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.
The photocatalytic conversion of CO2 to energy-rich CH4 solar fuel is an ideal strategy for future energy generation as it can resolve global warming and the imminent energy crisis concurrently. However, the efficiency of this technology is unavoidably hampered by the ineffective generation and utilization of photoinduced charge carriers. In this contribution, we report a facile in situ topotactic transformation approach where {001}-faceted BiOBr nanosheets (BOB-NS) were employed as the starting material for the formation of single-crystalline ultrathin Bi2WO6 nanosheets (BWO-NS). The as-obtained BWO-NS not only preserved the advantageous properties of the 2D nanostructure and predominantly exposed {001} facets but also possessed enlarged specific surface areas as a result of sample thickness reduction. As opposed to the commonly observed bandgap broadening when the particle sizes decrease to an ultrathin nanoscale owing to the quantum size effect, the developed BWO-NS exhibited a fascinating bandgap narrowing compared to those of pristine Bi2WO6 nanoplates (BWO-P) synthesized from a conventional one-step hydrothermal approach. Moreover, the electronic band positions of BWO-NS were modulated as a result of ion exchange for the reconstruction of the energy bands, where BWO-NS demonstrated significant upshifting of CB and VB levels; these are beneficial for photocatalytic reduction applications. This propitious design of BWO-NS through integrating the merits of BOB-NS caused BWO-NS to exhibit substantial 2.6 and 9.3-fold enhancements of CH4 production over BOB-NS and BWO-P, respectively.
ZnIn2S4 (ZIS) is an efficient photocatalyst for solar hydrogen (H2) generation from water splitting owing to its suitable band gap, excellent photocatalytic behaviour and high stability. Nevertheless, modifications are still necessary to further enhance the photocatalytic performance of ZIS for practical applications. This has led to our interest in exploring phosphorus doping on ZIS for photocatalytic water splitting, which has not been studied till date. Herein, phosphorus-doped ZnIn2S4 (P-ZIS) was modelled via Density Functional Theory to investigate the effects of doping phosphorus on the structural and electronics properties of ZIS as well as its performance toward photocatalytic water splitting. This work revealed that the replacement of S3 atom by substitutional phosphorus gave rise to the most stable P-ZIS structure. In addition, P-ZIS was observed to experience a reduction in band gap energy, an upshift of valence band maximum (VBM), an increase in electron density near VBM and a reduction of H* adsorption-desorption barrier, all of which are essential for the enhancement of the hydrogen evolution reaction. In overall, detailed theoretical analysis carried out in this work could provide critical insights towards the development of P-ZIS-based photocatalysts for efficient H2 generation via solar water splitting.
This study, for the first time, focused on the fabrication of nonporous polyurea thin films (~200 microns) using the electrospinning method as a novel approach for coating applications. Multi-walled carbon nanotubes (MWCNTs) and hydrophilic-fumed nanosilica (HFNS) were added separately into electrospun polyurea films as nano-reinforcing fillers for the enhancement of properties. Neat polyurea films demonstrated a tensile strength of 14 MPa with an elongation of 360%. At a loading of 0.2% of MWCNTs, the highest tensile strength of 21 MPa and elongation of 402% were obtained, while the water contact angle remained almost unchanged (89°). Surface morphology analysis indicated that the production of polyurea fibers during electrospinning bonded together upon curing, leading to a nonporous film. Neat polyurea exhibited high thermal resistance with a degradation temperature of 380 °C. Upon reinforcement with 0.2% of MWCNTs and 0.4% of HFNS, it increased by ~7 °C. The storage modulus increased by 42 MPa with the addition of 0.2% of MWCNTs, implying a superior viscoelasticity of polyurea nanocomposite films. The results were benchmarked with anti-corrosive polymer coatings from the literature, revealing that the production of nonporous polyurea coatings with robust strength, elasticity, and thermal properties was achieved. Electrospun polyurea coatings are promising candidates as flexible anti-corrosive coatings for heat exchanges and electrical wires.
As a fascinating conjugated polymer, graphitic carbon nitride (g-C3N4) has become a new research hotspot and drawn broad interdisciplinary attention as a metal-free and visible-light-responsive photocatalyst in the arena of solar energy conversion and environmental remediation. This is due to its appealing electronic band structure, high physicochemical stability, and "earth-abundant" nature. This critical review summarizes a panorama of the latest progress related to the design and construction of pristine g-C3N4 and g-C3N4-based nanocomposites, including (1) nanoarchitecture design of bare g-C3N4, such as hard and soft templating approaches, supramolecular preorganization assembly, exfoliation, and template-free synthesis routes, (2) functionalization of g-C3N4 at an atomic level (elemental doping) and molecular level (copolymerization), and (3) modification of g-C3N4 with well-matched energy levels of another semiconductor or a metal as a cocatalyst to form heterojunction nanostructures. The construction and characteristics of each classification of the heterojunction system will be critically reviewed, namely metal-g-C3N4, semiconductor-g-C3N4, isotype g-C3N4/g-C3N4, graphitic carbon-g-C3N4, conducting polymer-g-C3N4, sensitizer-g-C3N4, and multicomponent heterojunctions. The band structures, electronic properties, optical absorption, and interfacial charge transfer of g-C3N4-based heterostructured nanohybrids will also be theoretically discussed based on the first-principles density functional theory (DFT) calculations to provide insightful outlooks on the charge carrier dynamics. Apart from that, the advancement of the versatile photoredox applications toward artificial photosynthesis (water splitting and photofixation of CO2), environmental decontamination, and bacteria disinfection will be presented in detail. Last but not least, this comprehensive review will conclude with a summary and some invigorating perspectives on the challenges and future directions at the forefront of this research platform. It is anticipated that this review can stimulate a new research doorway to facilitate the next generation of g-C3N4-based photocatalysts with ameliorated performances by harnessing the outstanding structural, electronic, and optical properties for the development of a sustainable future without environmental detriment.
Photocatalysis is a perennial solution that promises to resolve deep-rooted challenges related to environmental pollution and energy deficit through harvesting the inexhaustible and renewable solar energy. To date, a cornucopia of photocatalytic materials has been investigated with the research wave presently steered by the development of novel, affordable, and effective metal-free semiconductors with fascinating physicochemical and semiconducting characteristics. Coincidentally, the recently emerged red phosphorus (RP) semiconductor finds itself fitting perfectly into this category ascribed to its earth abundant, low-cost, and metal-free nature. More notably, the renowned red allotrope of the phosphorus family is spectacularly bestowed with strengthened optical absorption features, propitious electronic band configuration, and ease of functionalization and modification as well as high stability. Comprehensively detailing RP's roles and implications in photocatalysis, this review article will first include information on different RP allotropes and their chemical structures, followed by the meticulous scrutiny of their physicochemical and semiconducting properties such as electronic band structure, optical absorption features, and charge carrier dynamics. Besides that, state-of-the-art synthesis strategies for developing various RP allotropes and RP-based photocatalytic systems will also be outlined. In addition, modification or functionalization of RP with other semiconductors for promoting effective photocatalytic applications will be discussed to assess its versatility and feasibility as a high-performing photocatalytic system. Lastly, the challenges facing RP photocatalysts and future research directions will be included to propel the feasible development of RP-based systems with considerably augmented photocatalytic efficiency. This review article aspires to facilitate the rational development of multifunctional RP-based photocatalytic systems by widening the cognizance of rational engineering as well as to fine-tune the electronic, optical, and charge carrier properties of RP.
Photocatalytic CO2 reduction over the UV-Vis-NIR broad spectrum was realized for the first time. The presence of surface oxygen vacancy defects on Bi2WO6 resulted in significant photocatalytic enhancement over the pristine counterpart under UV and visible light irradiation. Meanwhile, the photocatalytic responsiveness of Bi2WO6-OV was successfully extended to the NIR region.
Heterojunction photocatalysts have shown their immense capability in enhancing photogenerated charge carrier separation. Yet, the intrinsic scarcity of active sites in semiconductor components of heterojunction photocatalysts limits their potential for photocatalysis being used in practical applications. Herein, we employ a non-noble metal cocatalyst (i.e., NiS) for modulating a S-scheme heterojunction photocatalyst consisting of Cd3(C3N3S3)2 (CdCNS) and CdS. It is revealed that the formation of the CdCNS/CdS S-scheme heterojunction can enable optimal photogenerated charge carrier utilization efficiency and optimized redox capability. More importantly, the meticulous loading of NiS can play multiple roles in enhancing the photocatalytic performance of the CdCNS/CdS photocatalyst, including endowing it with abundant surface-active sites and acting as a photogenerated electron acceptor. As a result, the optimized NiS-loaded CdCNS/CdS attains an excellent hydrogen production rate of 38.17 mmol g-1 h-1, to reach a quantum efficiency of 29.02% at 420 nm. The results reported in this work provide an interesting insight into the important roles of surface-active site modulation in optimizing photocatalytic performances.
Switching to renewable, carbon-neutral sources of energy is urgent and critical for climate change mitigation. Despite how hydrogen production by electrolyzing water can enable renewable energy storage, current technologies unfortunately require rare and expensive platinum group metal electrocatalysts, which limit their economic viability. Transition metal dichalcogenides (TMDs) are low-cost, earth-abundant materials that possess the potential to replace platinum as the hydrogen evolution catalyst for water electrolysis, but so far, pristine TMDs are plagued by poor catalytic performances. Defect engineering is an attractive approach to enhance the catalytic efficiency of TMDs and is not subjected to the limitations of other approaches like phase engineering and surface structure engineering. In this minireview, we discuss the recent progress made in defect-engineered TMDs as efficient, robust, and low-cost catalysts for water splitting. The roles of chalcogen atomic defects in engineering TMDs for improvements to the hydrogen evolution reaction (HER) are summarized. Finally, we highlight our perspectives on the challenges and opportunities of defect engineering in TMDs for electrocatalytic water splitting. We hope to provide inspirations for designing the state-of-the-art catalysts for future breakthroughs in the electrocatalytic HER.
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.
Dye wastewater has raised a prevalent environmental concern due to its ability to prevent the penetration of sunlight through water, thereby causing a disruption to the aquatic ecosystem. Carbon quantum dots (CQDs) are particularly sought after for their highly tailorable photoelectrochemical and optical properties. Simultaneously, graphitic carbon nitride (g-C3N4) has gained widespread attention due to its suitable band gap energy as well as excellent chemical and thermal stabilities. Herein, a novel boron-doped CQD (BCQD)-hybridized g-C3N4 homojunction (CN) nanocomposite was fabricated via a facile hydrothermal route. The optimal photocatalyst sample, 1-BCQD/CN (with a 1:3 mass ratio of boron to CQD) accomplished a Rhodamine B (RhB, 10 mg/L) degradation efficiency of 96.8% within 4 h under an 18 W LED light irradiation. The kinetic rate constant of 1.39 × 10-2 min-1 achieved by the optimum sample was found to be 3.6- and 2.8-folds higher than that of pristine CN and un-doped CQD/CN, respectively. The surface morphology, crystalline structure, chemical composition and optical properties of photocatalyst samples were characterized via TEM, FESEM-EDX, XRD, FTIR, UV-Vis DRS and FL spectrometer. Based on the scavenging tests, it was revealed that the photogenerated holes (h+), superoxide anions (∙O2-) and hydroxyl radicals (∙OH) were the primary reactive species responsible for the photodegradation process. Overall, the highly efficient 1-BCQD/CN composite with excellent photocatalytic activity could provide a cost-effective and robust means to address the increasing concerns over global environmental pollution.
As the world decides on the next giant step for the renewable energy revolution, scientists have begun to reinforce their headlong dives into the exploitation of solar energy. Hitherto, numerous attempts are made to imitate the natural photosynthesis of plants by converting solar energy into chemical fuels which resembles the "Z-scheme" process. A recreation of this system is witnessed in artificial Z-scheme photocatalytic water splitting to generate hydrogen (H2). This work outlines the recent significant implication of the Z-scheme system in photocatalytic water splitting, particularly in the role of electron mediator and the key factors that improve the photocatalytic performance. The Review begins with the fundamental rationales in Z-scheme water splitting, followed by a survey on the development roadmap of three different generations of Z-scheme system: 1) PS-A/D-PS (first generation), 2) PS-C-PS (second generation), and 3) PS-PS (third generation). Focus is also placed on the scaling up of the "leaf-to-tree" challenge of Z-scheme water splitting system, which is also known as Z-scheme photocatalyst sheet. A detailed investigation of the Z-scheme system for achieving H2 evolution from past to present accompanied with in-depth discussion on the key challenges in the area of Z-scheme photocatalytic water splitting are provided.
Observation of visible light trapping in zinc oxide (ZnO) nanorods (NRs) correlated to the optical and photoelectrochemical properties is reported. In this study, ZnO NR diameter and c-axis length respond primarily at two different regions, UV and visible light, respectively. ZnO NR diameter exhibits UV absorption where large ZnO NR diameter area increases light absorption ability leading to high efficient electron-hole pair separation. On the other hand, ZnO NR c-axis length has a dominant effect in visible light resulting from a multiphoton absorption mechanism due to light reflection and trapping behavior in the free space between adjacent ZnO NRs. Furthermore, oxygen vacancies and defects in ZnO NRs are associated with the broad visible emission band of different energy levels also highlighting the possibility of the multiphoton absorption mechanism. It is demonstrated that the minimum average of ZnO NR c-axis length must satisfy the linear regression model of Z p,min = 6.31d to initiate the multiphoton absorption mechanism under visible light. This work indicates the broadening of absorption spectrum from UV to visible light region by incorporating a controllable diameter and c-axis length on vertically aligned ZnO NRs, which is important in optimizing the design and functionality of electronic devices based on light absorption mechanism.
Establishing an effective metal-free photocatalyst for sustainable applications remains a huge challenge. Herein, we developed ultrathin oxygen-doped g-C3N4 nanosheets with carbon defects (OCvN) photocatalyst via a facile gas bubble template-assisted thermal copolymerization method. A series of OCvN with different dopant amounts ranging from 0 to 10% were synthesized and used as photocatalysts under illumination of low-power (2 × 18 W, 0.18 mW/cm2) and commercially available energy-saving light bulbs. Upon testing for photocatalytic Escherichia coli inactivation, the best-performing sample, OCvN-3, demonstrated an astonishing disinfection activity of over 7-log reduction after 3 h of illumination, boasting an 18-fold improvement in its antibacterial activity compared to that of pristine g-C3N4. The enhanced performance was attributed to the synergistic effects of increased surface area, extended visible light harvesting, improved electronic conductivity, and ultralow resistance to charge transfer. This study successfully introduced a green photocatalyst that demonstrates the most effective disinfection performance ever recorded among metal-free g-C3N4 materials. Its disinfection capabilities are comparable to those of metal-based photocatalysts when they are exposed to low-power light.
Engineering an efficient semiconductor to sustainably produce green hydrogen via solar-driven water splitting is one of the cutting-edge strategies for carbon-neutral energy ecosystem. Herein, a superhydrophilic green hollow ZnIn2S4 (gZIS) was fabricated to realize unassisted photocatalytic overall water splitting. The hollow hierarchical framework benefits exposure of intrinsically active facets and activates inert basal planes. The superhydrophilic nature of gZIS promotes intense surface water molecule interactions. The presence of vacancies within gZIS facilitates photon energy utilization and charge transfer. Systematic theoretical computations signify the defect-induced charge redistribution of gZIS enhancing water activation and reducing surface kinetic barriers. Ultimately, the gZIS could drive photocatalytic pure water splitting by retaining close-to-unity stability for a full daytime reaction with performance comparable to other complex sulfide-based materials. This work reports a self-activated, single-component cocatalyst-free gZIS with great exploration value, potentially providing a state-of-the-art design and innovative aperture for efficient solar-driven hydrogen production to achieve carbon-neutrality.
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.
The ability of band offsets at multiferroic/metal and multiferroic/electrolyte interfaces in controlling charge transfer and thus altering the photoactivity performance has sparked significant attention in solar energy conversion applications. Here, we demonstrate that the band offsets of the two interfaces play the key role in determining charge transport direction in a downward self-polarized BFO film. Electrons tend to move to BFO/electrolyte interface for water reduction. Our experimental and first-principle calculations reveal that the presence of neodymium (Nd) dopants in BFO enhances the photoelectrochemical performance by reduction of the local electron-hole pair recombination sites and modulation of the band gap to improve the visible light absorption. This opens a promising route to the heterostructure design by modulating the band gap to promote efficient charge transfer.