Preparation of Biomass-based Mesoporous Carbon with Higher Nitrogen-/Oxygen-chelating Adsorption for Cu(II) Through Microwave Pre-Pyrolysis.

An environment-friendly technique for synthesizing biomass-based mesoporous activated carbon with high nitrogen-/oxygen-chelating adsorption for Cu(II) is proposed. Bagasse impregnated with phosphoric acid is utilized as the precursor. To pyrolyze the precursor, two separate heating modes are used: microwave pyrolysis and conventional electric-heating pyrolysis. The resulting bagasse-derived carbon samples are modified with nitrification and reduction modification. Nitrogen (N)/oxygen (O) functional groups are simultaneously introduced to the surface of activated carbon, enhancing its adsorption of Cu(II) by complexing and ion-exchange. Characterization and copper adsorption experiments are performed to investigate the physicochemical properties of four prepared carbon samples and determine which heating method favors the subsequent modification for doping of N/O functional groups. In this technique, based on analyzing data of nitrogen adsorption, Fourier transform infrared spectroscopy, and batch adsorption experiments, it is proven that microwave-pyrolyzed carbon has more defect sites and, therefore, time-saving effective microwave pyrolysis contributes more N/O species to the carbon, although it leads to a lower specific surface area. This technique offers a promising route to synthesis adsorbents with higher nitrogen and oxygen content and a higher adsorption capacity of heavy-metal ions in wastewater remediation applications.

Effects of N mono- and N/P dual-doping on H2O2, OH generation, and MB electrochemical degradation efficiency of activated carbon fiber electrodes.

Pure N mono- and N/P dual-doped cotton-stalk-derived activated carbon fibers (CSCFs) were synthesized by steam, HNO3(CSCF-N), NH3(CSCF-A), and (NH4)3PO4(CSCF-N/P) treatments. This study investigated how three different N/P modifiers affected the pore structure, chemical property, H2O2 generation ability, and electrocatalytic activity of methylene blue (MB) degradation of CSCFs in an electric-Fenton system. Results confirmed that the three employed treatments effectively doped N/P in the carbon lattice and slightly changed the pore structures. NH3 and (NH4)3PO4 were the most effective modifiers for the N mono-doping and N/P dual-doping of CSCFs, respectively. Among the fabricated CSCFs, the N/P dual-doped CSCF-N/P demonstrated the highest electrochemical activity in an electro-Fenton system, followed by the N mono-doped CSCF-A, the CSCF-N, and the raw CSCF. In contrast to the CSCF electrode, the CSCF-N/P electrode exhibited enhanced H2O2, OH generation, and MB degradation efficiency by 42%, 41%, and 35%, respectively. Under optimum conditions, the electrochemical decolorization efficiency of MB (initial concentration, 100 mg L-1) of the CSCF-N/P reached 93% after 150 min and was 24.1% higher than that of the CSCF. By the tenth cycle, 82.2% of the MB could still be decomposed, suggesting the excellent stability and reusability of the N/P co-doped CSCF electrode. The outstanding electrocatalytic performance of the CSCF-N/P electrode is primarily due to the simultaneous doping of active N/P sites with low activation energy and introduction of mesopores with strong trapping forces for MB. The MB reduction catalyzed by CSCF electrodes followed pseudo-first-order kinetics, and the reaction rate depended on the modifiers.

Effect of pre-pyrolysis mode on simultaneous introduction of nitrogen/oxygen-containing functional groups into the structure of bagasse-based mesoporous carbon and its influence on Cu(II) adsorption.

A convenient effective microwave pre-pyrolysis treatment to synthesize biomass-based mesoporous carbon with higher nitrogen/oxygen-chelating adsorption for Cu(II) is reported here, in which phosphoric acid impregnated bagasse was used as a microwave absorber and porogen. For comparison, conventional electric-heating pyrolyzed carbon was prepared and doped with nitrogen/oxygen groups. Nitrogen adsorption, scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy (XPS) and batch adsorption were employed to investigate the effects of the two pre-pyrolysis modes on the sample physicochemical and Cu(II) adsorptive properties. The 22-min-microwave-pyrolyzed bagasse mesoporous activated carbon (MBAC, 85.32% mesoporosity) contained 10.52% O, which is 3.94% more than electric-heating pyrolyzed mesoporous activated carbon (89.52% mesoporosity). After electrophilic aromatic substitutions of N/O doping, the former possessed more N (5.83%) and more O (21.40%), confirming that time-saving energy-efficient microwave pyrolysis favors the formation of defective C/O atoms in or at the edges of the graphite layer of MBAC, which are highly active and tend to act as preferred reactive positions for the doping of N/O-containing groups simultaneously compared with conventional electric-heating pyrolysis. These N and O species existed mainly as COOH, OH, NH and NH2 functional groups, and were confirmed by XPS to be active sites for metal binding via electrostatic attraction, hydrogen bonding, a chelate effect and complexation, resulting in the great enhancement of Cu(II) adsorption. Langmuir isotherm and pseudo-second-order kinetic fitting further proved that Cu(II) adsorption by N/O-doped MBAC is ascribed mainly to chemisorption. Therefore, rapid microwave pre-pyrolysis provides a promising route to prepare excellent-performance N/O-doped carbon adsorbents.