Disordered Carbon Structure Research Articles

Pitch-based carbon anode for high-energy and long-life sodium-ion battery

Pitch-based carbon generally demonstrate remarkable electrochemical performance for sodium-ion batteries (SIBs). In this paper, the medium temperature pitch is successively subjected to heat treatment under high pressure, extraction of toluene to remove soluble matter, and carbonization of toluene insoluble matter, to prepare the anode material, named pitch toluene insoluble anode (PTIA). The PTIA is characteristic of the coral-like morphology distributed with 100−200 nm pore channels and 2−3 nm mesopores for electrolyte immersion, and the disordered carbon structure is interwoven with graphitic carbon for sodium-ion insertion/desertion and electron transmission. In the PTIA half battery, the reversible specific capacity reaches 276.9 mAh g−1 at 0.1 A g−1 after 300 cycles with a coulombic efficiency of 99.22%. Importantly, the PTIA exhibits good compatibility with vanadium sodium phosphate (NVP) cathode materials, enabling a battery PTIA//NVP to achieve a capacity density of 154 mAh g−1, an energy density of 246.7 Wh kg−1 and a power density of 4800 W kg−1 for 1000 cycles at a current density of 3 A g−1 (16−18 C). The battery has a certain working efficiency at -10−70°C.

Carbon Structure Regulation Strategy for the Electrode of Vanadium Redox Flow Battery.

Vanadium redox flow battery (VRFB) is a type of energy storage device known for its large-scale capacity, long-term durability, and high-level safety. It serves as an effective solution to address the instability and intermittency of renewable energy sources. Carbon-based materials are widely used as VRFB electrodes due to cost-effectiveness and well-stability. However, pristine electrodes need proper modification to overcome original poor hydrophilicity and fewer reaction active sites. Adjusting the carbon structure is recognized as a viable method to boost the electrochemical activity of electrodes. This review delves into the advancements in research related to ordered and disordered carbon structure electrodes including the adjusting methods, structural characteristics, and catalytic properties. Ordered carbon structures are categorized into nanoscale and macroscale orderliness based on size, leading to improved conductivity and overall performance of the electrode. Disordered carbon structures encompass methods such as doping atoms, grafting functional groups, and creating engineered holes to enhance active sites and hydrophilicity. Based on the current research findings on carbon electrode structures, this work puts forth some promising prospects for future feasibility.

Disordered carbon structures enhance capacitive storage

Electrochemical energy storage (EES) is one of the key technologies in global research, focusing on the efficient storage and utilization of electrical energy generated from intermittent sources. The development of EES systems with high energy and power density is essential for meeting future energy demands electrochemical capacitors, such as capacitors, are capable of storing electrical energy obtained from intermittent sources and enabling the rapid energy transfer and transformation. Among these, electrical double-layer capacitances (EDLCs) within porous carbon materials (Fig. 1a), are commercially popular due to their excellent conductivity and relatively low cost. Despite their advantages, the complex structure of nanoporous carbon materials challenges in optimizing supercapacitor performance. While previous research has suggested that adjusting the pore size of nanoporous in carbon materials can enhance capacitive performance [1], conflicting reports and the lack of a definitive correlation between capacitance and pore size remain issues [2]. Understanding the relationship between the structure of carbon materials and their capacitance is crucial for the design of devices with high energy density effectively.

The development of B/Cr co-doped DLC coating by FCVA deposition system and its tribological properties at 300 °C

The diamond-like carbon (DLC) coating prepared using filtered cathodic arc deposition (FCVA) lost its promising wear resistance under high temperatures. Element-doped DLC coatings have been investigated to suppress carbon oxidation reaction and subsequently enhance the wear resistance in high-temperature environments. Previous research clarified the excellent tribological properties of boron-doped DLC (B-DLC) but identified challenge such as arc discharge extinguishment and coating declamation (under high-temperature friction test). In this study, the introduction of Argon gas (10 sccm) during the deposition process stabilized stable arc discharge, resulting in high hardness and deposition rate. Moreover, a chromium interlayer and varying concentration of Cr dopant (0.5 %, 1.0 %, 3.0 % at.) were added to B-DLC to develop a stable, co-doped DLC with low friction and high wear resistance. Raman spectroscopy and nano-indentation revealed an increase in the disordered carbon structure and reduction in hardness and Young's Modulus with Cr doping. Macroscopic ball-on-disk friction test, showed 1 % Cr-doped B-DLC (a-C:B:Cr1) coating exhibited super low friction (avg. coefficient 0.02) and a low specific wear rate (<5.0 × 10−6 mm3/Nm). Raman spectroscopy indicated that the transferred graphite-like tribo-film onto the surface of Si3N4 counterparts contributed to stable low friction. Additionally, XPS analysis on the DLC coatings' wear track suggested the rich BB bond might contribute to its high wear resistance. This successful improvement on element-doped DLC prepared by FCVA provided valuable insights for further exploration of DLC coating applied to various working situations.

Impacts of radiation sources on structures and electrochemical performance of SiO2/C composite anodes for Li-ion batteries

Application of radiation with highly energetic electrons and ions can be an alternative method to modify structures of crystalline materials. This radiation can potentially induce phase transformations while preserving some physical characteristics and morphology of the materials, hence impacting their useful properties. Here, we report the impacts of e-beam and gamma radiation on the structures and electrochemical performance of SiO2/C anodes for Li-ion batteries (LIB) obtained from rice husk ash (RHA). The effects of radiation sources on structural and physical properties are investigated using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray fluorescence spectrometry (XRF), electron microscopy, and Raman spectroscopy. After irradiation-induced processes using e-beam and gamma radiation at 1000 kGy, the mean diameters of the SiO2 particles were around 30 ± 10 and 27 ± 10 nm, respectively, while retaining their round-shaped particle morphology. Both radiation sources induce formation of disordered carbon structure as indicated by the higher ID/IG Raman peaks ratios than the pristine sample. Electrochemical properties were studied using half-coin type cells. The modified structure of SiO2/C anodes caused by irradiation showed improved electrochemical performance, compared with pristine material.

Mechanochemical regulation of microcrystalline in coal-derived disordered carbon for improved sodium storage: Metamorphic grade

Coals are common precursors of the disordered carbon anodes for sodium ion batteries. In order to hinder the long-range ordered development of coal precursors during thermal conversion, the acid reagents and calcination under air atmosphere have been adopted in the pre-oxidation procedure, not in accordance with the demand of green energy storage. Herein, the mechanochemical pretreatment was employed to break the aromatic structures and generate the edge defects and oxygen functional groups on the coal surface, which would suppress the long-range ordered tendency and promote the introduction of nitrogen heteroatoms during following calcination. With the increasing metamorphic grades, the molecular rigidity of coal precursors increases owing to more highly polycondensed aromatic structures and less interior buffer space. The aromatic structures in the highest-ranked anthracite are broken most heavily during the mechanochemical process. Thus the nitrogen-doped anthracite-based carbon materials have the most disordered carbon structures and deliver a high reversible capacity of 323 mA h g−1 under 0.03 A/g after 90 cycles. This work provides a facile and green solution to fabricate the highly disordered carbon anodes with low cost and high performance from the industrial raw materials.

Electronic conductivity in metal-graphene composites: the role of disordered carbon structures, defects, and impurities

This paper explores the transport properties of aluminum-carbon composite material via ab initio methods. Interfacial and electronic dynamics of the aluminum-graphene interface structure were investigated using models of amorphous graphene added to an aluminum matrix. We examine the impact on electronic conduction caused by the presence of nitrogen impurities within the interfacial amorphous graphene layer. We elucidate the conduction mechanisms by using a projection of the electronic conductivity into space.

Microwave-Assisted Synthesis of Nitrogen-Doped Carbon Catalysts for Oxygen Reduction Reaction with Tunable Selectivity

The oxygen reduction reaction (ORR) is the core reaction in electrocatalysis systems such as fuel cells, metal-air batteries and hydrogen peroxide (H2O2) electro-generation. The ORR reaction mechanism has two possible pathways, namely, two-electron (2e−) or four-electron (4e−) processes that enable a reduction of oxygen into H2O2 or water (H2O), respectively. Both paths are useful where the former can provide on-site direct production of H2O2 and the latter is desired in fuel cells and batteries since it enables higher energy efficiency. Optimal ORR electrocatalyst should exhibit high activity, selectivity, stability, and low cost. Carbon materials modified with heteroatoms (e.g. nitrogen (N)) are considered potential alternatives for costly noble metal catalysts including Pt for ORR in fuel cells, and Au for the ORR to H2O2 (1,2). The typical synthesis procedure for the porous nitrogen-doped carbons (N–C) is based on the single or multiple pyrolysis steps of nitrogen-rich carbon precursor. The reactions required a pyrolysis step at the temperature range of 500-1200 °C and timing of one to tens of hours. Such processes showed a highly negative environmental impact due to high energy consumption. The production of 1 ton of activated carbon from lignocellulosic biomass feedstock requires 669.83 kWh (equivalent to an emission of 62.78 tons of CO2) (3). The synthesis of the N–C by microwave (MW) irradiation can reduce energy usage and ensure a more environmentally sustainable and economically viable approach. This procedure necessitates non-transparent materials to electromagnetic waves that can convert MW energy into heat and simultaneously enable the carbonization of the starting material.This work investigated the electrocatalytic activity towards ORR for N–C–MW catalysts derived from polyaniline (PANI) prepared in a one-step MW carbonization approach. PANI was selected due to two reasons: (i) N–C made by thermal pyrolysis of PANI showed improved electrocatalytic activity toward ORR where both the 4e− and the 2e− electron transfer pathways are feasible depending on the nature of active sides (4), (ii) PANI displayed good MW adsorption properties (5). The work aimed to identify the influence of the MW reaction condition on the resulting structure of the N–C–MW and the direction of the ORR. The N–C–MW samples were prepared under MW power of 450 and 800 W and time of 70, 140 and 210 s. The ORR activity of N–C–MW samples was investigated by cyclic voltammetry in the alkaline media (O2-saturated 0.1 M KOH). The experiment was performed in a three-electrode configuration composed of a rotating ring (Pt)–disk (glassy carbon) electrode (RRDE), a graphite rod as the counter electrode and a reversible hydrogen electrode (RHE) as the reference electrode. An influence of catalyst loading on disk electrode (0.05, 0.1 and 0.2 mg/cm2) was analyzed. All investigated MW reaction conditions resulted in the formation of porous disordered carbon structures with nitrogen and oxygen functionalities confirmed by X-ray photon-electron spectroscopy. The shorter time (70 s) and lower power (450 W) of MW treatment resulted in the formation of structures with a low carbonization rate and simultaneously a relatively poor catalytic activity for ORR (an onset potential of ∼0.65 V vs RHE). The samples carbonized under moderate (power of 450 W and 800 W, time of 140 s) and severe (power of 450 W, time of 210 s) reaction conditions showed higher selectivity to H2O2 or water H2O, respectively. The selectivity of 80 % to H2O2 was achieved for the N–C–MW-800W-140s sample at the potential of 0.6 V vs RHE at the catalyst loading of 0.05 mg/cm2. The results showcase the potential of MW carbonization in producing ORR electrocatalysts with diverse functionalization, leading to modified reaction selectivity that can be utilized in various electrocatalytic applications. Acknowledgments The research leading to these results was supported by the Johannes Amos Comenius Programme, European Structural and Investment Funds, project 'CHEMFELLS V‘ (No. CZ.02.01.01/00/22_010/0003004). References Yang, S. et al., Toward the decentralized electrochemical production of H2O2: A focus on the catalysis. ACS Catalysis, 2018.Bouleau, L. et al., Best practices for ORR performance evaluation of metal-free porous carbon electrocatalysts. Carbon, 2022.Wang, YX. et al., Quantifying environmental and economic impacts of highly porous activated carbon from lignocellulosic biomass for high-performance supercapacitors. Energies, 2022.Silva, R. et al., Efficient metal-free electrocatalysts for oxygen reduction: Polyaniline-derived N- and O-doped mesoporous carbons. Journal of the American Chemical Society, 2013.Oyharçabal, M. et al., Influence of the morphology of polyaniline on the microwave absorption properties of epoxy polyaniline composites. Composites Science and Technology, 2013. Figure 1

Operando x-Ray Absorption Spectroscopy Investigation of Secondary Metal Doping into Iron-Nitrogen-Carbon Catalysts for Oxygen Electroreduction

Oxygen reduction reaction (ORR) plays a key role in the development of fuel cell technology, and great efforts have been made to reduce the amount of platinum, required to speed up this sluggish reaction, or, even more desirable, to use efficient electrocatalysts based on earth-abundant metals. To date, numerous single-atom catalysts in the form of metal-doped carbon-nitrogen materials (MNC) have proved to be a promising alternative to ORR Pt-based materials. [1-3]In this study we employed advanced spectroscopic techniques, namely Mössbauer spectroscopy and operando X-ray absorption (XAS) spectroscopy, to understand the structural and electronic factors underlying an increase in the catalytic turn over frequency (TOF) of bimetallic FeSnNC and FeCoNC catalysts, relative to the parent FeNC materials. In particular, 57Fe Mössbauer spectroscopy identified a larger ratio of D1/D2 species in both bimetallic catalysts, supporting a larger ratio of Fe(III)-Nx/Fe(II)-Nx sites. The combination of extended X-ray absorption fine structure (EXAFS) modeling, and the analysis of operando X-ray absorption near-edge spectroscopy (XANES) spectra revealed a disordered carbon structure around FeNx active sites, and variations in the iron oxidation state that can be linked to the enhanced intrinsic catalytic reactivity (TOF). This talk is therefore intended to draw attention to the potential of the XAS technique, especially when applied to in-situ/operando studies in the field of electrocatalysis. References F. Luo, A. Roy, L. Silvioli, D.A. Cullen, A. Zitolo, M.T. Sougrati, I.C. Oguz, T. Mineva, D. Teschner, S. Wagner, J. Wen, F. Dionigi, U.I. Kramm, J. Rossmeisl, F. Jaouen and P. Strasser. P-block single-metal-site tin/nitrogen-doped carbon fuel cell cathode catalyst for oxygen reduction reaction. Nature Materials 2020, 19, 1215-1223A. Zitolo, N. Ranjbar, T. Mineva, J. Li, Q. Jia, S. Stamatin, G.F. Harrington, S.M. Lyth, P. Krtil, S. Mukerjee, E. Fonda, F. Jaouen. Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction. Nature Communications 2017, 8(1), 957A. Zitolo, V. Goellner, V. Armel, M. T. Sougrati, T. Mineva, L. Stievano, E. Fonda, F. Jaouen. Identification of catalytic sites for oxygen reduction in iron and nitrogen doped graphene materials. Nature Materials 2015, 14, 937-942

Elaeis guineensisleaves for potential renewable sub‐bituminous coal: Optimization of biochar yield by response surface methodology and product characterization

AbstractPyrolysis of oil palm biomass residue can convert the rich organic matter in biomass into sustainable green energy, thereby addressing the challenge of surplus oil palm biomass residue generated during cultivation. Nonetheless, the pyrolysis of oil palm leaves (OPLs) has received limited attention. In this study, design of experiment‐response surface methodology (DoE‐RSM) was employed to identify the optimal combination of reaction temperature, residence duration, and nitrogen (N₂) flow rate for maximum biochar yield. The elemental analysis, high heating value (HHV), functional group, morphology, pore structure, and thermal behavior were assessed. By varying the operational parameters using response surface methodology, the biochar yield increased by 32.6–85.3%. TheDoE‐RSMpredicted a theoretical yield of 52.1% at 344 °C, 146 min, and 3.2 scfh N₂ flow rate. The experiment confirmed a comparable yield of 53.7% at the stated parameters. TheHHVof 24.14 MJ kg−1was recorded under optimal conditions, and was comparable to sub‐bituminous and bituminous coal. Fourier transform infrared analysis validated theOPLbiochar by weakeningO‐H, C=O,C‐OH, andC‐Hpeaks. Scanning electron microscopy images revealed enlarged pores and altered morphology in theOPLbiochar. X‐ray diffraction showed lower crystallinity of theOPLbiochar than the feedstock. Raman spectroscopy showed higherID/IG, indicating a more disordered carbon structure in theOPLbiochar. Thermogravimetric analysis confirmed higher temperature for main devolatilization ofOPLbiochar, and the differential thermogravimetric analysis curve pattern resembled that of Mukah Balingan coal. The findings are helpful for an initiative to convert a large amount of leftoverOPLsproduced during cultivation and to turn them into high value‐added material for a sustainable contribution to a circular carbon economy.

Application of the trinary discretization method for the structural analysis of natural disordered sp2 carbon

High-resolution transmission electron microscopy (HRTEM) is one of the most effective methods for analyzing the nanoscale structure of disordered carbon. Mathematical processing of HRTEM images made the quantification and description of the complex structure of disordered carbon more reliable. This work demonstrates the HRTEM image processing algorithm applied to four naturally occurring substances with a disordered carbon structure and different electrically conductive properties. The result of the algorithm is a quantitative estimation of the structural characteristics of disordered carbon by the method of structural discretization over three degrees of ordering. The algorithm consists of two main parts: (a) HRTEM image processing, which generates a trinary image, and (b) quantification, which generates nanoscale structure statistics. The reliability (reproducibility) of the results is about 66% and does not depend on the difference in the physical properties of the samples. The proposed image analysis algorithm can be applied to any similar disordered materials to characterize the structure at the nanometer scale, used to build models of disordered carbon materials and describe some of the physicochemical properties.

Flow-Through Electrochemical Membrane Reactor with a Self-Supported Carbon Membrane Electrode for Highly Efficient Synthesis of Hydrogen Peroxide.

In situ electroreduction of O2 to H2O2 by using electrons as reagents is known as a green process, which is highly desirable for environmental remediation and chemical industries. However, the development of a cost-effective electrode with superior H2O2 synthesis rate and stability is challenging. A self-supported carbon membrane (CM) was prepared in this study from activated carbon and phenolic resin by carbonization under a H2 atmosphere. It was employed as the cathode to build a flow-through electrochemical membrane reactor (FT-ECMR) for electrosynthesis of H2O2. The results showed that the CM had a small pore size (34 nm), a high porosity (42.3%), and a high surface area (450.7 m2 g-1). In contrast to most of the state-of-the-art self-supported carbon electrode reported in the previous works, the FT-ECMR exhibited a high concentration of continuous and stable H2O2 electrosynthesis (1042 mg L-1) as well as a H2O2 synthesis rate of 5.21 mg h-1 cm-2. It had also demonstrated a high oxygen conversion (0.37%) and current efficiency (88%). The outstanding performance of the FT-ECMR for H2O2 synthesis was attributed to the enhanced mass transfer of the reactor, the existence of a relatively high surface area of CM, and the abundant disordered carbon structures (sp3-C, defects, and edges). In conclusion, our work highlighted using the FT-ECMR with the CM to synthesize H2O2 efficiently and cost-effectively.

Hydrogen Peroxide/Phosphoric Acid Modification of Hydrochars for Sulfamethoxazole and Carbamazepine Adsorption: The Role of Oxygen-Containing Functional Groups.

Emerging pollutants, such as sulfonamide antibiotics and pharmaceuticals, have been widely detected in water and soils, posing serious environmental and human health concerns. Thus, it is urgent and necessary to develop a technology for removing them. In this work, a hydrothermal carbonization method was used to prepare the hydrochars (HCs) by pine sawdust with different temperatures. To improve the physicochemical properties of HCs, phosphoric acid (H3PO4) and hydrogen peroxide (H2O2) were used to modify these HCs, and they were referred to as PHCs and HHCs, respectively. The adsorption of sulfamethoxazole (SMX) and carbamazepine (CBZ) by pristine and modified HCs was investigated systematically. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) results indicated that the H2O2/H3PO4 modification led to the formation of a disordered carbon structure and abundant pores. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy results suggested that carboxyl (-COOH) and hydroxyl (-OH) functional groups of HCs increased after modification, which is the main reason for the higher sorption of SMX and CBZ on H3PO4/H2O2-modified HCs when compared with pristine HCs. In addition, the positive correlation between -COOH/C=O and logKd of these two chemicals also suggested that oxygen-containing functional groups played a crucial role in the sorption of SMX and CBZ. The strong hydrophobic interaction and π-π interaction between CBZ and pristine/modified HCs resulted in its higher adsorption when compared with SMX. The results of this study provide a novel perspective on the investigation of adsorption mechanisms and environmental behaviors for organic contaminants by pristine and modified HCs.

A comparative study on characterizations of biomass derived activated carbons prepared by both normal and inert atmospheric heating conditions

In the present study, cost effective activated carbon from wasteland biomass of Calotropis gigantea stem was prepared at 400 °C, 600 °C, 750 °C and 900 °C carbonization temperatures in normal atmosphere (NA) and at 600 °C, 750 °C in inert atmosphere (IA) of nitrogen by using Potassium Carbonate (K2CO3) as chemical activating agent in the impregnation ratios of 0.5, 1 and 2. Activated carbons prepared under NA and IA were characterized and compared. Field Emission Scanning Electron Microscopy (FESEM) study confirmed presence of micropores and mesopores. While Xray Diffraction (XRD) analysis confirmed presence of both disordered amorphous carbon humps and graphitic crystallite peaks. Presences of functional groups were more prominent in NAC; found from Fourier Transform Infra-Red Spectroscopy (FTIR) analysis. BET surface area at 750 °C at chemical impregnation ratio 1 under NA was recorded highest containing both micropores and mesopores. Disordered carbon structure was confirmed from RAMAN spectroscopic analysis and nanoporous structure of activated carbon was confirmed from HRTEM analysis. NA activated carbons processed from wasteland weed can be preferred for different adsorption related applications as they are reasonable with improved properties.

Effect of Iron Loading on Controlling Fe/N−C Electrocatalyst Structure for Oxygen Reduction Reaction

AbstractFe/N−C electrocatalysts were synthesized using iron chloride, ammonium chloride, glycine, and acetylene black by pyrolysis at 900 °C under nitrogen atmosphere. Acid leaching process successfully removed non‐bonded Fe which confirmed by X‐ray Diffraction (XRD) analysis. Deconvolution of Raman spectra showed that Fe1−NC had a high ID/IG value of 1.37 due to the presence of defect sites and disordered carbon structure. The calculation result showed that higher Fe loading leads to the carbon structure rearrangement into graphitic structure, thus reducing the ID/IG to 1.06. The cyclic voltammetry (CV) test of Fe1−NC shows the best catalytic performance for oxygen reduction reaction (ORR) compared to higher Fe‐loading samples. Rearrangement in the carbon structure into the more graphitic led to active sites decrease, thus resulted in a decrease of IORR from 4.6 to 1.7 μA for Fe1−NC and Fe20−NC. This study indicates that optimum iron loading could be an essential factor in improving catalyst performance.

Preparation and Characterization of Pulp and Paper Mill Sludge-Activated Biochars Using Alkaline Activation: A Box-Behnken Design Approach.

This study utilized pulp and paper mill sludge as a carbon source to produce activated biochar adsorbents. The response surface methodology (RSM) application for predicting and optimizing the activated biochar preparation conditions was investigated. Biochars were prepared based on a Box–Behnken design (BBD) approach with three independent factors (i.e., pyrolysis temperature, holding time, and KOH:biomass ratio), and the responses evaluated were specific surface area (SSA), micropore area (Smicro), and mesopore area (Smeso). According to the RSM and BBD analysis, a pyrolysis temperature of 800 °C for 3 h of holding and an impregnation ratio of 1:1 (biomass:KOH) are the optimum conditions for obtaining the highest SSA (885 m2 g–1). Maximized Smicro was reached at 800 °C, 1 h and the ratio of 1:1, and for maximizing Smeso (569.16 m2 g–1), 800 °C, 2 h and ratio 1:1.5 (445–473 m2 g–1) were employed. The biochars presented different micro- and mesoporosity characteristics depending on pyrolysis conditions. Elemental analysis showed that biochars exhibited high carbon and oxygen content. Raman analysis indicated that all biochars had disordered carbon structures with structural defects, which can boost their properties, e.g., by improving their adsorption performances. The hydrophobicity–hydrophilicity experiments showed very hydrophobic biochar surfaces. The biochars were used as adsorbents for diclofenac and amoxicillin. They presented very high adsorption performances, which could be explained by the pore filling, hydrophobic surface, and π–π electron–donor–acceptor interactions between aromatic rings of both adsorbent and adsorbate. The biochar with the highest surface area (and highest uptake performance) was subjected to regeneration tests, showing that it can be reused multiple times.

High-performance carbon molecular sieve membrane for C2H4/C2H6 separation: Molecular insight into the structure-property relationships

Carbon molecular sieve (CMS) membranes show attractive potential for energy-efficient separation of C2H4/C2H6 due to their unique slit-like pore structure. In this work, a novel precursor polymer of phenolphthalein-based poly(arylene ether ketone) (PEK-C) was introduced to prepare high-performance CMS membranes for C2H4/C2H6 separation. Molecular insight into the effect of the sp3/sp2 hybridized carbon ratio on the packing morphology of carbon layers, pore size and configuration, and C2H4/C2H6 diffusion and separation properties of CMS membranes was investigated via using in-depth characterization techniques combined with molecular simulations. Results show that the carbon layers with more sp3 hybridized carbons lead to forming a loose and disordered carbon structure and pore structure with large pore volume and micropore size (steric voids), resulting in low C2H4/C2H6 permselectivity of CMS membrane. With the reduction of the sp3/sp2 hybridized carbon ratio, a compact and graphite-like carbon structure with the two-dimensional slit-like ultramicropore structure is formed, and the C2H4/C2H6 permselectivity is obviously enhanced. The CMS membranes derived from the novel precursor of PEK-C exhibit high C2H4 permeability with superior C2H4/C2H6 selectivity, which have surpassed the trade-off bounds of both polymeric membrane and CMS membrane, and reveal a great potential in the industrial applications of C2H4/C2H6 separation.

Modeling adsorption of simple fluids and hydrocarbons on nanoporous carbons

Predicting adsorption on nanoporous carbonaceous materials is important for developing various adsorption and membrane separations, as well as for oil and gas recovery from shale reservoirs. Here, we explore the capabilities of 3D molecular models of disordered carbon structures to reproduce the morphological and adsorption features of practical adsorbents. Using grand canonical Monte Carlo simulations, we construct a series of adsorption isotherms of simple fluids (N2, Ar, CO2, and SO2) and a series of alkanes from methane to hexane on two model 3D structures, purely microporous structure A and micro-mesoporous structure B. We show that structure A reproduces the morphological properties of commercial Norit R1 Extra activated carbon and demonstrates outstanding agreement between the simulated and experimental adsorption isotherms reported in the literature for all adsorbates considered. Good agreement is also found for simulated and measured isosteric heats. Taking into account inherent variability of structural properties of commercial carbons and experimental adsorption data from different literature sources, the correlations with experiments are truly amazing. This work provides a new insight into the specifics of structural and adsorption properties of nanoporous carbons and demonstrates the advantages of using 3D molecular models for predicting adsorption hydrocarbons and other chemicals by MC simulations.

Inhibiting the cyclization of PAN by carboxyl groups for carbon nanofibers with balanced Na+ storage performance and ICE

Hard carbon nanofiber derived from electrospinning polyacrylonitrile (PAN) is regarded as the promising electrode featuring the low-cost and simple preparation advantages, while it possesses the low plateau capacity, limiting its application as anode for the sodium ion (Na+) storage technologies. The main obstacle is that the cyclization of PAN during stabilization leads to the formation of ordered carbon structures. Herein, nanofibers anodes with disordered structures and abundant internal nanopores are fabricated by using carboxyl-functionalized PAN. The cyan (–CN) of PAN turns to sodium carboxylate (–COONa) during the hydrolysis process in NaOH solution, so that the cyclization in stabilization process is limited and realizing disordered carbon structures. Meanwhile, the formation of –COONa can lead to hard carbon with abundant internal pores, thereby resulting in an extended plateau region during discharging. The optimized PCNFs2-700-1400 anode delivers a satisfactory reversible capacity of 286 mAh/g at 0.02 A/g with an initial coulombic efficiency (ICE) of 73%. The larger plateau capacity of 183 mAh/g is ascribed to the filling of Na+ in the internal pores and insertion in the pseudo-graphitic. This strategy is expected to help enhance the understanding of Na+ storage “adsorption-insertion-pore filling” mechanism in PAN-derived hard carbon.

Hardwood spent mushroom substrate–based activated biochar as a sustainable bioresource for removal of emerging pollutants from wastewater

Hardwood spent mushroom substrate was employed as a carbon precursor to prepare activated biochars using phosphoric acid (H3PO4) as chemical activator. The activation process was carried out using an impregnation ratio of 1 precursor:2 H3PO4; pyrolysis temperatures of 700, 800, and 900 °C; heating rate of 10 °C min−1; and treatment time of 1 h. The specific surface area (SSA) of the biochars reached 975, 1031, and 1215 m2 g−1 for the samples pyrolyzed at 700, 800, and 900 °C, respectively. The percentage of mesopores in their structures was 75.4%, 78.5%, and 82.3% for the samples pyrolyzed at 700, 800, and 900 °C, respectively. Chemical characterization of the biochars indicated disordered carbon structures with the presence of oxygen and phosphorous functional groups on their surfaces. The biochars were successfully tested to adsorb acetaminophen and treat two simulated pharmaceutical effluents composed of organic and inorganic compounds. The kinetic data from adsorption of acetaminophen were fitted to the Avrami fractional-order model, and the equilibrium data was well represented by the Liu isotherm model, attaining a maximum adsorption capacity of 236.8 mg g−1 for the biochar produced at 900 °C. The adsorption process suggests that the pore-filling mechanism mainly dominates the acetaminophen removal, although van der Walls forces are also involved. The biochar produced at 900 °C removed up to 84.7% of the contaminants in the simulated effluents. Regeneration tests using 0.1 M NaOH + 20% EtOH as eluent showed that the biochars could be reused; however, the adsorption capacity was reduced by approximately 50% after three adsorption–desorption cycles.