Carbonaceous Materials-Based Photothermal Process in Water Treatment: From Originals to Frontier Applications.

The photothermal process has attracted considerable attention in water treatment due to its advantages of low energy consumption and high efficiency. In this respect, photothermal materials play a crucial role in the photothermal process. Particularly, carbonaceous materials have emerged as promising candidates for this process because of exceptional photothermal performance. While previous research on carbonaceous materials has primarily focused on photothermal evaporation and sterilization, there is now a growing interest in exploring the potential of photothermal effect-assisted advanced oxidation processes (AOPs). However, the underlying mechanism of the photothermal effect assisted by carbonaceous materials remains unclear. This review aims to provide a comprehensive review of the photothermal process of carbonaceous materials in water treatment. It begins by introducing the photothermal properties of carbonaceous materials, followed by a discussion on strategies for enhancing these properties. Then, the application of carbonaceous materials-based photothermal process for water treatment is summarized. This includes both direct photothermal processes such as photothermal evaporation and sterilization, as well as indirect photothermal processes that assisted AOPs. Meanwhile, various mechanisms assisted by the photothermal effect are summarized. Finally, the challenges and opportunities of using carbonaceous materials-based photothermal processes for water treatment are proposed.

Tailoring 3D-printed sensor properties with reduced-graphene oxide: improved conductive filaments.

The development of a tailored filament is reported composed of reduced graphene oxide (rGO) and carbon black (CB) in a polylactic acid (PLA) matrix and its use in the production of electrochemical sensors. The electrodes containing rGO showed superior performance when compared with  those prepared in the absence of this material. Physicochemical and electrochemical characterizations of the electrodes showed the successful incorporation of both rGO and CB and an improved conductivity in the presence of rGO (lower resistance to charge transfer). As a proof-of-concept, the developed electrodes were applied to the detection of the forensic analytes TNT and cocaine. The electrodes containing rGO presented a superior analytical performance for both TNT and cocaine detection, showing the lower limit of detection values (0.22 and 2.1 µmol L-1, respectively) in comparison with pure CB-PLA electrodes (0.93 and 11.3 µmol L-1, respectively). Besides, better-defined redox peaks were observed, especially for TNT, as well as increased sensitivity for both molecules.

Carbonaceous materials from a petrol primary oily sludge: Synthesis and catalytic performance in the wet air oxidation of a spent caustic effluent.

Oil refineries produce annually large quantities of oily sludge and non-biodegradable wastewater during petroleum refining that require adequate management to minimize its environmental impact. The fraction solid of the oily sludge accounts for 25 wt% and without treatment for their valorization. This work is focused on the valorization of these solid particles through their transformation into porous materials with enhanced properties and with potential application in the catalytic wet air oxidation (CWAO) of a non-biodegradable spent caustic refinery wastewater. Hence, dealing with the valorization and treatment of both refinery wastes in a circular approach aligned with the petrol refinery transformations by 2050. The obtained oily sludge carbonaceous materials showed improved surface area (260-762 m2/g) and a high Fe content. The good catalytic performance of these materials in CWAO processes has been attributed to the simultaneous presence of surface basic sites and iron species. Those materials with higher content of Fe and basic sites yielded the highest degradation of organic compounds present in the spent caustic refinery wastewater. In particular, the best-performing material ACT-NP 1.1 (non-preoxidated and thermically treated with 1:1 mass ratio KOH:solid) showed a chemical oxygen demand (COD) removal of 60 % after 3 h of reaction and with a higher degradation rate than that achieved with thermal oxidation without catalyst (WAO) and that using an iron-free commercial activated carbon. Moreover, the biodegradability of the treated wastewater increased up to 80% (from ca. 31% initially of the untreated effluent). Finally, this material was reused up to three catalytic cycles without losing metal species and keeping the catalytic performance.

A review on carbon-based biowaste and organic polymer materials for sustainable treatment of sulfonamides from pharmaceutical wastewater.

Frequent detection of sulfonamides (SAs) pharmaceuticals in wastewater has necessitated the discovery of suitable technology for their sustainable remediation. Adsorption has been widely investigated due to its effectiveness, simplicity, and availability of various adsorbent materials from natural and artificial sources. This review highlighted the potentials of carbon-based adsorbents derived from agricultural wastes such as lignocellulose, biochar, activated carbon, carbon nanotubes graphene materials as well as organic polymers such as chitosan, molecularly imprinted polymers, metal, and covalent frameworks for SAs removal from wastewater. The promising features of these materials including higher porosity, rich carbon-content, robustness, good stability as well as ease of modification have been emphasized. Thus, the materials have demonstrated excellent performance towards the SAs removal, attributed to their porous nature that provided sufficient active sites for the adsorption of SAs molecules. The modification of physico-chemical features of the materials have been discussed as efficient means for enhancing their adsorption and reusable performance. The article also proposed various interactive mechanisms for the SAs adsorption. Lastly, the prospects and challenges have been highlighted to expand the knowledge gap on the application of the materials for the sustainable removal of the SAs.

Limited Effectiveness of Carbonaceous Sorbents in Sequestering Aged Organic Contaminants in Sediments.

Carbonaceous materials are often proposed for use in restoring soils or sediments contaminated with hydrophobic organic contaminants (HOCs). However, the contamination of most sites is a result of historical events, where HOCs have resided in the solid compartment for many years or decades. The prolonged contact time, or aging, leads to reduced contaminant availability and likely diminished effectiveness of using sorbents. In this study, three different carbonaceous sorbents, i.e., biochars, powdered activated carbon, and granular activated carbon, were amended to a Superfund site marine sediment contaminated with DDT residues from decades ago. The amended sediments were incubated in seawater for up to 1 year, and the freely dissolved concentration (Cfree) and the biota-sediment accumulation factors (BSAFs) for a native polychaete (Neanthes arenaceodentata) were measured. Even though the bulk sediment concentrations were very high (6.4-154.9 µg/g OC), both Cfree and BSAFs were very small, ranging from nd to 1.34 ng/L and from nd to 0.024, respectively. The addition of carbonaceous sorbents, even at 2% (w/w), did not consistently lead to reduced DDT bioaccumulation. The limited effectiveness of carbonaceous sorbents was attributed to the low DDT availability due to prolonged aging, highlighting the need for considering contaminant aging when using sorbents for remediation.

Biomass-Derived Carbonaceous Materials with Graphene/Graphene-Like Structures: Definition, Classification, and Environmental Applications.

Biomass-derived carbonaceous materials with graphene/graphene-like structures (BGS) have attracted tremendous attention in the field of environmental remediation. The introduction of graphene/graphene-like structures into raw biochars can effectively improve their properties, such as electrical conductivity, surface functional groups, and catalytic activity. In 2021, the International Organization for Standardization defined graphene as a "single layer of carbon atoms with each atom bound to three neighbours in a honeycomb structure". Considering this definition, several studies have incorrectly referred to BGS (e.g., biomass-derived few-layer graphene or porous graphene-like nanosheets) as "graphene". The definitions and classifications of BGS and their applications in environmental remediation have not been assessed critically thus far. Comprehensive analysis and sufficient and robust evidence are highly desired to accurately determine the specific structures of BGS. In this perspective, we provide a systematic framework to define and classify the BGS. The state-of-the-art methods currently used to determine the structural properties of BGS are scrutinized. We then discuss the design and fabrication of BGS and how their distinctive features could improve the applicability of biomass-derived carbonaceous materials, particularly in environmental remediation. The environmental applications of these BGS are highlighted, and future research opportunities and needs are identified. The fundamental insights in this perspective provide critical guidance for the further development of BGS for a wide range of environmental applications.

N-doped citrate-sludge-derived carbon (NCSC) effectively promotes peroxymonosulfate activation for perfluorooctanoic acid (PFOA) removal with surface-mediated electron transfer mechanism.

In traditional wastewater treatment methods, the removal of emerging contaminants including perfluorooctanoic acid (PFOA) can be challenging. To address this, biochar is commonly utilized as an activator for peroxymonosulphate (PMS) to effectively eliminate organic pollutants. Sewage sludge has shown potential as a biochar precursor, but its complex composition and variable iron content, as well as the low specific surface area of the product limit the practical use of iron-dominated sludge-derived catalysts. To overcome this limitation, N-doped citrate-sludge-derived carbon (NCSC) was synthesized, possessing a low iron content (0.29 at%) and a large specific surface area (315.31 m2 g-1). As a comparison, Fe-/N-doped citrate-sludge-derived carbon (Fe-NCSC) was prepared by introducing exogenous iron, resulting in a higher iron content (2.12 at%) but a significantly reduced specific surface area (73.87 m2 g-1). In performance evaluation, the NCSC/PMS system achieved impressive removal efficiency, effectively eliminating 99.8% of PFOA (at an initial concentration of 2 mg L-1) within 60 min, while Fe-NCSC/PMS only achieved 84.6%. The slightly lower reaction rate per specific surface area of NCSC/PMS proved that large specific surface area was NCSC's key advantage. The lower sensitivity of NCSC to pH and water substrates than FeNCSC suggested different activation mechanisms. Further analysis of reactive sites and species showed that the main oxidation mechanism of NCSC/PMS was forming the surface-bound PMS-NCSC complexes at the N sites, followed by PFOA donating electrons to the complexes to be oxidized, which was different from the Fe/N-dominated singlet oxygen mechanism of Fe-NSC/PMS. Furthermore, the reusability of the NCSC was demonstrated, with the removal rate decreasing to only 90.1% after four cycles and recovering to 94.8% after heated regeneration. In conclusion, this study provides a viable method for the elimination of emerging contaminants such as PFOA in water remediation.

Electrochemically reduced graphene oxide films from Zn-C battery waste for the electrochemical determination of paracetamol and hydroquinone.

Contributing to the development of sustainable electroanalytical chemistry, electrochemically reduced graphene oxide (ERGO) films obtained from residual graphite of discharged Zn-C batteries are proposed in this work. Graphite from the cathode of discarded Zn-C batteries was recovered and used in the synthesis of graphene oxide (GO) by the modified Hummer's method. The quality of the synthesized GO was verified using different characterization methods (FT-IR, XRD, SEM, and TEM). GO films were deposited on a glassy carbon electrode (GCE) by the drop coating method and then electrochemically reduced by cathodic potential scanning using cyclic voltammetry. The electrochemical features of the ERGO films were investigated using the ferricyanide redox probe, as well as paracetamol (PAR) and hydroquinone (HQ) molecules as model analytes. From the cyclic voltammetry assays, enhanced heterogeneous electron transfer rate constants (k0) were observed for all redox systems studied. In analytical terms, the ERGO-based electrode showed higher analytical sensitivity than the bare and GO-modified GCE. Using differential pulse voltammetry, wide linear response ranges and limits of detection of 0.14 µmol L-1 and 0.65 µmol L-1 were achieved for PAR and HQ, respectively. Furthermore, the proposed sensor was successfully applied to the determination of PAR and HQ in synthetic urine and tap water samples (recoveries close to 100%). The outstanding electrochemical and analytical properties of the proposed ERGO films are added to the very low cost of the raw material, being presented as a green-based alternative for the development of electrochemical (bio)sensors with unsophisticated resources.

Catalytic Properties of High Nitrogen Content Carbonaceous Materials.

The influence of structural modifications on the catalytic activity of carbon materials is poorly understood. A collection of carbonaceous materials with different pore networks and high nitrogen content was characterized and used to catalyze four reactions to deduce structure-activity relationships. The CO2 cycloaddition and Knoevenagel reaction depend on Lewis basic sites (electron-rich nitrogen species). The absence of large conjugated carbon domains resulting from the introduction of large amounts of nitrogen in the carbon network is responsible for poor redox activity, as observed through the catalytic reduction of nitrobenzene with hydrazine and the catalytic oxidation of 3,3',5,5'-tetramethylbenzidine using hydroperoxide. The material with the highest activity towards Lewis acid catalysis (in the hydrolysis of (dimethoxymethyl)benzene to benzaldehyde) is the most effective for small molecule activation and presents the highest concentration of electron-poor nitrogen species.

Recent Progress in Carbonaceous and Redox-Active Nanoarchitectures for Hybrid Supercapacitors: Performance Evaluation, Challenges, and Future Prospects.

Due to advancements in technology, the energy demand is becoming more intense with time. The rapid fossil fuels consumption and environmental concerns triggered intensive research for alternative renewable energy resources, including sunlight and wind. Yet, due to their time-dependent operations, significant electric energy storage systems are required to store substantial energy. In this regard, electrochemical energy storage devices, like batteries and supercapacitors (SCs), have recently attracted much research attention. Recent developments in SCs demonstrated that hybrid SCs (HSCs), which combine the excellent properties of batteries and SCs, increase the specific energy, specific power, specific capacitance, and life span. Carbonaceous and redox-active materials have been explored as efficient electrode materials for applications in HSCs, ultimately enhancing their electrochemical performances. The HSCs performance significantly depends on the porosity, specific surface area, and conductivity of the electrode materials. This review article gives an overview of recent advances in developing HSCs with high specific power, specific energy, and long cyclic-life. The fabrication of various HSCs materials using carbonaceous and redox-active nanoarchitectures and their characterization are explored in-depth, including electrode development, basic principles, and device engineering. A proper investigation has been conducted regarding state-of-the-art materials as HSC electrodes. This review focuses on the most up-to-date, cutting-edge, electrode materials for HSCs and their performance. The possibilities for novel electrode materials and their impact on the HSCs performance for future energy storage are also discussed.

Upcycling Plastic Waste into High Value-Added Carbonaceous Materials.

Even though plastic improved the human standard of living, handling the plastic waste represents an enormous challenge. It takes more than 100 years to decompose discarded or buried waste plastics. Microplastics are one of the causes of significantly pervasive environmental pollutants. The incineration of plastic waste generates toxic gases, underscoring the need for new approaches, in contrast to conventional strategies that are required for recycling plastic waste. Therefore, several studies have attempted to upcycle plastic waste into high value-added products. Converting plastic waste into carbonaceous materials is an excellent upcycling technique due to their diverse practical applications. This review summarizes various studies dealing with the upcycling of plastic waste into carbonaceous products. Further, this review discusses the applications of carbonaceous products synthesized from plastic waste including carbon fibers, absorbents for water purification, and electrodes for energy storage. Based on the findings, future directions for effective upcycling of plastic waste into carbonaceous materials are suggested.

From Cyclo[18]carbon to the Novel Nanostructures-Theoretical Predictions.

In this paper, we present a number of novel pure-carbon structures generated from cyclo[18]carbon. Due to the very high reactivity of cyclo[18]carbon, it is possible to link these molecules together to form bigger molecular systems. In our studies, we generated new structures containing 18, 36 and 72 carbon atoms. They are of different shapes including ribbons, sheets and tubes. All these new structures were obtained in virtual reactions driven by external forces. For every reaction, the energy requirement was evaluated exactly when the corresponding transition state was found or it was estimated through our new approach. A small HOMO-LUMO gap in these nanostructures indicates easy excitations and the multiple bonds network indicates their high reactivity. Both of these factors suggest that some potential applications of the new nanostructures are as components of therapeutically active carbon quantum dots, terminal fragments of graphene or carbon nanotubes obtained after fracture or growing in situ in catalytic reactions leading to the formation of carbonaceous materials.

The Influence of NH4NO3 and NH4ClO4 on Porous Structure Development of Activated Carbons Produced from Furfuryl Alcohol.

The influence of NH4NO3 and NH4ClO4 on the porous texture and structure development of activated carbons produced from a non-porous polymeric precursor synthesized from furfuryl alcohol has been studied. The non-doped counterparts were prepared and studied for comparison purposes. NH4NO3 and NH4ClO4-doped polymers were carbonized under N2 atmosphere at 600 °C, followed by CO2 activation at 1000 °C and the obtained carbon materials and activated carbons were thoroughly characterized. The porosity characterization data have shown that NH4NO3-derived ACs present the highest specific surface area (up to 1523 m2/g in the experimental conditions studied), and the resulting porosity distributions are strongly dependent on the activation conditions. Thus, 1 h activation is optimum for the microporosity development, whereas larger activation times lead to micropores enlargement and conversion into mesopores. The type of doping salts used also has a substantial impact on the surface chemical composition, i.e., C=O groups. Moreover, NH4NO3 and NH4ClO4 constitute good sources of nitrogen. The type and contribution of nitrogen species are dependent on the preparation conditions. Quaternary nitrogen only appears in doped samples prepared by carbonization and pyrrolic, pyrydinic, and nitrogen oxide groups appear in the NH4NO3 -series. NH4NO3 incorporation has led to optimized materials towards CO2 and C2H4 sorption with just 1 h activation time.

An electrochemical label-free DNA impedimetric sensor with AuNP-modified glass fiber/carbonaceous electrode for the detection of HIV-1 DNA.

In this study, a highly sensitive, electrochemical, and label-free DNA impedimetric sensor was developed using carbonized glass fiber-coal tar pitch (GF-CTP) electrodes supported with gold nanoparticles (AuNPs) for the detection of HIV-1 gene. Thiol-modified GF-CTP electrodes were prepared using amine crosslinking chemistry and AuNPs were self-assembled obtaining highly conductive nanoelectrodes, GF-CTP-ATP-Au. All steps of electrode modifications were characterized using electrochemical, spectroscopic, and microscopic methods. GF-CTP-ATP-Au electrode was then modified with a capture DNA probe (C-ssDNA) and optimized with a target DNA probe in terms of hybridization time and temperature between 30 and 180 min and 20-50 °C, respectively. Finally, the analytic performance of the developed ssDNA biosensor was evaluated using electrochemical impedance spectroscopy. The calibration of the sensor was obtained between 0.1 pM and 10 nM analyte working range. The limit of detection was calculated using signal to noise ratio of 3 (S/N = 3) as 13 fM. Moreover, interference results for two noncomplementary DNA probes were also tested to demonstrate non-specific ssDNA interactions. An electrochemical label-free DNA impedimetric sensor was successfully developed using a novel GF-CTP-ATP-Au electrode. This study suggests that highly sensitive DNA-based biosensors can be developed using relatively low-cost carbonaceous materials.

Personal exposure to fine particles (PM2.5) and respiratory inflammation of common residents in Hong Kong.

BACKGROUND: Given the lack of research on the personal exposure to fine particles (PM2.5) in Hong Kong, we examined the association between short-term personal exposure to PM2.5 and their constituents and inflammation in exhaled breath in a sample of healthy adult residents. METHOD: Forty-six participants underwent personal PM2.5 monitoring for averagely 6 days to obtain 276 samples. Fractional exhaled nitric oxide (FeNO), a biomarker of inflammation in exhaled breath, was measured at the end of each 24-h personal monitoring. PM2.5 chemical constituents, including organic carbon, elemental carbon, 16 polycyclic aromatic hydrocarbons (PAHs), and 6 phthalate esters, were speciated from the personal samples collected. A mixed-effects model was used to estimate the association of PM2.5 and their constituents with FeNO. The comparison was also made with parallel analyses using ambient concentrations. RESULTS: Personal exposures to PM2.5 (28.1 ±â€¯23.3 µg/m3) were higher than the ambient levels (13.3 ±â€¯6.4 µg/m3) monitored by stations. The composition profile and personal-to-ambient concentration ratio varied among subjects with different occupations. An interquartile range (IQR) change in personal exposure to PM2.5 was positively associated with 12.8% increase in FeNO (95% confidence interval, CI: 5.5-20.7%), while nil association was found for ambient PM2.5. Among the constituents measured, only the carcinogenic PAHs were significantly associated with 12% increase in FeNO responses (95% CI, 0.0-25.6%). CONCLUSION: In conclusion, our study provides the first understanding about personal exposure to PM2.5 and possible sources in Hong Kong. The results also showed that personal exposure to PM2.5 and c-PAHs were linked to increased FeNO levels among healthy adults.

Noncontinuous Super-Diffusive Dynamics of a Light-Activated Nanobottle Motor.

We report a carbonaceous nanobottle (CNB) motor for near infrared (NIR) light-driven jet propulsion. The bottle structure of the CNB motor is fabricated by soft-template-based polymerization. Upon illumination with NIR light, the photothermal effect of the CNB motor carbon shell causes a rapid increase in the temperature of the water inside the nanobottle and thus the ejection of the heated fluid from the open neck, which propels the CNB motor. The occurrence of an explosion, the on/off motion, and the swing behavior of the CNB motor can be modulated by adjusting the NIR light source. Moreover, we simulated the physical field distribution (temperature, fluid velocity, and pressure) of the CNB motor to demonstrate the mechanism of NIR light-driven jet propulsion. This NIR light-powered CNB motor exhibits fuel-free propulsion and control of the swimming velocity by external light and has great potential for future biomedical applications.

Seeded Synthesis of Monodisperse Core-Shell and Hollow Carbon Spheres.

Monodisperse carbon spheres between 500 and 900 nm are hydrothermally synthesized from glucose on polystyrene seeds. Control over temperature, time, glucose concentration, and seed size yields hybrid spheres without aggregation and no additional spheres population. Pyrolysis transforms the hybrid into hollow carbon spheres preserving monodispersity. This approach provides a basis for functional carbon spheres applicable in photonics and energy storage.

Superior Sodium Storage in 3D Interconnected Nitrogen and Oxygen Dual-Doped Carbon Network.

Carbonaceous materials have attracted immense interest as anode materials for Na-ion batteries (NIBs) because of their good chemical, thermal stabilities, as well as high Na-storage capacity. However, the carbonaceous materials as anodes for NIBs still suffer from the lower rate capability and poor cycle life. An N,O-dual doped carbon (denoted as NOC) network is designed and synthesized, which is greatly favorable for sodium storage. It exhibits high specific capacity and ultralong cycling stability, delivering a capacity of 545 mAh g(-1) at 100 mA g(-1) after 100 cycles and retaining a capacity of 240 mAh g(-1) at 2 A g(-1) after 2000 cycles. The NOC composite with 3D well-defined porosity and N,O-dual doped induces active sites, contributing to the enhanced sodium storage. In addition, the NOC is synthesized through a facile solution process, which can be easily extended to the preparation of many other N,O-dual doped carbonaceous materials for wide applications in catalysis, energy storage, and solar cells.

Reactive Oxygen-Doped 3D Interdigital Carbonaceous Materials for Li and Na Ion Batteries.

Carbonaceous materials as anodes usually exhibit low capacity for lithium ion batteries (LIBs) and sodium ion batteries (SIBs). Oxygen-doped carbonaceous materials have the potential of high capacity and super rate performance. However, up to now, the reported oxygen-doped carbonaceous materials usually exhibit inferior electrochemical performance. To overcome this problem, a high reactive oxygen-doped 3D interdigital porous carbonaceous material is designed and synthesized through epitaxial growth method and used as anodes for LIBs and SIBs. It delivers high reversible capacity, super rate performance, and long cycling stability (473 mA h g(-1) after 500 cycles for LIBs and 223 mA h g(-1) after 1200 cycles for SIBs, respectively, at the current density of 1000 mA g(-1) ), with a capacity decay of 0.0214% per cycle for LIBs and 0.0155% per cycle for SIBs. The results demonstrate that constructing 3D interdigital porous structure with reactive oxygen functional groups can significantly enhance the electrochemical performance of oxygen-doped carbonaceous material.

Effect of carbonaceous materials on phosphorus removal in flow-through packed column systems.

Phosphorus (P) overloading in aquatic environments has long-been recognized as the leading cause of water quality deterioration, harmful algal bloom, and eutrophication. This study investigated P removal performance by five cost-effective carbonaceous materials (CMs) in flow-through packed column systems. These CMs include biochars pyrolyzed from feedstocks of Eucalyptus (E-biochar) and Douglas fir (D-biochar), commercial biochar (C-biochar), iron oxide-coated biochar (Fe-biochar), and commercial activated carbon (AC). The physicochemical properties of CMs, such as specific surface area (SSA), pore volume, pore diameter, elemental composition, and surface charge, were characterized. The packed column experimental results showed that P removal performance followed the order: E-biochar < D-biochar < C-biochar < Fe-biochar < AC. Specifically, the sorption capacity of 1 mg/L of P in packed columns was 0.0036 mg P/g E-biochar, 0.0111 mg P/g D-biochar, 0.0369 mg P/g D-biochar, 0.077 mg P/g Fe-biochar, and 0.088 mg P/g AC, respectively. The largest SSA (1012 m2/g) and pore volume (0.57 cm3/g) of AC accounted for the most outstanding P removal efficiency mainly by physical sorption, while electrostatic interaction explained the high P removal by Fe-biochar (SSA as low as 32.4 m2/g). Our findings provide direct practical implications for effectively removing P in water by cost-effective CMs.