Efficient adsorption of radioactive iodine by covalent organic framework/chitosan aerogel.

Radioactive iodine is considered one of the most dangerous radioactive elements in nuclear waste. Therefore, effective capture of radioactive iodine is essential for developing and using nuclear energy to solve the energy crisis. Some materials that have been developed for removing radioactive iodine still suffer from complex synthesis, low removal capacity, and non-reusability. Herein, covalent organic framework (COF)/chitosan (CS) aerogels were prepared using vacuum freeze-drying, and the COF nanoparticles were tightly attached on the green biomass material CS networks. Due to the synergistic effect of both COF and CS, the composite aerogel shows a three-dimensional porous and stable structure in the recycle usage. The COF/CS aerogel exhibits excellent iodine adsorption capacity of 2211.58 mg g-1 and 5.62 g g-1 for static iodine solution and iodine vapor, respectively, better than some common adsorbents. Furthermore, COF/CS aerogel demonstrated good recyclability performance with 87 % of the initial adsorption capacity after 5 cycles. In addition, the interaction between iodine and imine groups, amino groups, and benzene rings of aerogel are the possible adsorption mechanisms. COF/CS aerogel has excellent adsorption properties, good chemical stability, and reusable performance, which is a potential and efficient adsorbent for industrial radioactive iodine adsorption from nuclear waste.

High-efficient removal of anionic dye from aqueous solution using metal-organic frameworks@chitosan aerogel rich in benzene structure.

With the exponentially increase of dye pollutants, the purification of dye wastewater has been an urgent ecological problem. As a novel type of porous adsorbent, metal-organic frameworks still face challenges in recyclability, agglomeration, and environmentally unfriendly synthesis. Herein, MOF-525 was in-situ growth onto the surface of the chitosan (CS) beads to fabricate MOF-525@CS aerogel. CS was utilized as substrate to uniformly disperse MOF-525, thereby significantly mitigating agglomeration and improving recyclability of MOF-525. The characterization results shown that MOF-525@CS aerogel had a high specific surface area of 103.0 m2·g-1, and MOF-525 was uniformly distributed in the 3D porous structure of CS, and the presence of benzoic acid was detected. The MOF-525@CS aerogel had a remarkable adsorption capacity of 1947 mg·g-1 for Congo red, which is greater than the sum of its parts. MOF-525@CS aerogel also inherited the rapid adsorption ability of MOF-525, removing 80 % of Congo red within 600 min. Such excellent adsorption performance can be attributed to the benzoic acid trapped by CS via CN band to enhance the π-π stacking interactions. Additionally, the utilization of benzoic acid makes the synthesis process of MOF-525@CS aerogel more environmentally friendly. The high-efficient MOF-525@CS aerogel is a competitive candidate for dye pollution adsorption.

Porous metal-organic framework-acrylamide-chitosan composite aerogels: Preparation, characterization and adsorption mechanism of azo anionic dyes adsorbed from water.

Micro- and nano-metal-organic frameworks with different adsorption properties were prepared by a time-modulation hydrothermal method. By comparing the adsorption properties, the most effective MIL-68(Fe)-12 was selected to be mixed with chitosan (CS), and porous metal-organic framework-acrylamide-chitosan composite aerogel (PMACA) was prepared by introducing acrylamide prior to glutaraldehyde crosslinking. The adsorption capacity of PMACA doped with acrylamide was as high as 2086.44 mg·g-1. The adsorption performance of PMACA was 1.48 times higher compared to the porous metal-organic framework-chitosan composite aerogel (PMCA) undoped with acrylamide. With the introduction of acrylamide, the stability of PMACA was improved, making it less prone to dispersion and decomposition. Structural characterization and adsorption properties were analyzed using methods such as XRD, FTIR, TGA, SEM, BET, and Zeta potential. The adsorption performance of PMACA was investigated further through batch tests with variables such as adsorbent dosage, pH, contact time, initial CR solution concentration, and temperature. The model fitting of PMACA was consistent with the pseudo-second-order model and the Sips model. The adsorption thermodynamics showed that high temperature promoted spontaneous adsorption behavior. PMACA showed a recovery rate of approximately 86 % after six cyclic adsorption tests. PMACA maintained a recovery rate of roughly 86 % after six cyclic adsorption tests. The combined effects of electrostatic attraction, hydrogen bonding, and π-π conjugation resulted in excellent adsorption performance, while pore filling also contributed to the efficient adsorption of Congo red (CR).

Investigation of the Mechanisms of CO2/O2 Adsorption Selectivity on Carbon Materials Enhanced by Oxygen Functional Groups.

Power plant flue gas and industrial waste gas are produced in large quantities. Using these as feedstocks for CO2 electroreduction has important practical significance for the treatment of excessive CO2 emissions. However, O2 in such sources strongly inhibits the electrochemical conversion of CO2. The inhibitory effect of O2 can be mitigated by constructing CO2-enriched regions on the surface of the cathode. In this study, the reaction zone was controlled by the selective adsorption of CO2 on oxygen-functionalized carbon materials. The results of quantum chemical simulations showed that CO2 adsorption was mainly influenced by electrostatic interactions, whereas O2 adsorption was completely regulated by dispersion interactions. This distinction indicated that introducing polar oxygen functional groups at the edge of the carbon plane can significantly enhance the selectivity for CO2/O2 adsorption. The difference in the adsorption energy between CO2 and O2 increased most noticeably after the carboxyl groups were introduced. The results of the adsorption experiments showed that oxygen-functionalization increased the CO2/O2 selectivity of the carbon material under an atmosphere of multicomponent gases by more than 4.9 times. The carboxyl groups played a dominant role. Our findings might act as a reference for the selective adsorption of polar molecules over nonpolar molecules.

Green preparation of magnetic ferroferric oxide-polyvinyl alcohol-alginate coated UiO-67 nanospheres: Characterization, adsorption properties and adsorption mechanism of methylene blue.

In this paper, a kind of magnetic ferric oxide/polyvinyl alcohol/calcium alginate/UiO-67 (Fe3O4/PVA/CA/UiO-67) nanospheres with homogeneous surface interconnecting structures was prepared by using macromolecular polymer polyvinyl alcohol and sodium alginate as carriers and zirconium organic skeleton as nanocrystals. The properties of magnetic nanospheres were studied by SEM, FT-IR, TGA, XRD, BET, VSM and Zeta potential. The impression of diverse temperatures, MB concentrations, interaction time, pH, and magnetic aerogel sphere dose on MB removal was studied. The optimum adsorption temperature and pH of magnetic nanospheres for MB were 298 K, and 10, respectively. Langmuir simulated that the maximum removal of MB by magnetic nanospheres at room temperature (298 K) was 1371.8 mg/g. The removal of MB by magnetic nanospheres complied with the pseudo-first-order kinetic model. The isotherm simulation can infer that the Langmuir model was more comply with MB adsorption on magnetic aerogel spheres. Thermodynamic studies have confirmed that the removal of MB by magnetic nanospheres was exothermic and spontaneous. The interaction mechanism of MB on magnetic nanospheres can be deduced by FT-IR and BET, including hydrogen bond, π-π bond, electrostatic interaction, and mesoporous pore flow. The removal rate of nanospheres for MB still reached 70.06 % after six cycles.

Efficient adsorption of methylene blue in water by nitro-functionalized metal-organic skeleton­calcium alginate composite aerogel.

This paper presents the first investigation of the adsorption performance of methylene blue by the nitro-functionalized metal-organic framework (MIL-88B-NO2). MIL-88B-NO2 has a specific surface area of 836.0 m2/g, which is 109.8 % higher than MIL-88B. The maximum adsorption capacity of methylene blue is 383.6 mg/g, which is 68.2 % higher than that of MIL-88B. This phenomenon can be attributed to the great increase in specific surface area and the introduction of nitro-functional groups. However, its microcrystalline nature makes it difficult to remove in practical applications and quickly causes secondary pollution. Therefore, the composite of MIL-88B-NO2 and calcium alginate (CA) to form aerogel maintains the inherent properties of the two materials and makes it easy to recycle. The utmost adsorption capability of MIL-88B-NO2/CA-2 aerogel is 721.0 mg/g. Compared with MIL-88B-NO2, the adsorption performance of MIL-88B-NO2/CA-2 aerogel is further improved by 88.0 %. The higher adsorption capacity of the adsorbent may be due to the synergistic interplay of electrostatic attraction, π-π conjugation, hydrogen bonding, metal coordination effect, and physicochemical properties. Also, MIL-88B-NO2/CA-2 aerogel has good recyclability, indicating that it has broad application prospects in the removal of positive dyes in contaminated water.

Efficient adsorption of azo anionic dye Congo Red by micro-nano metal-organic framework MIL-68(Fe) and MIL-68(Fe)/chitosan composite sponge: Preparation, characterization and adsorption performance.

Micro-nano metal-organic framework (MIL-68(Fe)) for efficient adsorption of azo anionic dye Congo red (CR) was successfully prepared by one-step hydrothermal method under acidic environment. And a MIL-68(Fe)/chitosan composite sponge (MIL-68(Fe)/CS) was prepared under the coating of chitosan (CS). After comparing the performance of MIL-68(Fe) and MIL-68(Fe)/CS, we focus on exploring MIL-68(Fe)/CS. It ensured the CR removal efficiency while reaching the adsorption equilibrium faster than MIL-68(Fe), and solved the defect that the powder was difficult to be stripped by water after adsorption. The physicochemical properties and surface morphology of the adsorbent were characterized by SEM, FTIR, XRD, TGA, BET, and Zeta potential. The effects of pH, contact time, adsorbent dosage, initial solution concentration and temperature on the adsorption performance of the adsorbent were systematically analyzed. The pseudo-second-order model and the Sips model were most consistent for the adsorption process, indicating that the adsorption process of MIL-68(Fe)/chitosan composite sponge on CR is a complex physicochemical process. The removal rates of CR by MIL-68(Fe) and MIL-68(Fe)/chitosan composite sponge reached the maximum values of 99.55 % and 99.51 % at 318 K, respectively. And the maximum adsorption capacity of CR by MIL-68(Fe)/chitosan composite sponge at 318 K was 1184.16 mg·g-1. After six cycles of adsorption and desorption, the removal rate of CR was still higher than 80 %. The synergistic effects of π-π stacking, electrostatic interactions, hydrogen bonding and pore filling have important effects on CR removal.

NiFe Nanoparticle-Encapsulated Ultrahigh-Oxygen-Doped Carbon Layers as Bifunctional Electrocatalysts for Rechargeable Zn-Air Batteries.

There is an urgent demand for developing highly efficient bifunctional electrocatalysts with excellent stability toward the oxygen evolution and reduction reactions (OER and ORR, respectively) for rechargeable Zn-air batteries (ZABs). In this work, NiFe nanoparticles encapsulated within ultrahigh-oxygen-doped carbon quantum dots (C-NiFe) as bifunctional electrocatalysts are successfully obtained. The accumulation of carbon layers formed by carbon quantum dots results in abundant pore structures and a large specific surface area, which is favorable for improving catalytic active site exposure, ensuring high electronic conductivity and stability simultaneously. The synergistic effect of NiFe nanoparticles enriched the number of active centers and naturally increased the inherent electrocatalytic performance. Benefiting from the above optimization, C-NiFe shows excellent electrochemical activity for both OER and ORR processes (the OER overpotential is only 291 mV to achieve 10 mA cm-2). Furthermore, the C-FeNi catalyst as an air cathode displays an impressive peak power density of 110 mW cm-2, an open-circuit voltage of 1.47 V, and long-term durability over 58 h. The preparation of this bifunctional electrocatalyst provides a design idea for the construction of bimetallic NiFe composites for high-performance Zn-air batteries.

The Defects, Physicochemical Properties, and Surface Charge of MIL-88A (Al) Crystal Were Regulated for Highly Efficient Removal of Anionic Dyes: Preparation, Characterization, and Adsorption Mechanism.

In this paper, the physicochemical properties, surface charge, and crystal defects of MIL-88A (Al) were controlled by adjusting the ratio of metal ligands and temperature in the synthetic system without the addition of surfactants. The adsorption properties of different crystals for Congo red (CR) were studied. Among them, MIL-88A (Al)-130 and MIL-88A (Al)-d have the best adsorption properties. The maximum adsorption capacities are 600.8 and 1167 mg · g-1, respectively. Compared with MIL-88A (Al)-130, the adsorption performance of MIL-88A (Al)-d was increased by 94.2%, and the adsorption rate was increased by about 4 times. It can be seen that increasing the proportion of metal ligands within a certain range will improve the adsorption capacity. The structure and morphology of the adsorbent were characterized by XRD, FTIR, SEM, EDS, TGA, BET, and zeta potential. The effects of time, temperature, pH, initial solution concentration, and dosage on CR adsorption properties were systematically discussed. The pseudo-second-order kinetic model and Langmuir isothermal model can well describe the adsorption process, which indicates that the adsorption process is a single-layer chemisorption occurring on a uniform surface. According to thermodynamics, this adsorption is an endothermic process. The mechanism of CR removal is proposed as the electrostatic attraction, hydrogen bond, metal coordination effect, π-π conjugation, crystal defect, and pore-filling effect. In addition, MIL-88A (Al)-d has good repeatability, indicating that it is a good material for treating anionic dye wastewater.

Simple synthesis of chitosan/alginate/graphene oxide/UiO-67 amphoteric aerogels: Characterization, adsorption mechanism and application for removal of cationic and anionic dyes from complex dye media.

A chitosan/alginate/graphene oxide/UiO-67 (CS/SA/GO/UiO-67) amphoteric aerogel was synthesized successfully. A series of characterization experiments of CS/SA/GO/UiO-67 amphoteric aerogel was performed by SEM, EDS, FT-IR, TGA, XRD, BET, and zeta potential. The competitive adsorption properties of different adsorbents for complex dyes wastewater (MB and CR) at room temperature (298 K) were compared. Langmuir isotherm model predicted that the maximum adsorption quantity of CS/SA/GO/UiO-67 for CR and MB was 1091.61 and 1313.95 mg/g, respectively. The optimum pH values of CS/SA/GO/UiO-67 for the adsorption of CR and MB were 5 and 10, respectively. The kinetic analysis showed that the adsorption of MB and CR on CS/SA/GO/UiO-67 was more suitable for the pseudo-second-order and pseudo-first-order kinetic model, respectively. The isotherm study revealed that the adsorption of MB and CR was consistent with the Langmuir isotherm model. The thermodynamic study demonstrated that the adsorption process of MB and CR was exothermic and spontaneous. FT-IR analysis and zeta potential characterization experiments revealed that the adsorption mechanism of MB and CR on CS/SA/GO/UiO-67 depended on π-π bond, hydrogen bond, and electrostatic attraction. Repeatable experiments showed that the removal rates of MB and CR of CS/SA/GO/UiO-67 after six cycles of adsorption were 67.19 and 60.82 %, respectively.

Efficient adsorption of Congo red by micro/nano MIL-88A (Fe, Al, Fe-Al)/chitosan composite sponge: Preparation, characterization, and adsorption mechanism.

MIL-88A crystals with three different metal ligands (Fe, Al, FeAl) were prepared by hydrothermal method for the first time. The three materials' crystal structure and surface morphology are different, leading to different adsorption properties of Congo red (CR). The maximum adsorption capacities of MIL-88A (Fe), MIL-88A (FeAl), and MIL-88A (Al) are 607.7 mg · g-1, 536.4 mg · g-1, and 512.1 mg · g-1 respectively. In addition, MIL-88A was combined with chitosan (CS) respectively, and MIL-88A/CS composite sponge was prepared by the freeze-drying method, which not only solved the defect that MIL-88A powder was difficult to recover but also further improved the removal ability of CR by the adsorbent. The maximum adsorption capacities of MIL-88A (FeAl)/CS, MIL-88A (Fe)/CS, MIL-88A (Al)/CS, and CS are 1312 mg · g-1, 1056 mg · g-1, 996.7 mg · g-1, and 769.6 mg · g-1, respectively. The structure and physicochemical properties of the materials were analyzed by SEM, FTIR, XRD, TGA, BET, and Zeta. The adsorption process of CR follows pseudo-second-order kinetics and Langmuir, Sips isotherm model. Combined with thermodynamic parameters, the adsorption behavior was described as endothermic monomolecular chemical adsorption. The removal of CR is attributed to electrostatic interactions, hydrogen bonding, metal coordination effects, and size-matching effects.

Enhanced methylene blue adsorption using zirconate alginate/graphene oxide/UiO-67 aerogel spheres: Synthesis, characterization, kinetic studies, and adsorption mechanisms.

Zirconium alginate/graphene oxide (ZA/GO) hydrogel spheres were prepared by crosslinking sodium alginate and GO with Zr4+. Then Zr4+ on the surface of the ZA/GO substrate acted as the metal nucleation site of the UiO-67 crystal and interacted with the organic ligand biphenyl 4-4'-dicarboxylic acid (BPDC) to make UiO-67 grow in situ on the surface of the ZA/GO hydrogel sphere by the hydrothermal method. The BET surface areas of ZA/GO, ZA/UiO-67, and ZA/GO/UiO-67 aerogel spheres were 1.29, 47.71, and 89.33 m2/g respectively. The maximum adsorption capacities of ZA/GO, ZA/UiO-67, and ZA/GO/UiO-67 aerogel spheres for methylene blue (MB) at room temperature (298 K) were 145.08, 307.49, and 1105.23 mg/g respectively. The kinetic analysis showed that the adsorption process of MB on the ZA/GO/UiO-67 aerogel sphere was consistent with the pseudo-first-order kinetic model. Isotherm analysis showed that MB was adsorbed on ZA/GO/UiO-67 aerogel spheres as a single layer. Thermodynamic analysis showed that the adsorption process of MB on the ZA/GO/UiO-67 aerogel sphere was exothermic and spontaneous. Adsorption of MB on ZA/GO/UiO-67 aerogel spheres is mainly dependent on π-π bond, electrostatic interaction, and hydrogen bond. After 8 cycles, ZA/GO/UiO-67 aerogel spheres still showed high adsorption performance and good reuse ability.

Methylene Blue Removed from Aqueous Solution by Encapsulation of Bentonite Aerogel Beads with Cobalt Alginate.

It can be difficult to remove dark methylene blue (MB) from water effectively. The use of sodium alginate and bentonite (Ben) as the matrix produced a displacement reaction that occurred in cobalt chloride, which allowed Ben to be successfully encapsulated in cobalt alginate (CA). Finally, a vacuum freeze-drying method was used to prepare a low-cost composite of CA/Ben aerogel for adsorbing MB in aqueous solutions. In addition to scanning electron microscopy, thermogravimetric analysis, and Fourier transform infrared spectroscopy, the composites were also characterized and analyzed. Different adsorption experiments were conducted in order to determine the effects of dosage, pH, adsorption time, and temperature on the adsorption performance of the adsorbent. According to the results of the experiment, the adsorption capacity of CA/Ben aerogel was 258.92 mg·g-1, and the pseudo-first-order kinetic model and Freundlich isotherm model can fully explain the adsorption process of MB on this aerogel. The composite material reported in this paper is easily recycled, and the removal rate reaches 65% after four times of recycling. Moreover, compared with other adsorbents, the composite material of the invention is highly environmentally friendly and has a simple preparation process. A large-scale application of this technology is the removal of dyes from water on a large scale.

Effective Removal of Tetracycline from Water Using Copper Alginate @ Graphene Oxide with In-Situ Grown MOF-525 Composite: Synthesis, Characterization and Adsorption Mechanisms.

For nanomaterials, such as GO and MOF-525, aggregation is the main reason limiting their adsorption performance. In this research, Alg-Cu@GO@MOF-525 was successfully synthesized by in-situ growth of MOF-525 on Alg-Cu@GO. By dispersing graphene oxide (GO) with copper alginate (Alg-Cu) with three-dimensional structure, MOF-525 was in-situ grown to reduce aggregation. The measured specific surface area of Alg-Cu@GO@MOF-525 was as high as 807.30 m2·g-1, which is very favorable for adsorption. The synthesized material has affinity for a variety of pollutants, and its adsorption performance is significantly enhanced. In particular, tetracycline (TC) was selected as the target pollutant to study the adsorption behavior. The strong acid environment inhibited the adsorption, and the removal percentage reached 96.6% when pH was neutral. Temperature promoted the adsorption process, and 318 K adsorption performance was the best under experimental conditions. Meanwhile, 54.6% of TC could be removed in 38 min, and the maximum adsorption capacity reached 533 mg·g-1, far higher than that of conventional adsorption materials. Kinetics and isotherms analysis show that the adsorption process accords with Sips model and pseudo-second-order model. Thermodynamic study further shows that the chemisorption is spontaneous and exothermic. In addition, pore-filling, complexation, π-π stack, hydrogen bond and chemisorption are considered to be the causes of adsorption.

Adsorption of Methylene Blue from Aqueous Solution Using Gelatin-Based Carboxylic Acid-Functionalized Carbon Nanotubes@Metal-Organic Framework Composite Beads.

A novel gelatin-based functionalized carbon nanotubes@metal-organic framework (F-CNTs@MOF@Gel) adsorbent was prepared by the green and simple method for the adsorption of methylene blue (MB). Cu-BTC (also known as HKUST-1) was selected as the MOF type. F-CNTs@Cu-BTC particles were fixed by gelatin, thus avoiding the secondary pollution of carbon nanomaterial particles to the environment. CNTs were used as the connecting skeleton to make more effective adsorption sites exposed on the surface of the internal pore structure of the adsorbent. In this paper, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (XRD), thermogravimetry (TGA) and BET analysis methods were used to characterize the new adsorbent. The effects of time, temperature, pH, dosage and initial concentration on the adsorption process were investigated by batch adsorption experiments. The adsorption mechanism was further analyzed by several commonly used kinetic and isotherm models, and the reliability of several fitting models was evaluated by the Akaike information criterion (AIC), Bayesian information criterion (BIC) and Hannan information criterion (HIC). After five regeneration experiments, the adsorbent still had 61.23% adsorption capacity. In general, the new adsorbent studied in this paper has an optimistic application prospect.

Metal-Organic Complexes@Melamine Foam Template Strategy to Prepare Three-Dimensional Porous Carbon with Hollow Spheres Structures for Efficient Organic Vapor and Small Molecule Gas Adsorption.

Three-dimensional (3D) porous carbon materials have received substantial attention owing to their unique structural features. However, the synthesis of 3D porous carbon, especially 3D porous carbon with hollow spheres structures at the connection points, still pose challenges. Herein, we first develop a metal-organic complexes@melamine foam (MOC@MF) template strategy, by using hot-pressing and carbonization method to synthesize 3D porous carbon with hollow spheres structures (denoted as NOPCs). The formation mechanism of NOPCs can be attributed to the difference in Laplace pressure and surface energy gradient between the carbonized MOC and carbonized MF. These rare 3D porous carbons exhibit high BET surface area (2453.8 m2 g-1), N contents (10.5%), and O contents (16.3%). Moreover, NOPCs show significant amounts of toluene and methanol at room temperature, reaching as high as 1360 and 1140 mg g-1. The adsorption amounts of SO2 and CO2 for NOPCs are up to 93.1 and 445 mg g-1. Theoretical calculation indicates surfaces of porous carbon with N and O coexistence could strongly enhance adsorption with high adsorption energy of -65.83 kJ mol g-1.

Micromesoporous Nitrogen-Doped Carbon Materials Derived from Direct Carbonization of Metal-Organic Complexes for Efficient CO2 Adsorption and Separation.

Metal-organic complexes (MOCs) are considered as excellent precursors to prepare carbon materials, due to the fact that heteroatoms and functional groups can be naturally reserved in the resulting carbon materials through the carbonization. Herein, micromesoporous nitrogen-doped carbons MPNC-1 and MPNC-2 are successfully obtained by direct carbonization (800 °C, KOH activation) of metal-organic complexes DQA-1 and DQA-2. MPNC-1 and MPNC-2 exhibit high BET surface area (2368.9 and 2327.6 m2 g-1), pore volume (1.95 and 1.89 cm3 g-1), and N contents (17.2% and 12.3%). At 25 °C and 1 bar, MPNC-1 and MPNC-2 show high CO2 adsorption of 7.53 and 6.58 mmol g-1, the estimated CO2/N2 selectivity are 20.5 and 22.6, indicating excellent promise for practical CO2 adsorption and separation applications. Theoretical calculation indicates carbon surfaces with pyridinic-N, pyrrolic-N, and graphitic-N coexistence could strongly change the local electronic distribution and electrostatic surface potential, enhancing the CO2 adsorption with adsorption energy of -58.96 kJ mol g-1. Theoretical calculation also highlights that CO2 adsorption mechanism is electrostatic interaction with a large green isosurface between CO2 molecules and the carbon surface.

A new insight into the SO2 adsorption behavior of oxidized carbon materials using model adsorbents and DFT calculations.

Heteroatom-doped carbon materials have been proven to be very effective for gas adsorption. Herein, edge-carboxylated graphene nanoplatelets with gradient oxygen contents and consistent pore structures were used as model adsorbents to independently determine the effects of the oxygen functionalization of carbon materials on the SO2 adsorption. The OGnPs were obtained by employing a simple ball milling method using dry ice by which an oxygen content as high as 14.06 wt% could be achieved, resulting in a 20 times increase in SO2 adsorption capacity as compared to that of oxygen-free graphene nanoplatelets. Both the experiments and density functional theory calculations demonstrated that the enhanced SO2 adsorption on the oxygenated carbon surface had a physisorption nature, which provided new insights into the development of advanced carbon materials with heteroatom doping for gas molecule adsorption.

Nitrogen-Doped Microporous Carbons Derived from Pyridine Ligand-Based Metal-Organic Complexes as High-Performance SO2 Adsorption Sorbents.

Heteroatom-doped porous carbons are emerging as platforms for gas adsorption. Herein, N-doped microporous carbon (NPC) materials have been synthesized by carbonization of two pyridine ligand-based metal-organic complexes (MOCs) at high temperatures (800, 900, 1000, and 1100 °C). For NPCs (termed NPC-1- T and NPC-2- T, where T represents the carbonization temperature), the micropore is dominant, pyridinic-N and other N atoms of MOC precursors are mostly retained, and the N content reaches as high as 16.61%. They all show high Brunauer-Emmett-Teller surface area and pore volume, in particular, NPC-1-900 exhibits the highest surface areas and pore volumes, up to 1656.2 m2 g-1 and 1.29 cm3 g-1, respectively, a high content of pyridinic-N (7.3%), and a considerable amount of SO2 capture (118.1 mg g-1). Theoretical calculation (int = ultrafine m062x) indicates that pyridinic-N acts as the leading active sites contributing to high SO2 adsorption and that the higher content of pyridinic-N doping into the graphite carbon layer structure could change the electrostatic surface potential, as well as the local electronic density, which enhanced SO2 absorption on carbon edge positions. The results show great potential for the preparation of microporous carbon materials from pyridine ligand-based MOCs for effective SO2 adsorption.

Broadening the pore size of coal-based activated carbon via a washing-free chem-physical activation method for high-capacity dye adsorption.

Aiming to overcome the limitations of the narrow pore size distributions of traditional activated carbon materials and to achieve wide adaptabilities towards large molecules adsorption, we herein demonstrate a new type of activated carbon with a broadened pore size distribution for high-rate and high-capacity aqueous dye molecule (Rhodamine B) adsorption. The preparation of CP-AC is achieved by a facile and one-step mineral-assisted chem-physical activation strategy from Chinese large-reserve Zhundong coal with ZnCl2 and CO2 as the activation agents. The method yields the activated carbon (CP-AC) that has a pore-size broadened hierarchical pore configuration with a high surface area and a large pore volume, favorably enabling a high-capacity Rhodamine B adsorption up to 881 mg g-1, which is among the highest levels of the reported activated carbons. A sonication-assisted adsorption test further demonstrates the high-rate adsorption capability of CP-AC with Rhodamine B adsorption capacity up to 842 mg g-1 within 30 min (96% of the saturation capacity) while microporous activated carbon obtained by solely ZnCl2 activation could just achieve a capacity of 374 mg g-1 within 30 min. In virtue of the low-cost resource materials and washing-free craft, this work offers a simple and green preparation strategy towards high-performance coal based activated carbons, holding great potentials for the industrial production and applications.