Investigation into the Structure and Properties of Biochar Co-Activated by ZnCl2 and NaHCO3 under Low Temperature Conditions.

Using sodium lignosulfonate as feedstock, ZnCl2 and NaHCO3 co-activated the hierarchical porous carbons (HPCs) were prepared by one-pot pyrolysis with different NaHCO3 dosages (0-4 g) and carbonization temperatures (400-600 °C). Subsequently, phosphotungstate (HPW) was supported with the resulting biochar for the α-pinene hydration reaction to produce α-terpineol. The optimum preparation conditions were determined according to the yield of α-terpineol. The formation mechanism and physicochemical properties of HPCs were analyzed through TG, SEM, XPS, XRD, FT-IR, and N2 adsorption-desorption isotherms. The results demonstrated that NaHCO3 underwent a two-step reaction which liberated a substantial quantity of CO2, thereby enhancing activated carbon's macroporous and mesoporous structures. Simultaneously, NaHCO3 mitigated strong acid gas (HCl) emissions during ZnCl2 activation. Compared with AC450-4:8:0 prepared by ZnCl2 activation alone, the total pore volume of AC450-4:8:2 prepared by co-activation is increased from 0.595 mL/g to 0.754 mL/g and the mesopore rate from 47.7% to 77.8%, which is conducive to reducing the steric hindrance of the hydration reaction and improving the selectivity. Hydration experiments show that the selectivity of α-terpineol is 55.7% under HPW/AC450-4:8:2 catalysis, higher than 31.0% for HPW and 47.4% for HPW/AC450-4:8:0.

3D Carbon Microspheres with a Maze-Like Structure and Large Mesopore Tunnels Built From Rapid Aerosol-Confined Coherent Salt/Surfactant Templating.

Hierarchically porous carbons with tailor-made properties are essential for applications wherein rich active sites and fast mass transfer are required. Herein, a rapid aerosol-confined salt/surfactant templating approach is proposed for synthesizing hierarchically porous carbon microspheres (HPCMs) with a maze-like structure and large mesopore tunnels for high-performance tri-phase catalytic ozonation. The confined assembly in drying microdroplets is crucial for coherent salt (NaCl) and surfactant (F127) dual templating without macroscopic phase separation. The HPCMs possess tunable sizes, a maze-like structure with highly open macropores (0.3-30 µm) templated from NaCl crystal arrays, large intrawall mesopore tunnels (10-45 nm) templated from F127, and rich micropores (surface area >1000 m2 g-1 ) and oxygen heteroatoms originated from NaCl-confined carbonization of phenolic resin. The structure formation mechanism of the HPCMs and several influencing factors on properties are elaborated. The HPCMs exhibit superior performance in gas-liquid-solid tri-phase catalytic ozonation for oxalate degradation, owing to their hierarchical pore structure for fast mass transfer and rich defects and oxygen-containing groups (especially carbonyl) for efficient O3 activation. The reactive oxygen species responsible for oxalate degradation and the influences of several structure parameters on performance are discussed. This work may provide a platform for producing hierarchically porous materials for various applications.

Hierarchically Porous Carbons with Highly Curved Surfaces for Hosting Single Metal FeN4 Sites as Outstanding Oxygen Reduction Catalysts.

Iron-nitrogen-carbon (FeNC) materials have emerged as a promising alternative to platinum-group metals for catalyzing the oxygen reduction reaction (ORR) in proton-exchange-membrane fuel cells. However, their low intrinsic activity and stability are major impediments. Herein, an FeN-C electrocatalyst with dense FeN4 sites on hierarchically porous carbons with highly curved surfaces (denoted as FeN4 -hcC) is reported. The FeN4 -hcC catalyst displays exceptional ORR activity in acidic media, with a high half-wave potential of 0.85 V (versus reversible hydrogen electrode) in 0.5 m H2 SO4 . When integrated into a membrane electrode assembly, the corresponding cathode displays a high maximum peak power density of 0.592 W cm-2 and demonstrates operating durability over 30 000 cycles under harsh H2 /air conditions, outperforming previously reported Fe-NC electrocatalysts. These experimental and theoretical studies suggest that the curved carbon support fine-tunes the local coordination environment, lowers the energies of the Fe d-band centers, and inhibits the adsorption of oxygenated species, which can enhance the ORR activity and stability. This work provides new insight into the carbon nanostructure-activity correlation for ORR catalysis. It also offers a new approach to designing advanced single-metal-site catalysts for energy-conversion applications.

Structure-Property Correlation of Hierarchically Porous Carbons for Fluorocarbon Adsorption.

Although traditional commercially available porous carbon-fluorocarbon working pairs have shown promising applicability for adsorption cooling, advancements in engineered carbons may further improve the performance. Moreover, insights into structure-property relationships that target higher sorption capacities within these synthesized carbons may guide such materials' future design. We utilized hierarchically porous carbons (HPCs), synthesized with colossal microporous and mesoporous content characterized by high surface areas (up to 2689 m2/g) and pore volume values (up to 10.31 cm3/g) toward fluorocarbon R134a adsorption. This unique pore topology leads to exceptional R134a uptake, ∼250 wt %, outperforming the highest uptake carbon material to date, Maxsorb III (∼220 wt %). Material characterizations reveal that the outstanding R134a capacity may be attributed to textural properties and oxygen-terminated functional groups more than graphitization of the material. Most importantly, HPCs are efficiently utilized in a two-bed model chiller device, where the performance shows excellent working capacity (105 wt %, ∼2 times the value of reported carbon materials/R134a). Fluorocarbon adsorption on HPCs also displays fast kinetics (equilibrium time: ∼2 min) mainly driven by physical adsorption (Qst: ∼27 kJ/mol), characteristic of swiftly reversible behavior adsorption-desorption behaviors. This work provides a fundamental understanding of the applicability of HPCs/R134a working pair for adsorption cooling.

Highly effective adsorption of antibiotics from water by hierarchically porous carbon: Effect of nanoporous geometry.

Pharmaceutical antibiotics have recently become emerging environmental contaminants. To enhance the removal efficiency of antibiotics in water, hierarchically porous carbons (HPCs) with designed porous patterns are used in both batch and column mode adsorption processes in this study, and the role of their nanoporous geometry in the adsorption dynamics are explored. THPC (HPC with trimodal pores) and DHPC (HPC with bimodal pores) exhibit remarkably superior adsorption performances to the selected antibiotics than those of commercial activated carbon (AC) with similar surface area, especially in column mode adsorption. The effective treatment volumes of the HPC-columns remain up to 8-10 times those of the AC-columns for the removal of tetracycline and 4-6 times for the removal of tylosin. The mass transfer rates of the carbon-based columns present the order of THPC > DHPC > AC. As comparison, the columns based on monomodal mesoporous carbon (MEC) and microporous carbon (MAC) exhibit low effective treatment volumes although their high mass transfer speed. The interconnected meso/macropores in HPCs benefit the intraparticle mass transfer of guest molecules and the accessibility of adsorption sites. The micropores linking to the meso/macropores not only provide adsorption sites but also facilitate adsorption affinity.

Nitrogen-Doped Hierarchically Porous Carbons Derived from Polybenzoxazine for Enhanced Supercapacitor Performance.

Nitrogen-doped hierarchically porous carbons (HPCs), which are synthesized from benzoxazine resins, were successfully prepared following the processes of polymerization, carbonization, and potassium hydroxide (KOH) activation. As the key factor, the KOH activation temperature influences the pore structure and surface functionality, which are crucial for the excellent performance. The HPC-800 material, with the highest activation temperature (800 °C), displays a hierarchical pore structure, a high specific surface area (1812.4 m²·g-1), large total pore volume (0.98 cm³·g-1), high nitrogen content (1.27%), and remarkable electrical conductivity. It has also presented an excellent electrochemical performance of high specific capacitance of 402.4 F·g-1 at 0.1 A·g-1, excellent rate capability of 248.6 F·g-1 at 10 A·g-1, and long-term cycling stability with >99.0% capacitance retention after 500 cycles at 1 A·g-1 in 6 M KOH aqueous solution.

Preparation of hierarchically porous carbon from cellulose as highly efficient adsorbent for the removal of organic dyes from aqueous solutions.

The hierarchically porous carbons were prepared from cellulose by a one-step method and studied as dye-adsorbents using chrysoidine as a model. With the increase of holding temperature, the prepared porous carbons had larger specific surface area and became more effective. Kinetic analysis revealed that adsorption kinetics obeyed the pseudo-second order kinetic model and adsorption equilibrium could reach within 1 h. The studies on isotherm indicated that the adsorption process could be best described by the Langmuir isotherm model and the maximum adsorption capacities was 598.8 mg g-1. Thermodynamic parameters demonstrated that the adsorption process was exothermic and spontaneous. Moreover, the porous carbon could effectively remove some other common dyes. Importantly, the prepared porous carbon was able to remove 98% of chrysoidine from polluted river water and its adsorption efficiency was inappreciably influenced by the water matrix. These results shown that the hierarchically porous carbons synthesized from biomass in this study had a wide application in water treatment.

Mesopore- and Macropore-Dominant Nitrogen-Doped Hierarchically Porous Carbons for High-Energy and Ultrafast Supercapacitors in Non-Aqueous Electrolytes.

Non-aqueous electrolytes (e.g., organic and ionic liquid electrolytes) can undergo high working voltage to improve the energy densities of supercapacitors. However, the large ion sizes, high viscosities, and low ionic conductivities of organic and ionic liquid electrolytes tend to cause the low specific capacitances, poor rate, and cycling performance of supercapacitors based on conventional micropore-dominant activated carbon electrodes, limiting their practical applications. Herein, we propose an effective strategy to simultaneously obtain high power and energy densities in non-aqueous electrolytes via using a cattle bone-derived porous carbon as an electrode material. Because of the unique co-activation of KOH and hydroxyapatite (HA) within the cattle bone, nitrogen-doped hierarchically porous carbon (referred to as NHPC-HA/KOH) is obtained and possesses a mesopore- and macropore-dominant porosity with an ultrahigh specific surface area (2203 m2 g-1) of meso- and macropores. The NHPC-HA/KOH electrodes exhibit superior performance with specific capacitances of 224 and 240 F g-1 at 5 A g-1 in 1.0 M TEABF4/AN and neat EMIMBF4 electrolyte, respectively. The symmetric supercapacitor using NHPC-HA/KOH electrodes can deliver integrated high energy and power properties (48.6 W h kg-1 at 3.13 kW kg-1 in 1.0 M TEABF4/AN and 75 W h kg-1 at 3.75 kW kg-1 in neat EMIMBF4), as well as superior cycling performance (over 89% of the initial capacitance after 10 000 cycles at 10 A g-1).