Chemically activated fungi-based porous carbons for hydrogen storage

A set of porous carbons has been prepared by chemical activation of various fungi-based chars with KOH. The resulting carbon materials have high surface areas (1600–2500 m²/g) and pore volumes (0.80–1.56 cm³/g), regardless of the char precursors. The porosities mainly derived from micropores in activated carbons strongly depend on the activation parameters (temperature and KOH amount). All activated carbons have uniform micropores with pore size of 0.8–0.9 nm, but some have a second set of micropores (1.3–1.4 nm pore size), further broadened to 1.9–2.1 nm as a result of increasing either the activation temperature to 750 °C or KOH/char mass ratio to 5/1. These fungi-based porous carbons achieve an excellent H₂ uptake of up to 2.4 wt% at 1 bar and −196 °C, being in agreement with results from other porous carbonaceous adsorbents reported in the literature. At high pressure (ca. 35 bar), the saturated H₂ uptake reaches 4.2–4.7 wt% at −196 °C for these fungi-based porous carbons. The results imply a great potential of these fungi-based porous carbons as H₂ on-board storage media.     

Nitrogen-doped porous carbons through KOH activation with superior performance in supercapacitors

A series of nitrogen-doped porous carbons are prepared through KOH activation of a nonporous nitrogen-enriched carbon which is synthesized by pyrolysis of the polymerized ethylenediamine and carbon tetrachloride. The porosity and nitrogen content of the nitrogen-doped porous carbons depend strongly on the weight ratio of KOH/carbon. As the weight ratio of KOH/carbon increases from 0.5 to 2, the specific surface area increases from 521 to 1913 m² g⁻¹, while the nitrogen content decreases from 10.8 to 1.1 wt.%. The nitrogen-doped porous carbon prepared with a moderate KOH/carbon weight ratio of 1, which possesses a balanced specific surface area (1463 m² g⁻¹) and nitrogen content (3.3 wt.%), exhibits the largest specific capacitance of 363 F g⁻¹ at a current density of 0.1 A g⁻¹ in 1 M H₂SO₄ aqueous electrolyte, attributed to the co-contribution of double-layer capacitance and pseudocapacitance. Moreover, it shows excellent rate capability (182 F g⁻¹ remained at 20 A g⁻¹) and good cycling stability (97% capacitance retention over 5000 cycles), making it a promising electrode material for supercapacitors.     

Effects of chemical modification of petroleum cokes on the properties of the resulting activated carbon

Activated carbons have been prepared from petroleum cokes by the combination of a chemical treatment with HClO₄ or H₂O₂ and a chemical activation with KOH at a constant KOH/coke ratio of 3/1. The influence of different chemical treatments on the properties of the activated carbon precursors and final carbons activated with KOH was invested by using XRD, FTIR, and BET techniques. XRD results indicated that the value of interplanar distance d₀₀₂ increased by chemical treatment and the disappearance of the peak corresponding to 0 0 2 faces correlated to high specific surface area. FTIR studies showed that chemical modification promoted the formation of surface oxygen functionalities. Significant effects on BET surface area, pore texture and iodine adsorption capacity were evidenced. The results show that chemical modification prior to activation dramatically increased the BET surface area and total pore volume of the resulting activated carbon. Modified petroleum coke based activated carbon with chemical activation had higher specific surface area (2336 m²/g) and better iodine adsorption value (1998 mg/g).     

Superior carbon-based CO2 adsorbents prepared from poplar anthers

A series of renewable nitrogen-containing granular porous carbons with developed porosities and controlled surface chemical properties were prepared from poplar anthers. The preparation conditions such as pre-carbonization and activation temperatures and KOH amount significantly influence the structures and chemical compositions of the porous carbons, the CO₂ adsorption capacities of which are highly dependent on their pore structures, surface areas, nitrogen contents and adsorption conditions. The sample with developed microporosity, especially with the pores between 0.43 and 1 nm and high nitrogen content shows high CO₂ adsorption capacity at 1 bar and 25 °C. In contrast, when the adsorption pressure is higher than 5 bar, its CO₂ adsorption capacity is dominated by its surface area, and more accurately by its pore volume. Irrespective of this, if the pressure was decreased to 0.1 bar, its CO₂ capture ability is closely correlated to its nitrogen content but not to its porosity. By optimizing the preparation conditions, a porous carbon with a surface area of 3322 m² g⁻¹ and a CO₂ adsorption capacity as high as 51.3 mmol g⁻¹ at 50 bar and 25 °C was prepared.     

Enhancement of CO2 adsorption on phenolic resin-based mesoporous carbons by KOH activation

Carbons with high surface area and large volume of ultramicropores were synthesized for CO₂ adsorption. First, mesoporous carbons were produced by soft-templating method using triblock copolymer Pluronic F127 as a structure directing agent and formaldehyde and either phloroglucinol or resorcinol as carbon precursors. The resulting carbons were mainly mesoporous with well-developed surface area, large total pore volume, and only moderate CO₂ uptake. To improve CO₂ adsorption, these carbons were subjected to KOH activation to enhance their microporosity. Activated carbons showed 2–3-fold increase in the specific surface area, resulting from substantial development of microporosity (3–5-fold increase in the micropore volume). KOH activation resulted in enhanced CO₂ adsorption at 760 mmHg pressure: 4.4 mmol g⁻¹ at 25 °C, and 7 mmol g⁻¹ at 0 °C. This substantial increase in the CO₂ uptake was achieved due to the development of ultramicroporosity, which was shown to be beneficial for CO₂ physisorption at low pressures. The resulting materials were investigated using low-temperature nitrogen physisorption, CO₂ sorption, and small-angle powder X-ray diffraction. High CO₂ uptake and good cyclability (without noticeable loss in CO₂ uptake after five runs) render ultramicroporous carbons as efficient CO₂ adsorbents at ambient conditions.     

Porous carbon spheres as anode materials for sodium-ion batteries with high capacity and long cycling life

Porous carbon spheres (PCSs) with high surface area were fabricated by the reaction of D-Glucose monohydrate precursor with sodium molybdate dihydrate (Na₂MoO₄·2H₂O) via a facile hydrothermal method followed by carbonization and aqueous ammonia solution (NH₃·H₂O) treatment. The as-prepared PCSs exhibit a highly developed porous structure with a large specific surface area and show an excellent electrochemical performance as anode material of sodium-ion batteries (SIBs). A reversible capacity of 249.9 mA h g⁻¹ after 50 cycles at a current density of 50 mA g⁻¹ and a long cycling life at a high current density of 500 mA g⁻¹ are achieved. The excellent cycling performance and high capacity make the PCSs a promising candidate for long cycling SIBs.     

Molecular hydrogen and spiltover hydrogen storage on high surface area carbon sorbents

A series of templated carbons with various high surface areas (2033–3798 m²/g) have been prepared using various microporous zeolites as hard templates. Molecular hydrogen storage and spiltover hydrogen storage on these templated carbons were investigated and compared with superactivated carbon AX-21 and other reported porous carbon sorbents at 298 K and 100 atm. Two relationships between the surface areas of these carbons and their hydrogen capacities were obtained. The relationship between molecular hydrogen capacity and surface area showed a 0.23 wt.% H₂/1000 m²/g of carbon sorbent at 298 K and 100 atm, indicating that merely increasing surface areas of the carbon sorbents cannot achieve a significant molecular hydrogen capacity at ambient temperature. Spiltover hydrogen storage was achieved by doping Pt nanoparticles (as dissociative hydrogen source) on these carbons (spiltover hydrogen receptor). Our first result on the relationship between the spiltover hydrogen capacity and surface area showed 0.4 wt.% H₂/1000 m²/g of carbon sorbent at 298 K and 100 atm, which indicated that storage via spillover can lead to an average of 70% enhancement compared to molecular hydrogen storage.     

The production of polycarbosilane-derived porous carbon fibers

When a C-rich polycarbosilane (PCS) fiber is pyrolyzed in the presence of KOH, a porous carbon fiber was obtained after acid washing. During the process, silicon was almost completely eliminated and a large microporosity was formed. The porous carbon fibers have a surface area of 1100 m²/g and an average pore size of 2.80 nm. These materials are called “organic-carbide-derived carbons”.     

Hierarchically porous carbon by activation of shiitake mushroom for capacitive energy storage

We present a facile yet effective two-step activation method to prepare a hierarchically porous carbon with natural shiitake mushroom as the starting materials. The first step involves the activation of shiitake mushroom with H₃PO₄, while the second step is to further activate the product with KOH. The resulting carbon is comprised of abundant micro-, mesopores and interconnected macropores that has a specific surface area up to 2988 m² g⁻¹ and pore volume of 1.76 cm³ g⁻¹. With the unique porous nature, the carbon exhibited a specific capacitance of 306 and 149 F g⁻¹ in aqueous and organic electrolyte, respectively. Moreover, this carbon also shows a high capacitance retention of 77% at large current density of 30 A g⁻¹ and exhibited an outstanding cycling stability with 95.7% capacitance preservation after 15,000 cycles in 6 M KOH electrolyte. The far superior performance as compared with those of the commercially most used activated carbon RP20 in both aqueous and non-aqueous electrolyte demonstrates its great potential as high-performance supercapacitor electrode. The two-step method developed herein also represents a very attractive approach for scalable production of various functional carbon materials using diverse biomasses as starting materials.     

Nested [Na6(H2O)]6+ encapsulation of nickel(II) coordination framework assembled from pyridyl-2,6-dicarboxylic acid

Hydrothermal reactions of pyridyl-2,6-dicarboxylic acid (H₂PDC) and NiCl₂ · 6H₂O in the presence of NaOH and KOH, respectively afforded the products, {[Ni(PDC)(Cl)](Na)(H₂O)/3}_n (1) and K₂[Ni(PDC)₂] · 7H₂O (2), of which 1 was characterized consisting of 3-D porous framework and [Na₆(H₂O)]⁶⁺ inclusions, and 2 was a mononuclear complex with potassium hydrate as counterion.     

Impregnation assisted synthesis of 3D nitrogen-doped porous carbon with high capacitance

Three-dimensional (3D) porous carbons with controlled mesopore and micropore structures were prepared through a simple and low-cost ultrasonic and impregnation assisted method from waste air-laid paper. The ammonia management was used to dope the 3D porous carbons with different types of nitrogen heteroatoms in a way that replaced carbon atoms. The N₂ adsorption–desorption characterization suggested that the nitrogen-doped carbons have a high surface area of 1470 m² g⁻¹ with the average pore diameter of 4.2 nm, which are conducive to form electric double layer under high current density. The resulting 3D carbon exhibited a higher capacitance at 296 F g⁻¹ in comparison with the nitrogen-free one at 252 F g⁻¹ in 6 M KOH electrolyte. Moreover, a high power density ca. 0.313 kW kg⁻¹ and energy density ca. 34.3 Wh kg⁻¹ were achieved in the ionic liquid ([EMIm]BF₄). The findings will open a new avenue to use waste materials for high-performance energy-storage devices.     

Facile synthesis of functionalized porous carbon with three-dimensional interconnected pore structure for high volumetric performance supercapacitors

Functionalized porous carbon with three-dimensional (3D) interconnected pore structure has been successfully synthesized through direct heat-treatment of KOH-soaked soybeans. Benefiting from heteroatoms (N, O) doping, interconnected porous carbon framework with high surface area as well as high packing density (up to 1.1 g cm⁻³), the as-obtained porous carbon material exhibits high volumetric capacitance of 468 F cm⁻³, good rate capability and excellent cycling stability (91% of capacitance retention after 10,000 cycles) in 6 M KOH electolyte. More importantly, the as-assembled symmetric supercapacitor delivers high volumetric energy density of 28.6 Wh L⁻¹ in 1 M Na₂SO₄ aqueous solution.     

Spherical carbons: Synthesis,characterization and activation processes

Spherical carbons have been prepared through hydrothermal treatment of three carbohydrates (glucose, saccharose and cellulose). Preparation variables such as treatment time, treatment temperature and concentration of carbohydrate have been analyzed to obtain spherical carbons. These spherical carbons can be prepared with particle sizes larger than 10 μm, especially from saccharose, and have subsequently been activated using different activation processes (H₃PO₄, NaOH, KOH or physical activation with CO₂) to develop their textural properties. All these spherical carbons maintained their spherical morphology after the activation process, except when KOH/carbon ratios higher than 4/1 were used, which caused partial destruction of the spheres. The spherical activated carbons develop interesting textural properties with the four activating agents employed, reaching surface areas up to 3100 m²/g. Comparison of spherical activated carbons obtained with the different activating agents, taking into account the yields obtained after the activation process, shows that phosphoric acid activation produces spherical activated carbons with higher developed surface areas. Also, the spherical activated carbons present different oxygen groups’ content depending on the activating agent employed (higher surface oxygen groups content for chemical activation than for physical activation).     

Preparation and one-step activation of microporous carbon nanofibers for use as supercapacitor electrodes

Microporous carbon nanofibers were prepared by electrospinning from resole-type phenolic resin, followed by one-step activation. KOH was utilized to tune the fiber diameter and improve porous texture. By adjusting KOH content in the spinning solution, the fiber diameter could be controlled in the range of 252–666 nm and the microporous volume and specific surface area could be greatly improved. The electrochemical measurements in 6 M KOH aqueous solution showed that the microporous carbon nanofibers possessed high specific capacitance, considerable rate performance, and superior specific surface capacitance to conventional microporous carbons. The maximal specific capacitance of 256 F g⁻¹ and high specific surface capacitance of 0.51 F m⁻² were achieved at 0.2 A g⁻¹. Furthermore, the specific capacitance could still remain 170 F g⁻¹ at 20 A g⁻¹ with the retention of 67%. Analysis showed that the high specific surface capacitance of the resultant carbons was mainly attributed to optimized pore size (0.7–1.2 nm) and the excellent rate performance should be principally due to the reduced ion transportation distance derived from the nanometer-scaled fibers.     

Additive and pyrolysis atmosphere effects on polysiloxane-derived porous SiOC ceramics

Porous silicon oxycarbide (SiOC) is emerging as a much superior ultrahigh surface area material that can be stable up to high temperatures with great tailorability through composition and additive modifications. In this study, bulk SiOCs were fabricated from a base polysiloxane (PSO) system by using different organic additives and pyrolysis atmospheres followed by hydrofluoric acid (HF) etching. The additives modify the microstructural evolution by influencing the SiO₂ nanodomain formation. The SiOC ceramics contain significantly less SiC and more SiO₂ with Ar + H₂O atmosphere pyrolysis compared to Ar atmosphere pyrolysis. Water vapor injection during pyrolysis also causes a drastic increase in specific surface areas. The addition of 10 wt% tetraethyl orthosilicate (TEOS) with Ar + H₂O pyrolysis produces a specific surface area of 1953.94 m²/g, compared to 880.09 m²/g for the base PSO pyrolyzed in Ar. The fundamental processes for the composition and phase evolutions are discussed as a novel pathway to creating ultrahigh surface area materials. The ability to drastically increase the specific surface area through the use of pyrolysis atmosphere and organic additives presents a promising processing route for highly porous SiOC ceramics.     

Heteroatom-doped carbon gels from phenols and heterocyclic aldehydes: Sulfur-doped carbon xerogels

Sulfur-doped carbon xerogels were obtained through carbonization of resorcinol/2-thiophenecarboxaldehyde organic gels. The acid-catalyzed sol–gel polymerization of resorcinol and 2-thiophenecarboxaldehyde leads to organic gels whose morphology and texture is dependent on the amount of catalyst used. As a result, monolithic organic gels with sulfur content of up to 19.6 wt.% and easily tailored properties can be produced. After carbonization, a substantial amount of sulfur is retained and porous carbon xerogels with S-content of up to 10 wt.% are produced (at 800 °C). Depending on the sol–gel synthesis conditions, monolithic S-doped carbon xerogels with controllable and enhanced mesoporosity, surface areas of up to 670 m²/g and enhanced mechanical integrity were obtained. Additional KOH activation of the organic or carbon xerogels enables production of micro–mesoporous carbons with surface areas of up to 2550 m²/g while retaining over 5 wt.% of sulfur. Preliminary CO₂ adsorption measurements were performed. On the basis of resorcinol/2-thiophenecarboxaldehyde gel synthesis a more general approach towards heteroatom-doped carbon gels is proposed: sol–gel polymerization of phenols and heterocyclic aldehydes. Thus a variety of heteroatom-doped porous carbon materials with a tailored pore texture and morphology are available via this procedure.     

Synthesis of mesoporous carbons for supercapacitors from coal tar pitch by coupling microwave-assisted KOH activation with a MgO template

Mesoporous carbons (MCs) for supercapacitors were prepared from coal tar pitch by a microwave-assisted one-step process coupling the potassium hydroxide (KOH) activation and magnesium oxide (MgO) template. MCs were characterized by scanning electron microscope and X-ray diffraction. The results show that the specific surface area (S_BET), micropore volume and specific capacitance of MCs made by microwave heating as well as the energy density of MC capacitors pass through a maximum with increasing mass of MgO and the relative mass ratio of KOH/pitch. The S_BET of MCs varies from 1003 to 1394 m²/g. The S_BET and total pore volume of MC and microporous carbon made by microwave heating are bigger than that made by conventional heating. Under optimum conditions with the masses of coal tar pitch, MgO, KOH at 9 g, 12 g, 6 g, and the microwave power at 600 W, MC (MC_9-12-6) made at 30 min heating time shows a high specific capacitance of 224 F/g in 6 M KOH aqueous electrolyte after 1000 cycles. The results have shown that microwave-assisted rapid KOH activation coupled with the MgO template is an efficient one-step approach to the preparation of low cost yet high performance MCs for supercapacitors.     

Effect of early hydration temperature on hydration product and strength development of magnesium phosphate cement (MPC)

This paper investigates the effect of early hydration temperatures on hydration products and strength development of magnesium phosphate cement (MPC). MPC paste specimens with borate contents of 3%, 6%, 9% and 12% are prepared and cured in different air temperatures and in the adiabatic condition. The internal hydration temperatures are measured by pre-embedded temperature probes. MPC samples with different hydration temperatures are also obtained by using thin slice samples. The hydration products in MPC samples with different hydration temperatures are analyzed by X-ray diffractometer (XRD) and scanning electron microscope (SEM) and the strength development is also measured. The results show that NH₄MgPO₄·6H₂O is the major hydration product and beneficial to strength development of MPC at hydration temperature below 70 °C. NH₄MgPO₄·H₂O is another major product, which significantly decreases the strength, when the temperature is higher than a critical temperature between 70 °C and 75 °C. NH₄MgPO₄·H₂O can directly form in the MPC paste, and comes from the decomposition of NH₄MgPO₄·6H₂O when the temperature is above 75 °C. With temperature elevation and duration extension, NH₄MgPO₄·6H₂O decomposes rapidly, and even entirely when the temperature is above 100 °C. The borate content has no effect on the types of major hydration products and the critical temperature.     

Effect of Nb2O5 content and sintering temperature on the microstructure and bending strength of porous Ni-YSZ cermets

Porous Ni-YSZ cermets are prepared by reducing NiO-YSZ composites upon exposure to (Ar+6% H₂) gas. The porous cermets are prepared by the addition of carbon black (0.123 mol) to mixed NiO-YSZ powders and the conversion of NiO to Ni in the NiO-YSZ composites. The microstructure and bending strength of porous Ni-YSZ cermets as functions of sintering temperature and Nb₂O₅ content are discussed. The Ni-YSZ cermets consist of uniformly distributed Ni and YSZ grains as well as pores. Both higher sintering temperature and higher Nb₂O₅ content yield lower porosity, thus increasing the bending strength. The bending strength of 0.00470 mol% Nb₂O₅–containing Ni-YSZ cermets sintered at 1400 °C (111 MPa) is about two times higher than that of Nb₂O₅–free Ni-YSZ cermets sintered at 1400 °C (59 MPa).     

Structural evolution of carbide-derived carbons upon vacuum annealing

Microstructure and surface moieties of porous carbons play a significant role in affecting their performance in a variety of applications. While it is well known that high-temperature treatments of porous carbons can influence the microstructure, no systematic studies have been done on carbide-derived carbons. We show that vacuum annealing increases the pore volume and specific surface area of titanium carbide-derived carbon with no significant change in the pore size up to 1500 °C. This treatment produces porous carbons with subnanometer porosity and a specific surface area up to 2000 m²/g, while treating the samples at temperatures above 1600 °C increases the pore size above 1 nm because of graphitization and collapse of the micropore structure. The results demonstrate that vacuum treatment can be used to further tune the pore structure and potentially the surface functionality of carbide-derived carbons for supercapacitor electrodes, gas chromatography, sorption, sensing and other applications. Vacuum annealing of carbide-derived carbon is therefore a suitable alternative to conventional microstructure modification methods, such as gas or liquid phase activation, which are subject to substantial sample loss and result in additional surface functionalization.