Municipal landfill leachate (MLL) contamination in surface water is a critical global issue due to the high concentration of toxic organics and recalcitrants. The biological treatment of MLL is ineffective due to an elevated concentration of ammoniacal nitrogen, which restricts the production of the recalcitrant degrading laccase enzyme. In this context, integrating an external laccase-anchored carbon catalyst (LACC) matrix system with the microbial system could be an efficient strategy to overcome the drawbacks of conventional biological MLL treatment technologies. In the present study, the LACC matrix was synthesized by utilizing nanoporous activated carbon (NAC) functionalized ethylene diamine (EDA) and glutaraldehyde (GA) (GA/EDA/NAC) matrix for the anchoring of laccase. The maximum anchoring capacity of laccase onto GA/EDA/ NAC was achieved to be 139.65 U/g GA/EDA/NAC at the optimized anchoring time, 60 min; pH, 5; temperature, 30 °C, and mass of GA/EDA/NAC, 300 mg and was confirmed by Fourier transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscope (SEM), and X-ray Diffraction (XRD) analyses. Further, the mechanistic study revealed the involvement of covalent bonding in the anchoring of laccase onto the functionalized surface of the GA/EDA/NAC matrix. The adsorption isotherm and kinetics of laccase anchoring onto the GA/EDA/NAC matrix were performed to evaluate its field-level application. Subsequently, the sequential microbial system (I-stage bacterial treatment followed by II-stage fungal treatment) and III-stage LACC matrix system could effectively reduce the COD by 94.2% and phenol by 92.36%. Furthermore, the Gas Chromatography-Mass Spectrophotometry (GC–MS) and FT-IR analyses confirmed the effective degradation of organic compounds and recalcitrants by the integrated microbial and LACC matrix system. The study suggested that the application of the LACC matrix system has resulted in the complete treatment of real-time MLL by overcoming the negative interference of elevated ammoniacal nitrogen concentration. Thus, the integrated microbial and LACC matrix approach could be considered to effectively treat the MLL without any secondary pollution generation.
Aqueous Zn-ion batteries (ZIBs) are very attractive owing to their high safety and low cost. Among various cathode materials, organic materials-based electrodes incorporating various redox functional groups have gained significant attention in the field of ZIBs due to their benefits of a tunable structural design, facility, eco-friendly, and possibility of multivalent energy storage. Herein, we demonstrate the nanostructured organic active materials deposited onto the CNT networks (HyPT@ CNT) for flexible ZIBs. This HyPT nanorods were obtained reassemblying the herringbone structured 3,4,9,10-tetracarboxylic dianhydride through a hydrothermal process in the presence of acid. These HyPT@CNT hybrids were electronically conductive and redox active, as well as could be fabricated into a flexible electrode achieving flexibility from mechanical integrity of robust networked structure. The as-fabricated flexible ZIBs delivered the high capacity of 100 Ah g− 1 at a current density of 0.1 A g− 1 and long-term cycling performance exceeding 5000 cycles. Consequently, these electrochemical performances are associated with the redox reactivity of carbonyl groups as verified by spectroscopic and electrochemical characterizations and the hybridization of HyPT nanorods with CNT networks.
The complexation of silicon with carbon materials is considered an effective method for using silicon as an anode material for lithium-ion batteries. In the present study, carbon frameworks with a 3D porous structure were fabricated using metal–organic frameworks (MOFs), which have been drawing significant attention as a promising material in a wide range of applications. Subsequently, the fabricated carbon frameworks were subjected to CVD to obtain silicon-carbon complexes. These siliconcarbon complexes with a 3D porous structure exhibited excellent rate capability because they provided sufficient paths for Li-ion diffusion while facilitating contact with the electrolyte. In addition, unoccupied space within the silicon complex, combined with the stable structure of the carbon framework, allowed the volume expansion of silicon and the resultant stress to be more effectively accommodated, thereby reducing electrode expansion. The major findings of the present study demonstrate the applicability of MOF-based carbon frameworks as a material for silicon complex anodes.
Carbon nanofibers (CNFs) are promising materials for the construction of energy devices, particularly organic solar cells. In the electrospinning process, polyacrylonitrile (PAN) has been utilized to generate nanofibers, which is the simplest and most popular method of creating carbon nanofibers (CNFs) followed by carbonization. The CNFs are coated on stainless steel (SS) plates and involve an electropolymerization process. The prepared Cu, CNF, CNF–Cu, PANI, PANI–Cu, CNF–PANI, and CNF–PANI–Cu electrode materials’ electrical conductivity was evaluated using cyclic voltammetry (CV) technique in 1 M H2SO4 electrolyte solution. Compared to others, the CNF–PANI–Cu electrode has higher conductivity that range is 3.0 mA. Moreover, the PANI, CNF–PANI, and CNF–PANI–Cu are coated on FTO plates and characterized for their optical properties (absorbance, transmittance, and emission) and electrical properties (CV and Impedance) for organic solar cell application. The functional groups, and morphology-average roughness of the electrode materials found by FT–IR, XRD, XPS, SEM, and TGA exhibit a strong correlation with each other. Finally, the electrode materials that have been characterized serve to support and act as the nature of the hole transport for organic solar cells.
Dissolved organic matter (DOM) is a key component in the biogeochemical cycling in freshwater ecosystem. However, it has been rarely explored, particularly complex river watershed dominated by natural and anthropogenic sources, such as various effluent facility and livestock. The current research developed a new analytical method for TOC/TN (Total Organic Carbon/Total Nitrogen) stable isotope ratio, and distinguish DOM source using stable isotope value (δ13C-DOC) and spectroscopic indices (fluorescence index [FI] and biological index [BIX]). The TOC/TN-IR/MS analytical system was optimized and precision and accuracy were secured using two international standards (IAEA-600 Caffein, IAEA-CH-6 Sucrose). As a result of controlling the instrumental conditions to enable TOC stable isotope analysis even in low-concentration environmental samples (<1 mgC L-1), the minimum detection limit was improved. The 12 potential DOM source were collected from watershed, which includes top-soils, groundwater, plant group (fallen leaves, riparian plants, suspended algae) and effluent group (pig and cow livestock, agricultural land, urban, industry facility, swine facility and wastewater treatment facilities). As a result of comparing characteristics between 12 sources using spectroscopic indices and δ13C-DOC values, it were divided into four groups according to their characteristics as a respective DOM sources. The current study established the TOC/TN stable isotope analyses system for the first time in Korea, and found that spectroscopic indices and δ13C-DOC are very useful tool to trace the origin of organic matter in the aquatic environments through library database.
In recent years, supercapacitors have attracted extensive attention due to their advantages such as fast charge and discharge rate, high power density and long cycle life. Because of its unique porous structure and excellent electrochemical properties, heteroatom-doped porous carbon (HPC) is deemed as a promising electrode material for supercapacitors. However, it is a great challenge to synthesize electrode materials with large surface area, ultra-high porosity and good electrochemical performance. In this work, two-dimensional conjugated microporous polymers (CMPs) containing ketones were synthesized by a simple one-step coupling reaction and used as carbon precursors. A series of samples (CMP-Ts) were prepared with the procedures of coupling reaction and carbonization. The optimized carbon material has high specific surface area (up to 2229.85 m2 g− 1), porous structure, high specific capacitance (375 F g− 1 at 0.5 A g− 1), and good cycling stability (capacitance retention of 98.8% after 1000 cycles at 5 A g− 1). Further, the supercapacitor has an energy density of 28.8 Wh kg− 1 at a power density of 5000 W kg− 1. This work lays a foundation for the preparation of carbon materials using microporous polymer as a precursor system, provides a new way of thinking, and demonstrates a great potential of high-performance supercapacitors.
In this study, we synthesized pH-controlled resorcinol-formaldehyde (RF) gels through the polymerization of two starting materials: resorcinol and formaldehyde. The prepared RF gels were dried using an acetone substitution method, and they were subsequently carbonized under nitrogen atmosphere to obtain carbon xerogels (CX_Y) prepared at different pH (Y). The carbon xerogels were utilized as active materials for coin-type organic supercapacitor electrodes to investigate the influence of pH on the electrochemical properties of the carbon xerogels. The carbon xerogels prepared at lower pH (CX_9.5 and CX_10) exhibited sufficient particle growth, with a three-dimensional network of particles during the RF gel formation, resulting in the development of abundant mesopores. Conversely, the carbon xerogels prepared at higher pH (CX_11 and CX_12) retained densely packed structures of small particles, leading to pore collapse and low specific surface areas. Consequently, CX_9.5 and CX_10 showed high specific surface areas, and provided ample adsorption sites for the formation of electric double layers with electrolyte ions. Moreover, the three-dimensional particle network in CX_9.5 and CX_10 significantly enhanced electrical conductivity. The presence of well-developed mesopores in these materials further facilitated the effective transport of electrolyte ions, contributing to their superior performance as organic supercapacitor electrodes. This study confirmed that pH-controlled carbon xerogels are one of the promising active materials for organic supercapacitor electrodes. Furthermore, we concluded that pH during RF gel formation is a crucial factor determining the electrode performance of the carbon xerogels, highlighting the need for precise pH control to obtain high-performance carbon xerogel electrodes.
The disposal of organic pollutants is one of the important research topics. Some of the studies in this field are based on the degradation of organic pollutants with a catalytic agent. The cobalt tetraoxide/peroxymonosulfate system is an important catalytic system used for the radical degradation of organic pollutants. To increase the catalytic efficiency of such reactions, graphitization of activated carbon used as a support solid and nitrogen doping to the carbon structure are commonly used methods. In this study, cobalt tetraoxide production, N-doping and graphitization were carried out in a single step by heat treatment of activated carbon doped with the phthlocyanine cobalt (II) complex. The catalytic performance of the catalyst/ peroxymonosulfate system was investigated by changing the pH, catalyst, and PMS concentration parameters on rhodamine B and 1,3,5 trichlorophenol, which were used as models. It was seen that the catalysts had 97% activity on rhodamine B in 16 min and 100% on 1,3,5 trichlorophenol in 6 min. It was observed that the catalysts continued to show high catalytic activity for five cycles in reusability studies and had a very low cobalt leaching rate. These results are in good agreement with previously published studies. In line with these results, the synthesized N-doped graphitic carbon/Co3O4 catalyst can be used as an effective catalyst for wastewater treatments.
Volatile organic compounds (VOCs) are a paramount factor in air pollution of the environment. VOCs are vastly present in the wastewater discharged by the pharmaceutical industries. As it is evaporative in nature, it enters the environment spontaneously and causes air pollution, global warming, acid rain and climate change. VOCs must be treated before discharging or any other aerobic methods using an efficient catalyst. As the catalytic oxidation in the liquid phase is facile compared to the gas phase, this study investigated on catalytic liquid-phase oxidation of VOCs in model and real pharmaceutical wastewater. The model compounds of toluene-, ethylbenzene- and chlorobenzene-contaminated waters were treated separately along with the VOCs present in real pharmaceutical wastewater using a tungsten-based carbon catalyst. The tungsten was impregnated on the low-cost activated carbon matrix as it has good selectivity and catalytic property toward VOCs for facile catalytic operations. The metal catalysts were characterised by Fourier transform infrared spectroscopy, X-ray diffraction studies, and scanning electron microscopy with elemental and mapping analysis. The treatability was monitored by total organic carbon, ultra-violet spectroscopy and high-pressure liquid chromatography analysis. The tungsten-impregnated activated carbon matrix (WACM) has a catalytic efficiency toward toluene by 85.45 ± 1.78%, ethylbenzene by 93.9 ± 1.16%, chlorobenzene by 85.9 ± 2.26% and pharmaceutical VOCs by 85.05 ± 1.73% in 20 treatment cycles. The results showed that WACM worked efficiently in VOCs treatment, preventing the environment from air pollution. Furthermore, liquid-phase oxidation could easily be implementable on an industrial scale.
Polymeric carbon nitride (p-C3N4) is a promising platform as a metal-free photo-catalyst for various reactions. The p-C3N4 can be produced by thermal poly-condensation of organic precursors. Their morphological and chemical structures depend on reaction conditions during the poly-condensation. In this study, two p-C3N4 materials are produced by heat treatment of urea under different gaseous conditions with air (urea-derived carbon nitride under air, UCN-A) and N2 (UCN-N), respectively. UCN-A and UCN-N samples are mesoporous materials and show excellent photocatalytic activities for degrading rhodamine B, an organic pollutant, under the irradiation of visible light. The UCN-A shows the better photocatalytic activity than UCN-N. Various characterizations reveal that more porous structures and larger surface areas of UCN-A are reasons for the better photocatalytic performance.
A promising approach to enhance catalytic performance of supported heterogeneous nano-metal catalysts is to uniformly disperse active nanoparticles on the support. In this work, N-doped carbon-modified graphene (G@NC) nanosheet is designed and prepared to anchor Pd–Fe bimetallic nanoparticles (Pd–Fe/G@NC). The N-doped carbon modification on graphene surface could construct a sandwich-like structure (G@NC), which not only prevented the re-stacking of graphene nanosheets but also provided confined space for stable anchoring of bimetallic Pd–Fe nanoparticles. Benefitted from the unique structural property and synergetic effect of metal Pd and Fe species, the as-obtained Pd–Fe/G@NC composite displays excellent catalytic activity toward 4-nitrophenol reduction reaction with a turnover frequency of 613.2 min− 1, which is far superior to that of the mono-metal counterparts (Fe/G@NC and Pd/G@NC). More importantly, Pd–Fe/G@NC catalyst also exhibits favorable catalytic performance in the reduction of other nitroaromatic compounds (nitrobenzene, 4-nitrotoluene, 4-chloronitrobenzene, and so on). In addition, Pd–Fe/G@NC can catalyze the oxidation of furfuraldehyde to furoic acid with a high yield of 88.64%. This work provides a new guide for rationally designing and developing advanced supported heterogeneous bimetallic catalyst.
In this work, a nanocomposite containing gold (Au) nanofibers decorated iron-metal–organic framework (Fe-MOF) was successfully synthesized for electrochemical detection of acetaminophen (AAP). The as-synthesized Au@Fe-MOF nanocomposite was confirmed by various characterization techniques. Morphological analysis showed that the Au nanofibers with an average size of less than 10 nm were dispersed on the Fe-MOF. Cyclic voltammetric analysis showed that the Au@Fe-MOF nanocomposite showed well-defined redox peaks with higher current than that of GCE and Fe-MOF. The Au@Fe-MOF/ GCE exhibited a linear range, sensitivity, and detection limit of 0.5–18 μM, 4.95 μM/μA/cm2, and 0.12 μM, respectively. The Au@Fe-MOF/GCE showed a very low response for the interference materials. The real sample analysis revealed that the Au@Fe-MOF/GCE showed good recovery towards the AAP in urine and paracetamol. Therefore, the developed sensor can be used for quality control of AAP.
We investigated physicochemical properties and isotopic compositions of organic matter (δ13CTOC and δ15NTN) in the old fish farming (OFF) site after the cessation of aquaculture farming. Based on this approach, our objective is to determine the organic matter origin and their relative contributions preserved at sediments of fish farming. Temporal and spatial distribution of particulate and sinking organic matter (OFF sites: 2.0 to 3.3 mg L-1 for particulate matter concentration, 18.8 to 246.6 g m-2 day-1 for sinking organic matter rate, control sites: 2.0 to 3.5 mg L-1 for particulate matter concentration, 25.5 to 129.4 g m-2 day-1 for sinking organic matter rate) between both sites showed significant difference along seasonal precipitations. In contrast to variations of δ13CTOC and δ15NTN values at water columns, these isotopic compositions (OFF sites: -21.5‰ to - 20.4‰ for δ13CTOC, 6.0‰ to 7.6‰ for δ15NTN, control sites: - 21.6‰ to - 21.0‰ for δ13CTOC, 6.6‰ to 8.0‰ for δ15NTN) investigated at sediments have distinctive isotopic patterns (p<0.05) for seawater-derived nitrogen sources, indicating the increased input of aquaculture-derived sources (e.g., fish fecal). With respect to past fish farming activities, representative sources (e.g., fish fecal and algae) between both sites showed significant difference (p<0.05), confirming predominant contribution (55.9±4.6%) of fish fecal within OFF sites. Thus, our results may determine specific controlling factor for sustainable use of fish farming sites by estimating the discriminative contributions of organic matter between both sites.
In this report, we successfully prepared nitrogen-doped porous carbon (N-PC)/manganese dioxide ( MnO2) composite for a high-performance supercapacitor. X-ray diffraction data revealed the α-MnO2 phase. Transmission electron microscopy confirmed that the nanostructured α-MnO2 nanoparticles were coated on the surface of N-PC. The N-PC/α-MnO2 composite delivered a capacitance of 525.7 F g− 1 at the charging current of 1.0 A g− 1. The higher capacitance of the composite could be owing to the synergy of MnO2 and N-PC. Besides, the electrode exhibited a 14.7% capacitance loss after 6000 charge– discharge cycles at 10 A g− 1 indicating good electrochemical stability.
Here, a novel nitrogen-doped carbon nano-material (N-CGNM) with hierarchically porous structure was prepared from spent coffee ground for efficient adsorption of organic dyes by a simple one-step carbonization process (the uniform mixture consists of spent coffee ground, urea, and CaCl2 with the ratio of 1:1:1, which was heated to 1000 °C with a rate of 10 °C min− 1 and held at 1000 °C for 90 min in N2 atmosphere to carry out carbonization, activation, and N-doping concurrently). The morphology and structure analysis show that the prepared N-CGNM exhibits hierarchical pore structure, high specific surface area (544 m2/ g), and large numbers of positively charged nitrogen-containing groups. This unique structure and chemical composition endow N-CGNM with an excellent adsorption capacity toward anion Congo red (623.12 ± 21.69 mg/g), which is obviously superior to that (216.47 ± 18.43 mg/g) of untreated spent coffee ground-based carbon nano-materials (CGM). Oppositely, the adsorption capacity of N-CGNM towards cation methylene blue is inferior to that of CGM due to the existence of electrostatic repulsion. These findings show a great guidance for the development of low-cost but efficient selective adsorbent.
Sensing of volatile organic compounds (VOCs) is a growing research topic because of the concern about their hazard for the environment and health. Furan is a VOC produced during food processing, and it has been classified as a risk molecule for human health and a possible biomarker of prostate cancer. The use of carbon nanotubes for VOCs sensing systems design could be a good alternative. In this work, a theoretical evaluation of the interactions between furan and zigzag single-wall carbon nanotubes takes into account different positions and orientations of the furan molecule, within a density-functional theory first-principles approach. The van der Waals interactions are considered using different exchange-correlation functionals (BH,C09, DRSLL and KBM). The results indicate that vdW-functionals do not significantly affect geometry; however, the binding energy and the distance between furan and nanotube are strongly dependent on the selected exchange-correlation functional. On the other hand, the effects of single and double vacancies on carbon nanotube are considered. It was found that the redistribution of charge around the single-vacancy affects the bandgap, magnetic moment, and binding energy of the complex, while furan interaction with a double-vacancy does not considerably change the electronic structure of the system. Our results suggest that to induce changes in the electronic properties of carbon nanotubes by furan, it is necessary to change the nanotube surface, for example, by means of structural defects.
Doped porous carbon materials have attracted great interest owing to their excellent electrochemical performance toward energy storage applications. In this report, we described the synthesis of nitrogen-doped porous carbon (N-PC) via carbonization of a triazine-based covalent organic framework (COF) synthesized by Friedel–Crafts reaction. The as-synthesized COF and N-PC were confirmed by X-ray diffraction. The N-PC exhibited many merits including high surface area (711 m2 g−1), porosity, uniform pore size, and surface wettability due to the heteroatom-containing lone pair of electron. The N-PC showed a high specific capacitance of 112 F g−1 at a current density of 1.0 A g−1 and excellent cyclic stability with 10.6% capacitance loss after 5000 cycles at a current density of 2.0 A g−1. These results revealed that the COF materials are desirable for future research on energy storage devices.
Abstract In this study, we investigated that the activated carbon (AC)-based supercapacitor and introduced SIFSIX-3-Ni as a porous conducting additive to increase its electrochemical performances of AC/SIFSIX-3-Ni composite-based supercapacitor. The AC/SIFSIX-3-Ni composites are coated onto the aluminum substrate using the doctor blade method and conducted an ion-gel electrolyte to produce a symmetrical supercapacitor. The electrochemical properties of the AC/SIFSIX-3-Ni composite-based supercapacitor are evaluated through cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge/discharge tests (GCD). The AC/SIFSIX-3-Ni composite-based supercapacitor showed reasonable capacitive behavior in various electrochemical measurements, including CV, EIS, and GCD. The highest specific capacitance of the AC/SIFSIX-3-Ni composite-based supercapacitor was 129 F g−1 at 20 mV s−1.
Nanostructured ZnO materials have been studied extensively because of their functional properties. This paper presents a composite material of zinc oxide quantum dots (ZnO QDs) and porous carbon using a one-step carbonization process. The direct carbonization of a metal–organic complex generates mesostructured porous carbon with a homogeneous distribution of ZnO QDs. The structural and morphological properties are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The resulting ZnO QDs@porous carbon composite delivers a high specific capacity of 990 mAh g−1 at 100 mA g−1, 357 mAh g−1 at 2 A g−1, and high reversibility when evaluated as an anode for lithium ion batteries.