Graphitic carbon nitride (g-C3 N4 ) is a kind of ideal metal-free photocatalysts for artificial photosynthesis. At present, pristine g-C3 N4 suffers from small specific surface area, poor light absorption at longer wavelengths, low charge migration rate, and a high recombination rate of photogenerated electron-hole pairs, which significantly limit its performance. Among a myriad of modification strategies, point-defect engineering, namely tunable vacancies and dopant introduction, is capable of harnessing the superb structural, textural, optical, and electronic properties of g-C3 N4 to acquire an ameliorated photocatalytic activity. In view of the burgeoning development in this pacey field, a timely review on the state-of-the-art advancement of point-defect engineering of g-C3 N4 is of vital significance to advance the solar energy conversion. Particularly, insights into the intriguing roles of point defects, the synthesis, characterizations, and the systematic control of point defects, as well as the versatile application of defective g-C3 N4 -based nanomaterials toward photocatalytic water splitting, carbon dioxide reduction and nitrogen fixation will be presented in detail. Lastly, this review will conclude with a balanced perspective on the technical and scientific hindrances and future prospects. Overall, it is envisioned that this review will open a new frontier to uncover novel functionalities of defective g-C3 N4 -based nanostructures in energy catalysis.
The widespread consumption of pharmaceutical drugs and their incomplete breakdown in organisms has led to their extensive presence in aquatic environments. The indiscriminate use of antibiotics, such as sulfonamides, has contributed to the development of drug-resistant bacteria and the persistent pollution of water bodies, posing a threat to human health and the safety of the environment. Thus, it is paramount to explore remediation technologies aimed at decomposing and complete elimination of the toxic contaminants from pharmaceutical wastewater. The review aims to explore the utilization of metal-oxide nanoparticles (MONPs) and graphitic carbon nitrides (g-C3N4) in photocatalytic degradation of sulfonamides from wastewater. Recent advances in oxidation techniques such as photocatalytic degradation are being exploited in the elimination of the sulfonamides from wastewater. MONP and g-C3N4 are commonly evolved nano substances with intrinsic properties. They possessed nano-scale structure, considerable porosity semi-conducting properties, responsible for decomposing wide range of water pollutants. They are widely applied for photocatalytic degradation of organic and inorganic substances which continue to evolve due to the low-cost, efficiency, less toxicity, and more environmentally friendliness of the materials. The review focuses on the current advances in the application of these materials, their efficiencies, degradation mechanisms, and recyclability in the context of sulfonamides photocatalytic degradation.
In this work, we describe the genome of Lysinibacillus sp. strain A1, which was isolated from tropical soil. Analysis of its genome sequence shows the presence of a gene encoding for a putative peptidase responsible for nitrogen compounds.
Photocatalytic CO2 reduction is a revolutionary approach to solve imminent energy and environmental issues by replicating the ingenuity of nature. The past decade has witnessed an impetus in the rise of two-dimensional (2D) structure materials as advanced nanomaterials to boost photocatalytic activities. In particular, the use of 2D carbon-based materials is deemed as highly favorable, not only as a green material choice, but also due to their exceptional physicochemical and electrical properties. This Review article presents a diverse range of alterations and compositions derived from 2D carbon-based nanomaterials, mainly graphene and graphitic carbon nitride (g-C3 N4 ), which have remarkably ameliorated the photocatalytic CO2 performance. Herein, the rational design of the photocatalyst systems with consideration of the aspect of dimensionality and the resultant heterostructures at the interface are systematically analyzed to elucidate an insightful perspective on this pacey subject. Finally, a conclusion and outlook on the limitations and prospects of the cutting-edge research field are highlighted.
Universal access to clean water has been a global ambition over the years. Photocatalytic water disinfection through advanced oxidation processes has been regarded as one of the promising methods for breaking down microbials. The forefront of this research focuses on the application of metal-free photocatalysts for disinfection to prevent secondary pollution. Graphitic carbon nitride (g-C3 N4 ) has achieved instant attention as a metal-free and visible-light-responsive photocatalyst for various energy and environmental applications. However, the photocatalytic efficiency of g-C3 N4 is still affected by its rapid charge recombination and sluggish electron-transfer kinetics. In this contribution, two-dimensionally protonated g-C3 N4 was employed as metal-free photocatalyst for water treatment and demonstrated 100 % of Escherichia coli within 4 h under irradiation with a 23 W light bulb. The introduction of protonation can modulate the surface charge of g-C3 N4 ; this enhances its conductivity and provides a "highway" for the delocalization of electrons. This work highlights the potential of conjugated polymers in antibacterial application.
In the past few decades, there has been a rapid growth in the concentration of nitrogenous compounds such as nitrate-nitrogen and ammonia-nitrogen in rivers, primarily due to increasing agricultural and industrial activities. These nitrogenous compounds are mainly responsible for eutrophication when present in river water, and for 'blue baby syndrome' when present in drinking water. High concentrations of these compounds in rivers may eventually lead to the closure of treatment plants. This study presents a training and a selection approach to develop an optimum artificial neural network model for predicting monthly average nitrate-N and monthly average ammonia-N. Several studies have predicted these compounds, but most of the proposed procedures do not involve testing various model architectures in order to achieve the optimum predicting model. Additionally, none of the models have been trained for hydrological conditions such as the case of Malaysia. This study presents models trained on the hydrological data from 1981 to 2017 for the Langat River in Selangor, Malaysia. The model architectures used for training are General Regression Neural Network (GRNN), Multilayer Neural Network and Radial Basis Function Neural Network (RBFNN). These models were trained for various combinations of internal parameters, input variables and model architectures. Post-training, the optimum performing model was selected based on the regression and error values and plot of predicted versus observed values. Optimum models provide promising results with a minimum overall regression value of 0.92.
Graphitic carbon nitride (g-C3N4) has been regarded as a promising visible light-driven photocatalyst ascribable to its tailorable structures, thermal stability and chemical inertness. Enhanced photocatalytic activity is achievable by the construction of homojunction nanocomposites to reduce the undesired recombination of photogenerated charge carriers. In the present work, a novel g-C3N4/g-C3N4 metal-free homojunction photocatalyst was synthesized via hydrothermal polymerization. The g-C3N4/g-C3N4 derived from urea and thiourea demonstrated admirable photocatalytic activity towards rhodamine B (RhB) degradation upon irradiation of an 18 W LED light. The viability of the photoreaction with a low-powered excitation source highlighted the economic and environmental benefits of the process. The optimal g-C3N4/g-C3N4 homojunction photocatalyst exhibited a 2- and 1.8-fold increase in efficiency in relative to pristine g-C3N4 derived from urea and thiourea respectively. The enhanced photocatalytic performance is credited to the improved interfacial transfer and separation of electron-hole pairs across the homojunction interface. Furthermore, an excellent photochemical stability and durability is displayed by g-C3N4/g-C3N4 after three consecutive cycles. In addition, a plausible photocatalytic mechanism was proposed based on various scavenging tests. Overall, experimental results generated from this study is expected to intrigue novel research inspirations in developing metal-free homojunction photocatalysts to be feasible for large-scale wastewater treatment without compromising economically. Graphical abstract.
This work demonstrates a high-performance hybrid asymmetric supercapacitor (HASC) workable in very high current density of 30 A g-1 with in-situ pyrolytic processed sulfur-doped graphitic carbon nitride/cobalt disulfide (S-gC3N4/CoS2) materials and bio-derived carbon configuration and achievement of high electrochemical stability of 89% over 100,000 cycles with the coulombic efficiency of 99.6%. In the electrochemical studies, the S-gC3N4/CoS2-II electrode showed a high specific capacity of 180 C g-1 at 1 A g-1 current density in the half-cell configuration. The HASC cell was fabricated using S-gC3N4/CoS2-II material and orange peel derived activated carbon as a positive and negative electrode with a maximum operating cell potential of 1.6 V, respectively. The fabricated HASC delivered a high energy density of 26.7 Wh kg-1 and power density of 19.8 kW kg-1 in aqueous electrolyte. The prominent properties in specific capacity and cycling stability could be attributed to the CoS2 nanoparticles engulfed into the S-gC3N4 framework which provides short transport distance of the ions, strong interfacial interaction, and improving structural stability of the S-gC3N4/CoS2-II materials.
Cobalt incorporated sulfur-doped graphitic carbon nitride with bismuth oxychloride (Co/S-gC3N4/BiOCl) heterojunction is prepared by an ultrasonically assisted hydrothermal treatment. The heterojunction materials have employed in photoelectrochemical (PEC) water splitting. The PEC activity and stability of the materials are promoted by constructing an interface between the visible light active semiconductor photocatalyst and cocatalysts. The photocurrent density of Co-9% S-gC3N4/BiOCl has attained 393.0 μA cm-2 at 1.23 V vs. RHE, which is 7-fold larger than BiOCl and ~3-fold higher than 9% S-gC3N4/BiOCl. The enhanced PEC activity can be attributed to the improved electron-hole charge separation and the boosted charge transfer is confirmed by photoluminescence (PL) and electrochemical impedance spectroscopy (EIS) analysis. The fabricated Co/S-gC3N4/BiOCl nanohybrid material has exhibited high stability of up to 10,800 s (3 h) at 1.23 V vs. RHE during PEC water splitting reaction and the obtained photo-conversion efficiency is 3.7-fold greater than S-gC3N4/BiOCl and 17-fold higher than BiOCl. The FESEM and HRTEM images have revealed the formation of heterojunction interface between S-gC3N4 and BiOCl and the elemental mapping has confirmed the presence of cobalt over S-gC3N4/BiOCl. The heterojunction interface has facilitated the photo-excited charge separation and transport across the electrode/electrolyte interface and also the flat-band potential, which is confirmed by Mott-Schottky analysis.
One of the most crucial attributes of synthetic organic chemistry is to design organic reactions under the facets of green chemistry for the sustainable production of chemicals. Thus, due to the intensified environmental and safety concern, the need for new technologies for conducting chemical transformation has grown. In this regard, there is enormous interest in the use of heterogeneous catalysts as they generally avoid the generation of waste, require fewer toxic reagents, as well as entail easier separation and recycling of the catalyst. α,β-Unsaturated acids have been widely used in various industrial applications and have been identified as one of the most promising chemicals obtained via the Knoevenagel condensation reaction. This review aims to discuss the most pertinent heterogeneous catalytic systems such as zeolites, mesoporous silica, ionic liquids, metal oxides, and graphitic carbon nitride-based catalysts in the Knoevenagel reaction. Ultimately, this review focuses not only on the catalyst but also provides an overall idea and guide for the preparation of new catalysts with outstanding properties by looking at the chemical and engineering aspects such as the reaction conditions and the mechanisms.
The development of semiconductor heterojunctions is a promising and yet challenging strategy to boost the performance in photoelectrochemical (PEC) water splitting. This paper describes the fabrication of a heterojunction photoanode by coupling α-Fe2O3 and g-C3N4via aerosol-assisted chemical vapour deposition (AACVD) followed by spin coating and air annealing. Enhanced PEC performance and stability are observed for the α-Fe2O3/g-C3N4 heterojunction photoanode in comparison to pristine α-Fe2O3 and the reason is systematically discussed in this paper. Most importantly, the fabricated α-Fe2O3/g-C3N4 film shows impressive stability, retaining more than 90% of the initial current over 12 h operating time. The excellent stability of the heterojunction photoanode is achieved due to the unique nanoflake structure of α-Fe2O3 induced by AACVD. This nanostructure promotes good adhesion with the g-C3N4 particles, as the particles tend to be trapped within the α-Fe2O3 valleys and eventually create strong and large interfacial contacts. This leads to improved separation of charge carriers at the α-Fe2O3/g-C3N4 interface and suppression of charge recombination in the photoanode, which are confirmed by the transient decay time, charge transfer efficiency and electrochemical impedance analysis. Our findings demonstrate the importance of nanostructure engineering for developing heterojunction structures with efficient charge transfer dynamics.
In this work, fibrous silica-titania (FST) was successfully prepared by the microemulsion method prior to the addition of three types of carbonaceous materials: graphitic-carbon nitride, g-C3N4 (CN), graphene nanoplatelets (GN), and multi-wall carbon nanotubes, MWCNT (CNT), via a solid-state microwave irradiation technique. The catalysts were characterized using XRD, FESEM, TEM, FTIR, UV-Vis DRS, N2 adsorption-desorption, XPS and ESR, while their photoactivity was examined on the degradation of toxic 2-chlorophenol (2-CP). The result demonstrated that the initial reaction rate was in the following order: CNFST (5.1 × 10-3 mM min-1) > GNFST (2.5 × 10-3 mM min-1) > CNTFST (2.3 × 10-3 mM min-1). The best performance was due to the polymeric structure of g-C3N4 with a good dispersion of C and N on the surface FST. This dispersion contributed towards an appropriate quantity of defect sites, as a consequence of the greater interaction between g-C3N4 and the FST support, that led to narrowed of band gap energy (2.98 eV to 2.10 eV). The effect of scavenger and ESR studies confirmed that the photodegradation over CNFST occurred via a Z-scheme mechanism. It is noteworthy that the addition of green carbonaceous materials on the FST markedly enhanced the photodegradation of toxic 2-CP.
Herein, we performed an encyclopedic analysis on the photoelectrocatalytic hydrogen production of BiVO4/g-C3N4 decorated with reduced graphene oxide (RGO) or graphene quantum dots (GQDs). The differences between RGO and GQDs as an electron mediator was revealed for the first time in the perspective of theoretical DFT analysis and experimental validation. It was found that the incorporation of GQDs as an electron mediator promotes better photoelectrocatalytic hydrogen performance in comparison to the RGO. The addition of GQD can significantly improve the activity by 25.2 and 75.7% in comparison to the BiVO4/RGO/g-C3N4 and binary composite samples, respectively. Correspondingly, the BiVO4/GQD/g-C3N4 attained the highest photocurrent density of 19.2 mA/cm2 with an ABPE of 0.57% without the presence of any sacrificial reagents. This enhancement is stemming from the low photocharge carrier transfer resistance which was further verified via DFT study. The DFT analysis revealed that the BiVO4/GQD/g-C3N4 sample shared their electronic cloud density through orbital hybridization while the BiVO4/RGO/g-C3N4 sample show less mutual sharing. Additionally, the charge redistribution of the GQDs-composite at the heterostructure interface articulates a more stable and stronger heterojunction than the RGO-composite. Notably, this study provides new insights on the effect of different carbonaceous materials (RGO and GQDs) which are often used as an electron mediator to enhance photocatalytic activity.
Catalysts prepared from industrial wastes rich in Fe, Ca, Si, and Al were used in catalytic upgrading of pyrolysis vapour derived from durian shell and their effect on product yield and properties were compared. With same silica-to-alumina ratio, catalyst prepared from oil palm ash (AS-OPA) with lower Fe and Ca contents gave higher liquid yield (8.32 wt%) with alcohols (28.90%), hydrocarbons (46.00%), and nitrogen-containing compounds (21.46%) while catalyst prepared from electric arc furnace slag (AS-EAF) with higher Fe and Ca contents produced lower liquid yield (50.21 wt%) with high amount of esters (25.80%) and hydrocarbons (72.82%). The presence of AS-OPA and AS-EAF catalysts enhanced deoxygenation degree of bio-oil to 81.13% and 85.49%, respectively. The catalytic performance of AS-EAF at different temperatures (400-600 °C) and AS-EAF/durian shell ratios (1:30, 2:30, 3:30) was investigated. Increasing catalytic temperature enhanced production of bio-oil, reduced oxygenates and enhanced formation of esters. The liquid yield and yield of esters decreased with increasing catalyst loading. Hydrocarbons (mainly neopentane) were the major chemical compounds found in bio-oil produced over AS-EAF. Besides that, AS-EAF showed good deoxygenation performance with highest selectivity of hydrocarbons at 500 °C and AS-EAF/durian shell ratio of 2:30. Catalytic fast pyrolysis of durian shell using waste-derived catalysts is an effective waste management strategy as the bio-oil produced can be a potential alternative source of energy or chemical feedstocks.
Growing concerns of water pollution by dye pollutants from the textile industry has led to vast research interest to find green solutions to address this issue. In recent years, heterogeneous photocatalysis has harvested tremendous attention from researchers due to its powerful potential applications in tackling many important energy and environmental challenges at a global level. To fully utilise the broad spectrum of solar energy has been a common aim in the photocatalyst industry. This study focuses on the development of an efficient, highly thermal and chemical stable, environmentally friendly and metal-free graphitic carbon nitride (g-C3N4) to overcome the problem of fast charge recombination which hinders photocatalytic performances. Nitrogen-doped carbon quantum dots (NCQDs) known for its high electronic and optical functionality properties is believed to achieve photocatalytic enhancement by efficient charge separation through forming heterogeneous interfaces. Hence, the current work focuses on the hybridisation of NCQDs and g-C3N4 to produce a composite photocatalyst for methylene blue (MB) degradation under LED light irradiation. The optimal hybridisation method and the mass loading required for maximum attainable MB degradation were systematically investigated. The optimum photocatalyst, 1 wt% NCQD/g-C3N4 composite was shown to exhibit a 2.6-fold increase in photocatalytic activity over bare g-C3N4. Moreover, the optimum sample displayed excellent stability and durability after three consecutive degradation cycles, retaining 91.2% of its original efficiency. Scavenging tests were also performed where reactive species, photon-hole (h+) was identified as the primary active species initiating the pollutant degradation mechanism. The findings of this study successfully shed light on the hybridisation methods of NCQDs which improve existing g-C3N4 photocatalyst systems for environmental remediation by utilising solar energy.
A bacterium capable of biodegrading surfactant sodium dodecyl sulphate (SDS) was isolated from Antarctic soil. The isolate was tentatively identified as Pseudomonas sp. strain DRY15 based on carbon utilization profiles using Biolog GN plates and partial 16S rDNA molecular phylogeny. Growth characteristic studies showed that the bacterium grew optimally at 10 degrees C, 7.25 pH, 1 g l(-1) SDS as a sole carbon source and 2 g l(-1) ammonium sulphate as nitrogen source. Growth was completely inhibited at 5 g l(-1) SDS. At a tolerable initial concentration of 2 g l(-1), approximately 90% of SDS was degraded after an incubation period of eight days. The best growth kinetic model to fit experimental data was the Haldane model of substrate inhibition with a correlation coefficient value of 0.97. The maximum growth rate was 0.372 hr(-1) while the saturation constant or half velocity constant (Ks) and inhibition constant (Ki), were 0.094% and 11.212 % SDS, respectively. Other detergent tested as carbon sources at 1 g l(-1) was Tergitol NP9, Tergitol 15S9, Witconol 2301 (methyl oleate), sodium dodecylbenzene sulfonate (SDBS), benzethonium chloride, and benzalkonium chloride showed Tergitol NP9, Tergitol 15S9, Witconol 2301 and the anionic SDBS supported growth with the highest growth exhibited by SDBS.
In this study, the potential of a pilot-scale granular activated carbon sequencing batch biofilm reactor (GAC-SBBR) for removing chemical oxygen demand (COD), ammoniacal nitrogen (NH3-N) and 2,4-dichlorophenol (2,4-DCP) from recycled paper wastewater was assessed. For this purpose, the response surface methodology (RSM) was employed, using a central composite face-centred design (CCFD), to optimise three of the most important operating variables, i.e., hydraulic retention time (HRT), aeration rate (AR) and influent feed concentration (IFC), in the pilot-scale GAC-SBBR process for recycled paper wastewater treatment. Quadratic models were developed for the response variables, i.e., COD, NH3-N and 2,4-DCP removal, based on the high value (>0.9) of the coefficient of determination (R(2)) obtained from the analysis of variance (ANOVA). The optimal conditions were established at 750 mg COD/L IFC, 3.2 m(3)/min AR and 1 day HRT, corresponding to predicted COD, NH3-N and 2,4-DCP removal percentages of 94.8, 100 and 80.9%, respectively.
Since landfilling is the common method of waste disposal in Malaysia, river water is greatly exposed to the risk of contamination from leachate unless proper leachate management is carried out. In this study, leachates from three different types of landfills, namely active uncontrolled, active controlled and closed controlled, were characterized, and their relationships with river water chemistry were examined monthly for a year. The influence of leachate on river water chemistry from each type of landfill depended on many factors, including the presence of a leachate control mechanism, leachate characteristics, precipitation, surface runoff and the applied treatment. The impact of leachate from an active uncontrolled landfill was the highest, as the organic content, NH(4)(+)-N, Cd and Mn levels appeared high in the river. At the same time, influences of leachate were also observed from both types of controlled landfills in the form of inorganic nitrogen (NH(4)(+)-N, NO(3)(-)-N and NO(2)(-)-N) and heavy metals (Fe, Cr, Ni and Mn). Improper treatment practice led to high levels of some contaminants in the stream near the closed controlled landfill. Meanwhile, the active controlled landfill, which was located near the coastline, was exposed to the risk of contamination resulting from the pyrite oxidation of the surrounding area.
The objective of this study is to evaluate the performance of sequencing batch biofilm reactors (SBBRs) and sequencing batch reactor (SBR) in the simultaneous removal of p-nitrophenol (PNP) and ammoniacal nitrogen. SBBRs involved the use of polyurethane sponge cubes and polyethylene rings, respectively, as carrier materials. The results demonstrate that complete removal of PNP was achievable for the SBR and SBBRs up to the PNP concentration of 350 mg/l (loading rate of 0.368 kg/m3 d). At this loading rate, the average ammoniacal nitrogen removal efficiency for the SBR and SBBR (with polyethylene rings) was reduced to 86% and 96%, respectively. However, the SBBR (with polyurethane sponge cubes) still managed to achieve an almost 100% ammoniacal nitrogen removal. Based on the results, the performance of the SBBRs was better than that of SBR in PNP and ammoniacal nitrogen removal. The results of the gas chromatography mass spectroscopy, high-performance liquid chromatography and ultraviolet-visible analyses indicate that complete mineralization of PNP was achieved in all of the reactors.
Aquaculture activities in developing countries have raised deep concern about nutrient pollution, especially excess phosphorus in wastewater, which leads to eutrophication. NF, NF90, NF450 and XLE membranes were studied to forecast the potential of nanofiltration and low pressure reverse osmosis in the removal of phosphorus from aquaculture wastewater. Cross-sectional morphology, water contact angle, water permeability and zeta potential of these membranes were first examined. Membrane with higher porosity and greater hydrophilicity showed better permeability. Membrane samples also commonly exhibited high zeta potential value in the polyphosphate-rich solution. All the selected membranes removed more than 90% of polyphosphate from the concentrated feed (75 mg/L) at 12 bar. The separation performance of XLE membrane was well maintained at 94.6% even at low pressure. At low feed concentration, more than 70.0% of phosphorus rejection was achieved using XLE membrane. The formation of intermolecular bonds between polyphosphate and the acquired membranes probably had improved the removal of polyphosphate at high feed concentration. XLE membrane was further tested and its rejection of polyphosphate reduced with the decline of pH and the addition of ammonium nitrate.