Microporous Carbon Materials Research Articles

Understanding the improved performances of Lithium–Sulfur batteries containing oxidized microporous carbon with an affinity-controlled interphase as a sulfur host

Li–S batteries (LSBs) based on the solid-phase conversion reaction that contain microporous carbon (MC) materials as their S hosts exhibit high cycling stabilities. Oxidized MC with O-containing functional groups increases the capacity of LSBs and lowers their internal resistance. Although these polar functional groups should improve the electrolyte affinities of electrode materials, their effects on the MC–S cathode/electrolyte interface have not yet been clarified. Herein, we report the affinity between the MC–S cathode and electrolyte. Contrary to conventional wisdom, the O-containing functional groups form affinity-controlled interphases on the MC–S cathodes, alleviating electrolyte decomposition and the formation of a cathode–electrolyte interphase during LSB cycling. This lowers the internal resistance of the LSB by facilitating unhindered Li-ion conduction, which stabilizes cycling at a low electrolyte [μL]/S [mg] ratio of 2.0, with an improved capacity (from 6.58 to 309.4 mAh g−1) in the second cycle. Thus, the use of an affinity-controlled interphase should improve the energy densities of LSBs and other energy storage devices.

Inducing One-Step Dehydrogenation of Magnesium Borohydride via Confinement in Robust Dodecahedral Nitrogen-Doped Porous Carbon Scaffold.

A dodecahedral activated N-doped porous carbon scaffold is synthesized and used for the nanoconfinement of Mg(BH4)2. The optimized mesoporous scaffold possesses an accumulated pore width of 2.65nm, high specific surface area (3955.9 m2g-1), and large pore volume (2.15 cm3g-1), providing ample space for the confinement of Mg(BH4)2 particles and numerous surface active sites for interactions with the same. The confined Mg(BH4)2 system features a dehydrogenation onset temperature of 81.5°C, an extremely high capacity of 10.2 wt% H2, and an almost single-step dehydrogenation profile. Moreover, the system exhibits superior capacity retention of 82.7% after 20 cycles at a moderate temperature of 250°C. Precise activation control enables a transformation from microporous carbon materials to mesoporous ones, and hence the efficient nanoconfinement of Mg(BH4)2 and realization of one-step dehydrogenation. The evolution of borohydride intermediates is systematically revealed throughout the cycling process. Density functional theory calculations demonstrate defective N heteroatoms within the scaffold are vital in reducing the strength of B─H bonds, and the N-doped carbon can facilitate decomposition of the irreversible MgB12H12 intermediate. This study opens up new avenues for designing robust carbon scaffolds doped with heteroatoms and analyzing intermediate evolution in nanoconfined Mg-based borohydride systems.

Activated Iron-Porous Carbon Nanomaterials as Adsorbents for Methylene Blue and Congo Red.

The adsorption properties of microporous carbon materials modified with iron citrate were investigated. The carbon materials were produced based on resorcinol-formaldehyde resin, treated in a microwave assisted solvothermal reactor, and next carbonized in the tube furnace at a temperature of 700 °C under argon atmosphere. Iron citrate was applied as a modifier, added to the material precursor before the synthesis in the reactor, in the quantity enabling to obtain the nanocomposites with C:Fe mass ratio equal to 10:1. Some samples were additionally activated using potassium oxalate or potassium hydroxide. The phase composition of the produced nanocomposites was determined using the X-ray diffraction method. Scanning and transmission electron microscopy was applied to characterize the changes in samples' morphology resulting from the activation process and/or the introduction of iron into the carbon matrix. The adsorption of nitrogen from gas phase and dyes (methylene blue and congo red) from water solution on the obtained materials was investigated. In the case of methylene blue, the adsorption equilibrium isotherms followed the Langmuir isotherm model. However, in the case of congo red, a linear dependency of adsorption and concentration in a broad equilibrium concentration range was found and well-described using the Henry equation. The most efficient adsorption of methylene blue was noticed for the sample activated with potassium hydroxide and modified with iron citrate, and a maximum adsorption capacity of 696 mg/g was achieved. The highest congo red adsorption was noticed for the non-activated sample modified with iron citrate, and the partition coefficient for this material equaled 171 dm3/g.

Polyphthalonitrile as a novel precursor for carbon membranes: Tunable microstructure characteristics and gas permeation behavior

Carbon molecular sieve (CMS) membranes hold great promise for energy-efficient gas separation, contributing to mitigating greenhouse gas emissions. Exploring new types of microstructurally tunable polymeric precursors is critical for understanding the evolution of carbon microstructure arrangement and adjusting the gas permeation behavior of CMS membranes. As a precursor for CMS membranes, polyphthalonitrile (PPN) resin with both tunable intermolecular distance and π-π stacking arrangement is reported for the first time. We have demonstrated that the aforementioned two key features of the thermally crosslinked PPN network are beneficial to forming PPN-CMS membranes with enlarged intermolecular distance and small-sized, narrow-distributed ultramicropores (<7 Å), thereby improving gas permeability and ideal selectivity. This study provides new insights into the microstructure evolution of PPN-derived microporous carbon materials. Owing to its excellent thermal stability, tunable microstructure arrangement, and flexibility of chemical synthesis, PPN represents a promising class of polymeric precursor materials for fabricating CMS membranes.

Rational bottom-up synthesis of sulphur-rich porous carbons for single-atomic platinum catalyst supports

S-rich microporous carbon materials are fabricated by the carbonization of rationally designed precursor molecules, which in turn function as catalyst supports for single-atomic Pt species for the electrochemical hydrogen oxidation reaction.

Valorization of waste coffee grounds into microporous carbon materials for CO2 adsorption

Our research is primarily focused on the valorization of the vast accumulation of coffee-waste for mitigating the alarming levels of greenhouse gas by adsorption from flue gas.

N-rich chitosan-derived porous carbon materials for efficient CO2 adsorption and gas separation.

Capturing and separating carbon dioxide, particularly using porous carbon adsorption separation technology, has received considerable research attention due to its advantages such as low cost and ease of regeneration. In this study, we successfully developed a one-step carbonization activation method using freeze-thaw pre-mix treatment to prepare high-nitrogen-content microporous nitrogen-doped carbon materials. These materials hold promise for capturing and separating CO2 from complex gas mixtures, such as biogas. The nitrogen content of the prepared carbon adsorbents reaches as high as 13.08wt%, and they exhibit excellent CO2 adsorption performance under standard conditions (1 bar, 273K/298K), achieving 6.97mmol/g and 3.77mmol/g, respectively. Furthermore, according to Ideal Adsorption Solution Theory (IAST) analysis, these materials demonstrate material selectivity for CO2/CH4 (10 v:90 v) and CO2/CH4 (50 v:50 v) of 33.3 and 21.8, respectively, at 1 bar and 298K. This study provides a promising CO2 adsorption and separation adsorbent that can be used in the efficient purification process for carbon dioxide, potentially reducing greenhouse gas emissions in industrial and energy production, thus offering robust support for addressing climate change and achieving more environmentally friendly energy production and carbon capture goals.

Nitrogen-doped coal-based microporous carbon material co-activated by HCOOK and urea for high performance supercapacitors

The doping of heteroatoms can adjust the surface chemical state of porous carbons, which is conducive to improving the surface activity, and enhancing the hydrophicity and conductivity of carbon electrodes. Herein, we developed a facile and green strategy to obtain nitrogen-doped coal-derived porous carbon dominated by micropores for high performance supercapacitor. The hydrothermal treatment of coal and urea can not only achieve the doping of nitrogen atoms, but also conducive to the subsequent activation process. Benefiting from the large micropore volume and specific surface area (0.68 cm3 g−1 and 1563 m2 g−1), suitable micropore size, and high content of surface CO, N-Q and N-5, the optimal sample exhibits a large capacitance of 371 F g−1 (1 A g−1), high capacitance retention of 67% (50 A g−1), and outstanding cyclic durability in a three-electrode system (aqueous electrolyte). Furthermore, the symmetrical supercapacitor in neat EMIM BF4 shows a high energy density of 40 Wh kg−1 (625 W kg−1). This work proposes a facile and potential strategy for preparing nitrogen-doped porous carbon materials with outstanding electrochemical property for supercapacitors and provides a novel insight for the efficient and low carbonization utilization of coal resources.

Peat-Derived ZnCl2-Activated Ultramicroporous Carbon Materials for Hydrogen Adsorption.

Highly microporous adsorbents have been under considerable scrutiny for efficient adsorptive storage of H2. Of specific interest are sustainable, chemically activated, microporous carbon adsorbents, especially from renewable and organic precursor materials. In this article, six peat-derived microporous carbon materials were synthesized by chemical activation with ZnCl2. N2 and CO2 gas adsorption data were measured and simultaneously fitted with the 2D-NLDFT-HS model. Thus, based on the obtained results, the use of a low ratio of ZnCl2 for chemical activation of peat-derived carbon yields highly ultramicroporous carbons which are able to adsorb up to 83% of the maximal adsorbed amount of adsorbed H2 already at 1 bar at 77 K. This is accompanied by the high ratio of micropores, 99%, even at high specific surface area of 1260 m2 g-1, exhibited by the peat-derived carbon activated at 973 K using a 1:2 ZnCl2 to peat mass ratio. These results show the potential of using low concentrations of ZnCl2 as an activating agent to synthesize highly ultramicroporous carbon materials with suitable pore characteristics for the efficient low-pressure adsorption of H2.

Pore engineering of ultramicroporous carbon from an N-doped polymer for CO2 adsorption and conversion

Microporous carbon materials are widely used in CO2 adsorption because of their unique structure and excellent stability. In this work, N-doped porous carbon (NPC) with an ultramicroporous structure was prepared through the carbonization of an N-doped polymer and KOH at 600 °C, 700 °C, and 800 °C, respectively. The prepared NPC exhibited excellent CO2 adsorption properties of up to 6.95 mmol·g−1 at 1 bar and 0 °C, and this value is considerably higher than that of the parent N-doped polymer. The excellent CO2 adsorption performance is due to the well-defined ultramicroporous structure and high specific surface area of NPC. Moreover, these porous carbons can be combined with tetrabutylammonium bromide (TBAB) to fix CO2 into various cyclic carbonates, with a yield of up to 99% without any solvent. Whether the cause is the adsorption or catalytic conversion of CO2, NPC-700 exhibits excellent stability and can be cycled multiple times without significant reduction in its performance.

Robust nitrogen-doped microporous hollow carbon spheres for energy-efficient CO2 capture from flue gas

Nitrogen (N)-doped microporous hollow carbon spheres were prepared by facilely nanocasting spherical SiO2 with N-containing melamine phenolic resin through a simple in-situ polymerization process. Through regulating the dosage of melamine, N content in microporous hollow carbons could be easily tuned to an unprecedented level of 49.2 wt%. Additionally, in order to address the common problem of relatively poor structural porosity of N-doped carbons, especially after incorporating vast N into carbon frameworks in reported literature, a comprehensive strategy including optimizing carbonization temperature and performing further activation by CO2 and KOH were explored, and their effects on material textural properties and CO2 capacity were systematically studied. Although this strategy did not completely avoid the N loss during activation of carbon materials, it sharply promoted the textural properties of carbon materials at the expenses of partial N and efficiently produced a series of highly microporous carbon materials, still with abundant N species (11.5 ∼ 29.9 wt%) and large structural porosity (330 ∼ 1263 m2/g). More importantly, these N-doped microporous hollow carbons, when used for CO2 capture, showed superior CO2 capacities of 3.00 mmol/g (25 °C and 1 bar) and 1.05 mmol/g (40 °C and 0.1 bar), exceptionally robust cyclic stability, and low regeneration energy of 2.75 GJ/ton CO2, which is much lower than aqueous amine-based absorbents and comparable to amine-supported adsorbents. Thus, these outstanding adsorption performances make the N-doped microporous hollow carbon spheres prepared in this study more promising for energy-effective CO2 capture from dilute gas streams.

PEO-based mixed matrix membranes containing N-doped microporous carbon microparticles for enhanced CO2/N2 separation

As a promising strategy to reduce greenhouse gas emissions, carbon dioxide capture from industrial and power plants has been proposed. Due to its advantages of low consumption and a modest environmental impact, membrane technology has been widely used in the gas separation process. Advanced porous fillers can be successfully added into the polymer matrix to create mixed matrix membranes (MMMs) with simple processing and applicable gas separation performance. The high porosity and stability of microporous carbon materials make them desirable for use in the gas separation process. Herein, N-doped microporous carbon microparticles (NMCP) were successfully synthesized and incorporated into UV crosslinked polyethylene oxide (XLPEO) matrix membranes. Fast CO2 transport channels are created in MMMs by rationally constructing NMCP fillers with ultra-micropores (∼0.53 nm), high-content heteroatoms (N, 13.94%), and two-dimensional morphology. The relationship between the structure of the NMCP samples and the gas separation performance of MMMs was discussed. Additionally, tests were conducted on the effects of NMCP loading, operating conditions, and long-term stability of NMCP/XLPEO membranes. NMCP/XLPEO membranes with a 2.5 wt% NMCP loading displayed a CO2 permeability of 606 Barrer and a CO2/N2 selectivity of 56.4, approaching the 2019 upper bound. This work offers a novel perspective to build fast gas transport channels in porous carbon-based MMMs for carbon capture.

CO2 capture by microporous carbon based on Brazil nut shells.

The increase in burning, deforestation, and the exorbitant use of fossil fuels have contributed to the increase in carbon dioxide emissions; this gas is responsible for the intensification of the greenhouse effect and radical climate changes. In this way, it becomes necessary to find alternatives to reduce its emission. Porous carbon materials synthesized from lignocellulosic waste can be employed in technologies for capture and utilization of CO2 due to the advantages such as selectivity, low-cost synthesis, high surface area and pore volume, and thermal and chemical stability. Considering the availability of Brazil nut biomass residues in the Amazon region, this article proposes to synthesize activated carbon from the lignocellulosic residue using physical and chemical activation methods for CO2 capture. The analysis of N2 adsorption-desorption isotherms proves the predominance of a microporous structure when using the two synthesis methods described here. In physical activation, the surface area was 912 m2/g, while, in chemical activation, it was 1421 to 2730 m2/g. The sample treated via the chemical method (BS6-K1) showed better performance in CO2 adsorption, with adsorption results of 3.8 and 6mmol/g of CO2 at 25 ℃ and 0°C, respectively, at 101kPa. CO2 adsorption capacity is due to the high volume of ultramicropores. It is believed that the microporous carbon material synthesized from Brazil nut residues is an alternative precursor for carbon materials used as CO2 capture.

Highly microporous and mesoporous nanomaterials derived from Agave sisalana waste for supercapacitors

AbstractNanostructured electrodes with large surface area are essential for studying charge storage mechanisms in supercapacitors. Biomass‐based carbonaceous porous electrodes have proven to be good candidates for supercapacitor application. In this study, micropore and mesopore dominated carbon materials derived from Agave sisalana sisal waste were prepared through carbonization and chemical activation with ZnCl2. Scanning electron microscopy, energy‐dispersive X‐ray, transmission electron microscopy, Raman spectroscopy, and X‐ray diffraction studies show that the microstructure and composition of the as‐prepared microporous carbon materials are influenced by adjusting the ZnCl2 to the carbon mass ratio. Sorption studies demonstrated a high Brunauer–Emmett–Teller (BET) surface area of 1464 m2 g−1, type I isotherms for low temperature, type IV at 900 °C, and 99% micropore content in all the samples. The fabricated electrodes exhibited high specific capacitances of 497 F g−1at 5 mV s−1, which is indicative of our carbon materials’ strong potential for use in the production of high‐performance supercapacitors. Specific capacitance increased with increasing micropore surface areas.

Microporous N- and O-Codoped Carbon Materials Derived from Benzoxazine for Supercapacitor Application

Heteroatom-doped porous carbon materials are highly desired for supercapacitors. Herein, we report the preparation of such material from polybenzoxazine (PBZ), a kind of phenolic resin. Four different N- and O-codoped microporous carbon materials were obtained by changing carbonization temperature (600, 700, 800, and 900 °C). Their structures were characterized by scanning electron microscopy (SEM), nitrogen isothermal absorption and desorption, X-ray diffraction (XRD), Raman spectroscopy, elemental analysis and X-ray photoelectron spectroscopy (XPS), and their electrochemical performances were evaluated by cyclovoltammetry (CV) and galvanostatic charge–discharge (GCD) test in a three-electrode system. It was found that the carbon material (C-700) prepared at the carbonization temperature of 700 °C possesses the largest specific surface area (SSA), total pore volume and average pore size among the family, and thus displays the highest specific capacitance with a value of 205 F g−1 at a current density of 0.25 A g−1 and good cycling stability. The work demonstrates that the N- and O-codoped microporous carbon materials with high electrochemical performance can be derived from benzoxazine polymers and are promising for supercapacitor application.

Self-Templated Formation of Carbon Nanotubes Interpenetrating Ordered Microporous Carbon Nanospheres for High-Performance Li-S Batteries.

Lithium-sulfur (Li-S) batteries are known as a prospective new generation of battery systems owing to their high energy density, low cost, non-toxicity, and environmental friendliness. Nevertheless, several issues remain in the practical application of Li-S batteries, such as low sulfur usage, poor rate performance, and poor cycle stability. Ordered microporous carbon materials and carbon nanotubes (CNTs) can effectively limit the diffusion of polysulfides (LiPSs) and have high electrical conductivity, respectively. Here, inspired by the evaporation of zinc at high temperatures, we constructed CNTs interpenetrating ordered microporous carbon nanospheres (CNTs/OMC NSs) by high-temperature calcination and used them as a sulfur host material. With the benefit from the excellent electrical conductivity of CNTs and OMC achieving uniform sulfur dispersion and effectively limiting LiPS dissolution, the S@CNTs/OMC NS cathodes show outstanding cycling stability (initial discharge capacity of 879 mAh g-1 at 0.5 C, maintained at 629 mAh g-1 for 500 cycles) and excellent rate performance (521 mAh g-1 at 5.0 C). Furthermore, the current study can serve as a significant reference for the synthesis of CNTs that interpenetrate various materials.

Facile preparation of nitrogen-doped microporous carbon from potassium citrate/urea for effective CH4 separation and uptake

N-doped microporous carbons have attracted much attention for micromolecule gas separation and accumulation owning to their superior adsorption potential and surface polarizability. However, to prepare N-doped microporous carbon usually acquire excess corrosive KOH as activator, which limits its application in industry. Here, we propose a non-corrosion method for the manufacture of narrow N-doped microporous carbons using potassium citrate acts as activating agent, and urea acts as both a nitrogen doping agent and coactivator without any solvent. The BET surface area, micropore volume, pore size distribution and N content can be easily adjusted by changing the potassium citrate/urea ratio and activating temperature. The influence of porous structure and N content on CH4 uptake and separation was investigated, and ultra-micropore volume (<1nm) plays a dominate role in CH4 selectivity adsorption. ACK2N1 had the largest CH4 adsorption capacity of 3.00 mmol/g and CH4/N2 selectivity of 7.11 at 273.15 K and 100 KPa due to its largest ultra-micropore volume and N content. The adsorption breakthrough, regeneration experiments and adsorption thermodynamics showed that the prepared well-developed N-doped microporous carbons have very good potential for CH4 separation and enrichment from low coal bed methane. Furthermore, the pore formation mechanism of the well microporous carbon materials is proposed.

Characterization of solid and liquid carbonization products of polyvinyl chloride (PVC) and investigation of the PVC-derived adsorbent for the removal of organic compounds from water

The transformation of plastic wastes into value-added carbon materials is a promising strategy for the recycling of plastics. Commonly used polyvinyl chloride (PVC) plastics are converted into microporous carbonaceous materials using KOH as an activator via simultaneous carbonization and activation for the first time. The optimized spongy microporous carbon material has a surface area of 2093 m2 g−1 and a total pore volume of 1.12 cm3 g−1, and aliphatic hydrocarbons and alcohols are yielded as the carbonization by-products. The PVC-derived carbon materials exhibit outstanding adsorption performance for removing tetracycline from water, and the maximum adsorption capacity reaches 1480 mg g−1. The kinetic and isotherm patterns for tetracycline adsorption follow the pseudo-second-order and Freundlich models, respectively. Adsorption mechanism investigation indicates that pore filling and hydrogen bond interaction are mainly responsible for the adsorption. This study provides a facile and environmentally friendly approach for valorizing PVC into adsorbents for wastewater treatment.

A portable electrochemical immunosensor for ovarian cancer uses hierarchical microporous carbon material from waste coffee grounds.

A simple label-free electrochemical immunosensor for ovarian cancer (OC) detection was developed using a hierarchical microporous carbon material fabricated from waste coffee grounds (WCG). The analysis method exploited near-field communication (NFC) and a smartphone-based potentiostat. Waste coffee grounds were pyrolyzed with potassium hydroxide and used to modify a screen-printed electrode. The modified screen-printed electrode was decorated with gold nanoparticles (AuNPs) to capture a specific antibody. The modification and immobilization processes were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The sensor had an effective dynamic range of 0.5 to 50.0 U mL-1 of cancer antigen 125 (CA125) tumor marker with a correlation coefficient of 0.9995. The limit of detection (LOD) was 0.4 U mL-1. A comparison of the results obtained from human serum analysis with the proposed immunosensor and the results obtained from the clinical method confirmed the accuracy and precision of the proposed immunosensor.

Microporous Carbons Obtained via Solvent-Free Mechanochemical Processing, Carbonization and Activation with Potassium Citrate and Zinc Chloride for CO2 Adsorption

In this study, the facile and sustainable synthesis of highly microporous carbons is explored to reduce the extensive use of harsh activating agents and solvents. The role of potassium citrate (PC) as a greener activating agent in addition to the conventional ZnCl2 is investigated in the mechanochemical solvent-free preparation of highly microporous carbon materials from chestnut tannin (CT), a biomass-type carbon precursor. A small amount of potassium citrate as a chemical activator coupled with CO2 activation at 700 °C afforded carbons with higher specific surface area (1256 m2 g−1) and larger micropore volume (0.54 cm3 g−1) as compared to the carbons activated with both PC and ZnCl2. The high microporosity of the PC-activated carbon materials, significantly enlarged after CO2 activation from micropore volume of 0.16 to 0.54 cm3 g−1, makes them favorable for CO2 adsorption, as evidenced by high adsorption capacity of 3.55 mmol g−1 at ambient conditions (25 °C, 1 bar). This study shows that the solvent-free mechanochemical processing of tannin in the presence of PC is a promising method for obtaining highly microporous carbon materials.