 mbar CO2 at room temperature. The interaction of CO2 molecules with oxygen vacancies begins when the CO2 pressure increases to 0.25 mbar. The adsorbed CO3 species on the Nb-doped SrTiO3 surface increases continuously as the pressure increases but starts to leave the surface as the surface temperature increases, which occurs at approximately 373 K on the defect-free surface. On the undoped TiO2-enriched (1 × 1) SrTiO3 surface, CO2 adsorption also occurs first at the lattice oxygen sites. Both the doped and undoped SrTiO3 surfaces exhibit an enhancement of the CO3 species with the presence of oxygen vacancies, thus indicating the important role of oxygen vacancies in CO2 dissociation. When OH species are removed from the undoped SrTiO3 surface, the CO3 species begin to form under 10-6 mbar at 573 K, thus indicating the critical role of OH in preventing CO2 adsorption. The observed CO2 adsorption properties of the various SrTiO3 surfaces provide valuable information for designing SrTiO3-based CO2 catalysts.

Nanosized Zeolite P for Enhanced CO2 Adsorption Kinetics.

Downsizing zeolite crystals is a rational solution to address the challenge of slow adsorption rates for industrial applications. In this work, we report an environmentally friendly seed-assisted method for synthesizing nanoscale zeolite P, which has been shown to be promising for binary separations. The potassium-exchanged form of nanoagglomerates demonstrates dramatically enhanced CO2 adsorption capacity, improved diffusion rate, and separation performance. Single-component CO2 adsorption at equilibrium demonstrated higher CO2 uptake and faster adsorption kinetics (ca. 1400 s vs >130000 s) for nanosized zeolite (KP1) compared to its micron-sized (KP2) counterpart. The diffusion kinetics analysis revealed the relation between the crystal size and the transport mechanism. The micron-sized KP2 sample was primarily governed by a surface barrier resistance mechanism, while in KP1, the diffusion process involved both intracrystalline and surface barrier resistance, facilitating the surface diffusion process and enhancing the overall diffusion rate. Breakthrough curve analysis confirmed these findings as fast and efficient CO2/N2 and CO2/CH4 separations recorded for the nanosized sample. The results showed remarkably enhanced breakthrough time for KP2 vs KP1 in CO2/N2 (1.0 vs 10.9 min) and CO2/CH4 (1.1 vs 9.9 min) mixtures, along with much higher adsorption capacity for CO2/N2 (0.18 vs 1.33 mmol/g) and CO2/CH4 (0.18 vs 1.21 mmol/g) mixtures. The set of experimental data demonstrates the importance of zeolite crystal engineering for improving the gas separation performance of processes involving CO2, N2, and CH4.

Characterisation of Basic Sites on Ga2O3, MgO, and ZnO with Preadsorbed Ethanol and Ammonia-IR Study.

The effect of adsorption of ethanol and ammonia on the basicity of Ga2O3, MgO, and ZnO was examined via IR studies of CO2 adsorption. Ethanol reacts with OH groups on Ga2O3, and MgO, forming ethoxyl groups. The substitution of surface hydroxyls by ethoxyls increases the basicity of the neighbouring oxygen. The ethoxyl groups that also form on ZnO do not contain surface OH groups, but the mechanism of their formation is different. On ZnO, ethoxy groups are formed by the reaction of ethanol with surface oxygens. The presence of ethoxyls on ZnO decreases the basicity because some surface oxygens are already engaged in the bonding of ethoxyl groups. The effect of ammonia adsorption on basicity is different for each oxide. For Ga2O3, ammonia adsorption increases the basicity of neighbouring oxygen sites. Ammonia is not adsorbed on MgO; therefore, it does not change the basicity of this oxide. Ammonia adsorbed on ZnO forms coordination bonds with Zn sites; it does not change the number of basic sites but changes how carbonate species are bonded to surface sites.

Utilizing silica fume and synthetically produced mesoporous silicas for simulated flue gas CO2 adsorption.

Carbon capture and storage (CCS) is crucial in mitigating greenhouse gas emissions. Solid adsorbents, notable for their reusability and corrosion resistance, are gaining attention in CO2 gas separation. This study uses Silica fume as an adsorbent and silica source for SiO2 and MCM-41 silica-based adsorbents. Silica was extracted via an alkaline dissolution method, and adsorbents were synthesized using a CO2-induced precipitation method, chosen for its shorter synthesis time and CO2 utilization. The effects of pore volume, average pore diameter, and specific surface area on amine loading and CO2 adsorption capacity were investigated using CTAB surfactant in SiO2 synthesis, resulting in MCM-41. The synthesized adsorbents were modified with TEPA and DEA amines due to their high affinity for CO2. After determining optimal amine loading, the impact of combining TEPA with DEA was examined. The highest CO2 adsorption capacity under simulated flue gas conditions (15% volume CO2 and 85% volume N2) was 198 milligrams per gram of adsorbent for the SiO2 adsorbent functionalized with 50% by weight amine (28% TEPA and 22% DEA). Variations in CO2 adsorption over time, the influence of adsorbent quantity on adsorption capacity, the affinity of the adsorbent for N2 adsorption, and the adsorption-desorption cycle were investigated. The 28%TEPA-22%DEA-SiO2 adsorbent emerged as the optimal choice due to its large total volume and average pore diameter, absence of a template in its structure, excellent performance in CO2 adsorption, lack of affinity for N2, and robust adsorption-desorption stability.

Harmonizing Between Chemical Functionality and Surface Area of Porous Organic Polymeric Nanotraps for Tuning Carbon Dioxide Capture.

The energy sector has demonstrated significant enthusiasm for investigating post-combustion CO2 capture, storage, and separation. However, the practical application of current porous adsorbents is impeded by challenges related to cost competitiveness, stability, and scalability. Intregation of heteroatoms in the porous organic polymers (POPs) dispense it more susceptible for CO2 adsorption to attenuate green house gases. In this regard, two hydroxy rich hypercrosslinked POPs, namely Ph/Tt-POP have been developed by one-pot condensation polymerization using a facile synthetic strategy. The high surface areas of both the Ph/Tt-POP (1057 and 893 m2g-1, respectively), and the heteroatom functionality in the POP framework instigated us to explore our material for CO2 adsorption study. The CO2 uptake capacities in Ph/Tt-POP are found to be 2.45 and 2.2 mmol g-1, at 273 K respectively. Further, in-situ static 13C NMR experiment shows that CO2 molecules in Tt-POP appear to be less mobile than those in Ph-POP which probably due to the presence of triazine functional groups along with high abundant -OH groups in the Tt-POP framework. An in-depth study of the CO2 adsorption mechanism by density functional theory (DFT) calculations also shows that CO2 adsorption at the cages formed by two benzyl rings represents the most stable interaction and CO2 molecule is more favorably adsorbed on the Ph-POP with the more negative interaction energies values compared to that of Tt-POP. Further, Non-covalent interaction (NCI) plot reveals that CO2 molecules adsorb more on the Ph-POP than Tt-POP, which can be explain by hydrogen bond formation in case of Tt-POP repeating units turning aside CO2 molecule to interact with the Ph component. Overall, our present study reflects the comprising effects of surface area of the solid adsorbents as well as their functionality can be beneficial for developing efficient hypercrosslinked porous polymers as solid CO2 adsorbent.

Microsolvation of cobalt, nickel, and copper atoms with ammonia: a theoretical study of the solvated electron precursors.

CONTEXT: The s-block metals dissolved in ammonia form metal-ammonia complexes with diffuse electrons which could be used for redox catalysis. In this theoretical paper, we investigated the possibility of the d-bloc transition metals (Mn, Fe, Co, Ni, and Cu) solvated by ammonia. It has been demonstrated that both Mn and Fe atoms undergo into an oxidative reaction with NH3 forming an inserted species, HMNH2. On the contrary, the Co, Ni, and Cu atoms can accommodate four NH3, via the coordination bond, to form the first solvation sphere within C2v, D2d, and Td point groups, respectively. Addition of a fifth NH3 constitute the second solvation shell by forming hydrogen bond with the other NH3s. Interestingly, M(NH3)4 (M = Co, Ni, and Cu) is a so-called solvated electron precursor and should be considered as a monocation M(NH3)4+ kernel in tight contact with one electron distributed over its periphery. This nearly free electron could be used to capture a CO2 molecule and engages in a reduction reaction. METHODS: Geometry optimization of the stationary points on the potential energy surface was performed using density functional theory - CAM-B3LYP functional including the GD3BJ dispersion contribution - in combination with the 6-311 + + G(2d, 2p) basis set for all the atoms. All first-principles calculations were performed using the Gaussian 09 quantum chemical packages. The natural electron configuration of transition atom engaged in the compounds has been found using the natural bond orbital (NBO) method. We used the EDR (electron delocalization range) approach to analyze the structure of solvated electrons in real space. We also used the electron localization function (ELF) to measure the degree of electronic localization within a chemical compound. The EDR and ELF analyses are done using the TopMod and Multiwfn packages, respectively.

Determination of concentration of basic sites on oxides by IR spectroscopy.

As it is commonly known, CO2 reacts simultaneously with basic O2- and basic OH sites on oxides forming carbonates and bicarbonates, which can be followed by infrared spectroscopy (IR). However, here, we succeeded to elaborate experimental conditions under which CO2 reacted solely with O2- forming CO32- for ZrO2 and CeO2, and calculated the extinction coefficients of diagnostic bands of carbonate and bicarbonate species. For the first time, the developed IR method enabled the concentrations of O2- and basic OH for ZrO2, CeO2, Al2O3 and CuO to be measured separately. Moreover, in the case of all IR studied oxides, the sum of concentrations of O-2 and basic OH basic sites was comparable with the concentration determined by pulse adsorption of CO2. Thus, the presented extinction coefficients can be applied for IR basicity studies of various basic catalysts. We also followed the effect of thermal treatment on basicity of oxides.

Mechanochemical Synthesis of MOF-303 and Its CO2 Adsorption at Ambient Conditions.

Metal-organic structures have great potential for practical applications in many areas. However, their widespread use is often hindered by time-consuming and expensive synthesis procedures that often involve hazardous solvents and, therefore, generate wastes that need to be remediated and/or recycled. The development of cleaner, safer, and more sustainable synthesis methods is extremely important and is needed in the context of green chemistry. In this work, a facile mechanochemical method involving water-assisted ball milling was used for the synthesis of MOF-303. The obtained MOF-303 exhibited a high specific surface area of 1180 m2/g and showed an excellent CO2 adsorption capacity of 9.5 mmol/g at 0 °C and under 1 bar.

Extra-High CO2 Adsorption and Controllable C2H2/CO2 Separation Regulated by the Interlayer Stacking in Pillar-Layered Metal-Organic Frameworks.

Pillar-layered metal-organic frameworks (PLMOFs) are promising gas adsorbents due to their high designability. In this work, high CO2 storage capacity as well as controllable C2H2/CO2 separation ability are acquired by rationally manipulating the interlayer stacking in pillar-layered MOF materials. The rational construction of pillar-layered MOFs started from the 2D Ni-BTC-pyridine layer, an isomorphic structure of pioneering MOF-1 reported in 1995. The replacement of terminal pyridine groups by bridging pyrazine linkers under optimized solvothermal conditions led to three 3D PLMOFs with different stacking types between adjacent Ni-BTC layers, named PLMOF 1 (ABAB stacking), PLMOF 2 (AABB stacking), and PLMOF 3 (AAAA stacking). Regulated by the layer arrangements, CO2 and C2H2 adsorption capacities (273 K and 1 bar) of PLMOFs 1-3 vary from 173.0/153.3, 185.0/162.4, to 203.5/159.5 cm3 g-1, respectively, which surpass the values of most MOF adsorbents. Dynamic breakthrough experiments further indicate that PLMOFs 1-3 have controllable C2H2/CO2 separation performance, which can successfully overcome the C2H2/CO2 separation challenge. Specially, PLMOFs 1-3 can remove trace CO2 (3%) from the C2H2/CO2 mixture and produce high-purity ethylene (99.9%) in one step with the C2H2 productivities of 1.68, 2.45, and 3.30 mmol g-1, respectively. GCMC simulations indicate that the superior CO2 adsorption and unique C2H2/CO2 separation performance are mainly ascribed to different degrees of CO2 agglomeration in the ultramicropores of these PLMOFs.