Construction of heterostructured g-C3N4@TiATA/Pt composites for efficacious photocatalytic hydrogen evolution

Construction of heterostructured photocatalysts is a feasible method for improving hydrogen production from water splitting because of its good charge transport efficiency. Herein, we coupled the Ti-MOFs (TiATA) with metal-free graphitic carbon nitride (g-C₃N₄) to synthesize composites, g-C₃N₄@TiATA, in which a heterostructure was formed between g-C₃N₄ and TiATA. The establishment of heterojunctions not only broadens the light absorption range of g-C₃N₄@TiATA (490 nm) by contrast with g-C₃N₄ (456 nm), but also greatly accelerates charge migration. Photocatalytic studies present that the construction of heterostructure steering the charges flow from g-C₃N₄ to TiATA and then delivery to the cocatalyst of Pt nanoparticles, exhibiting an impressively photocatalytic hydrogen production rate (265.8 μmol·h⁻¹) in assistance of 300 W Xenon lamp, which is about 3.4 times as much as g-C₃N₄/Pt.     

Synthesis and photo-catalytic activity of porous g-C3N4: Promotion effect of nitrogen vacancy in H2 evolution and pollutant degradation reactions

Different density nitrogen vacancy modified g-C₃N₄ photocatalysts were successfully prepared, and investigated their photocatalytic performance for H₂ evolution and pollutant degradation. In this system, the increase of nitrogen vacancy density could enable the conduction band position of resultant g-C₃N₄ to negative shift compared to previous g-C₃N₄. Meanwhile, various positive factors were also introduced in this system, such as larger surface areas, the improvement of light response capacity, effective separation of photogenerated charge, resulting in resultant g-C₃N₄ photocatalysts exhibiting evident improvement of photocatalytic performance for H₂ evolution and pollutant degradation. Obviously, this work provides physico-chemical insights for the nature of the promotion effect of nitrogen vacancies.     

A facile one-step strategy to construct 0D/2D SnO2/g-C3N4 heterojunction photocatalyst for high-efficiency hydrogen production performance from water splitting

Fabricating 0D/2D heterojunctions is considered to be an efficient mean to improve the photocatalytic activity of g-C₃N₄, whereas their applications are usually restricted by complex preparation process. Here, the 0D/2D SnO₂/g-C₃N₄ heterojunction photocatalyst is prepared by a simple one-step polymerization strategy, in which SnO₂ nanodots in-situ grow on the surface of g-C₃N₄ nanosheets. It shows the outstanding photocatalytic H₂ production activity relative to g-C₃N₄ under the visible light, which is due to the formation of 0D/2D heterojunction significantly contributing to the separation of photogenerated charge carriers. In particular, the H₂ production rate over the optimal SnO₂/g–C₃N₄–1 sample is 1389.2 μmol h⁻¹ g⁻¹, which is 6.06 times higher than that of g-C₃N₄ (230.8 μmol h⁻¹ g⁻¹). Meanwhile, the AQE value of H₂ production over the SnO₂/g–C₃N₄–1 sample reaches up to a maximum of 4.5% at 420 nm. This work develops a simple approach to design and fabricate g–C₃N₄–based 0D/2D heterojunctions for the high-efficiency H₂ production from water splitting.     

A visible-light-driven heterojunction for enhanced photocatalytic water splitting over Ta2O5 modified g-C3N4 photocatalyst

The photocatalytic water splitting for generation of clean hydrogen energy has received increasingly attention in the field of photocatalysis. In this study, the Ta₂O₅/g-C₃N₄ heterojunctions were successfully fabricated via a simple one-step heating strategy. The photocatalytic activity of as-prepared photocatalysts were evaluated by water splitting for hydrogen evolution under visible-light irradiation (λ > 420 nm). Compared to the pristine g-C₃N₄, the obtained heterojunctions exhibited remarkably improved hydrogen production performance. It was found that the 7.5%TO/CN heterojunction presented the best photocatalytic hydrogen evolution efficiency, which was about 4.2 times higher than that of pure g-C₃N₄. Moreover, the 7.5%TO/CN sample also displayed excellent photochemical stability even after 20 h photocatalytic test. By further experimental study, the enhanced photocatalytic activity is mainly attributed to the significantly improve the interfacial charge separation in the heterojunction between g-C₃N₄ and Ta₂O₅. This work provides a facile approach to design g-C₃N₄-based photocatalyst and develops an efficient visible-light-driven heterojunction for application in solar energy conversion.     

Surface defect and rational design of TiO2−x nanobelts/ g-C3N4 nanosheets/ CdS quantum dots hierarchical structure for enhanced visible-light-driven photocatalysis

TiO_2-x/g-C₃N₄/CdS ternary heterojunctions are fabricated through thermal polymerization-chemical bath deposition combined with in-situ solid-state chemical reduction approach. The prepared materials are characterized by X-ray diffraction, Fourier transform infrared spectra, scanning electron microscopy, transmission electron microscopy, nitrogen adsorption-desorption, and X-ray photoelectron spectroscopy. The results show that the ternary heterojunctions are formed successfully and CdS quantum dots (QDs) and TiO₂ are anchored on surface of g-C₃N₄ nanosheets simultaneously. The visible-light-driven photocatalytic degradation ratio of Bisphenol A and hydrogen production rate are up to 95% and ∼254.8 μmol h⁻¹, respectively, which are several times higher than that of pristine TiO₂. The excellent visible-light-driven photocatalytic activity can be ascribed to the synergistic effect of TiO_2−x, g-C₃N₄ and CdS QDs which extend the photoresponse to visible light region and favor the spatial separation of photogenerated charge carriers.     

Mesoporous g-C3N4/Zn–Ti LDH laminated van der Waals heterojunction nanosheets as remarkable visible-light-driven photocatalysts

Mesoporous g-C₃N₄/Zn–Ti layered double hydroxide (LDH)-laminated van der Waals heterojunction nanosheets were prepared by a facile one-step in situ hydrothermal method. Due to the strong electrostatic interactions between the positively charged Zn–Ti LDH and negatively charged g-C₃N₄ nanocrystal, a laminated van der Waals heterostructure was successfully formed between Zn–Ti LDH and g-C₃N₄. The mesoporous g-C₃N₄/Zn–Ti LDH-laminated van der Waals heterojunction, which had a narrow bandgap of 2.41 eV extended the photoresponse to the visible light region. The obtained heterojunctions showed excellent visible-light-driven photocatalytic performance for the complete removal of ceftriaxone sodium (up to ∼97%) and a high hydrogen production rate (∼161.87 μmol h⁻¹ g⁻¹). This was mainly attributed to the formation of the laminated van der Waals heterojunctions, which favoured charge separation and the absorption of visible light, and the mesoporous structure, which provided more surface active sites. This facile strategy for preparing mesoporous g-C₃N₄/Zn–Ti LDH-laminated van der Waals heterojunctions offers new insights for the fabrication of high-performance van der Waals heterojunction photocatalytic materials.     

Rationally designed ternary CdSe/WS2/g-C3N4 hybrid photocatalysts with significantly enhanced hydrogen evolution activity and mechanism insight

Excellent light harvest, efficient charge separation and sufficiently exposed surface active sites are crucial for a given photocatalyst to obtain excellent photocatalytic performances. The construction of two-dimensional/two-dimensional (2D/2D) or zero-dimensional/2D (0D/2D) binary heterojunctions is one of the effective ways to address these crucial issues. Herein, a ternary CdSe/WS₂/g-C₃N₄ composite photocatalyst through decorating WS₂/g-C₃N₄ 2D/2D nanosheets (NSs) with CdSe quantum dots (QDs) was developed to further increase the light harvest and accelerate the separation and migration of photogenerated electron-hole pairs and thus enhance the solar to hydrogen conversion efficiency. As expected, a remarkably enhanced photocatalytic hydrogen evolution rate of 1.29 mmol g⁻¹ h⁻¹ was obtained for such a specially designed CdSe/WS₂/g-C₃N₄ composite photocatalyst, which was about 3.0, 1.7 and 1.3 times greater than those of the pristine g-C₃N₄ NSs (0.43 mmol g⁻¹ h⁻¹), WS₂/g-C₃N₄ 2D/2D NSs (0.74 mmol g⁻¹ h⁻¹) and CdSe/g-C₃N₄ 0D/2D composites (0.96 mmol g⁻¹ h⁻¹), respectively. The superior photocatalytic performance of the prepared ternary CdSe/WS₂/g-C₃N₄ composite could be mainly attributed to the effective charge separation and migration as well as the suppressed photogenerated charge recombination induced by the constructed type-II/type-II heterojunction at the interfaces between g-C₃N₄ NSs, CdSe QDs and WS₂ NSs. Thus, the developed 0D/2D/2D ternary type-II/type-II heterojunction in this work opens up a new insight in designing novel heterogeneous photocatalysts for highly efficient photocatalytic hydrogen evolution.     

Controlled photoinduced electron transfer from g-C3N4 to CuCdCe-LDH for efficient visible light hydrogen evolution reaction

Ample visible-light response and efficient charge transfers in semiconductor heterojunction are still enslaved to the limited photocatalytic water splitting. In most cases, the rational design of hybrid composites tune in atomic level interaction led to remarkable stability and superior activity. Here, this work is a systematic investigation of metal ion substitution in the LDH and LDH/g-C₃N₄ hybrid composites for hydrogen evolution reaction (HER) under visible light. The construction of heterostructure not only facilitates the charge separation and transfer owing to the formed heterojunction through band gap engineering and tunable optical properties which are inherited from morphology of as grown CuCdCe-LDH over the exfoliated g-C₃N₄ but also provides plenty of surface active sites due the increased surface area photostability. The CuCdCe-LDH/g-C₃N₄ exhibits superior HER rate of 3.5 mmolg^?1h^?1 with AQY of 5.78% over their binary counterparts. The density functional theory calculations also suggest that the HER activity of CuCdCe-LDH is substantially enhanced by coupling with g-C₃N₄ the electrochemical results leading to high photocurrent response. The high photocatalytic activity of the composite was due to efficient photoexcited charge transfer process and the synergistic effect between CuCdCe-LDH and g-C₃N₄. These finding will open scopes for designing inexpensive high performance materials for broad applications of photocatalytic energy conversion.     

Two-dimensional carbon nitride-based composites for photocatalytic hydrogen evolution

Photocatalytic hydrogen evolution plays a critical role in the exploration of the clean and sustainable energy. Owing to its special structure and features, two-dimensional (2D) graphitic carbon nitride (g-C₃N₄) has attracted tremendous attention. However, some deficiencies of pristine g-C₃N₄ inhibit its photocatalytic application, particularly the low quantum efficiency of hydrogen evolution. Therefore, it is valuable to develop 2D new composites based on g-C₃N₄ so that the synergistic effects of the two original materials can be achieved. This article attempts to summarize the modification strategies of 2D g-C₃N₄-based composites, including the construction of heterojunctions, morphology control, doping method, surface modification and co-catalyst loading. The application and progress in photocatalytic hydrogen evolution are also highlighted. The limitations are taken into account to provide further information for the improvement in the quantum efficiency of hydrogen by 2D g-C₃N₄-based composites.     

Hierarchical TiO2 spheroids decorated g-C3N4 nanocomposite for solar driven hydrogen production and water depollution

A novel hierarchical TiO₂ spheroids embellished with g-C₃N₄ nanosheets has been successfully developed via thermal condensation process for efficient solar-driven hydrogen evolution and water depollution photocatalyst. The photocatalytic behaviour of the as-prepared nanocomposite is experimented in water splitting and organic pollutant degradation under solar light irradiation. The optimal ratio of TiO₂ spheroids with g-C₃N₄ in the nanocomposite was found to be 1:10 and the resulting composite exhibits excellent photocatalytic hydrogen production of about 286 μmol h^?1g^?1, which is a factor of 3.4 and 2.3 times higher than that of pure TiO₂ and g-C₃N₄, respectively. The outstanding photocatalytic performance in this composite could be ascribed as an efficient electron-hole pair's separation and interfacial contact between TiO₂ spheroids with g-C₃N₄ nanosheets in the formed TiO₂/g-C₃N₄ nanocomposite. This work provide new insight for constructing an efficient Z-scheme TiO₂/g-C₃N₄ nanocomposites for solar light photocatlyst towards solar energy conversion, solar fuels and other environmental applications.     

Effect of nonmetal element dopants on photo- and electro-chemistry performance of ultrathin g-C3N4 nanosheets

Increased charge transfer and light absorption as well as large specific surface area are effective ways to improve the catalytic efficiency of photocatalysts. In this paper, barbituric acid, urea and thiourea were separately freeze-dried to form a homogeneous precursor with melamine, followed by thermal polymerization at 750 °C, g-C₃N₄ was doped successfully with C, N and S. Among them, C-doped g-C₃N₄ revealed well photocatalytic hydrogen production which reached to 2.45 mmol g⁻¹ h⁻¹. N-doped g-C₃N₄ exhibited enhanced photocatalytic degradation properties for organic dye (RhB) which is completely degraded within 8 min while the performance S-doped sample is not satisfied. The introduction of C resulted in planarized sample which has a larger specific surface area and provides more active sites. N doping makes the valence band position moving in the direction of high energy. Thus, holes have stronger oxidizing ability. Accordingly, the effect of C and N ratios in g-C₃N₄ photocatalysis was fully discussed for more comprehensive understanding of g-C₃N₄.     

High-efficiency of novel hierarchical 3D macroporous g-C3N4 material on solar-driven photocatalytic water-splitting for hydrogen evolution

The use of multi-pore nanostructured g-C₃N₄ photocatalysts is an efficient approach to separate photogenerated charge carriers and increase visible light photocatalytic performance. Recent progress has yielded nanostructured material through hard templating, which limits potential applications. Integrating the 2D building block into multidimensional porous structures remains a significant challenge in scalable production. Herein, a novel technique based on P407 bubble clusters templating and fixation by freezing is described for the first time to fabricate a 3D opened-up macroporous g-C₃N₄ nanostructures for photocatalytic H₂ evolution. Three-dimensional hierarchical nanostructures provide more contact active sites and synergistically promote the creation of heterogeneous catalytic interfaces. This feature is very useful for understanding the transfer path of photoinduced charges as well as the origins of the high charge separation efficiency in photocatalytic reactions, thus yielding a remarkable visible light-induced H₂ evolution rate of 4213.6 μmol h⁻¹ g⁻¹, which is nearly 5.6 times (716 μmol h⁻¹ g⁻¹) higher than that of lamellar bulk g-C₃N₄. This newly developed approach offers a promising alternative to synthesize broad-spectral response 3D hierarchal g-C₃N₄ nanostructures and can be extended to assemble other functional nanomaterials as building blocks into macroscopic configurations coupled with electronic modulation strategy simultaneously.     

Two dimensional N-doped ZnO-graphitic carbon nitride nanosheets heterojunctions with enhanced photocatalytic hydrogen evolution

The effective separation of photogenerated charge carriers, their transport and interfacial contact is of great significance for excellent performance of semiconductor based photocatalysts. Herein, we report the fabrication of two dimensional (2D) nanosheets heterojunction comprising of N-doped ZnO nanosheets loaded over graphitic carbon nitride (g-C₃N₄) nanosheets for enhanced photocatalytic hydrogen evolution. The prepared 2D-2D heterojunctions with varying amount of g-C₃N₄ nanosheets have been characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and x-ray photoelectron spectroscopy (XPS) techniques. The optimized heterojunction photocatalyst with 30 wt% of g-C₃N₄ nanosheets (NZCN30) exhibit hydrogen evolution rate of 18836 μmol h^?1 g_cat^?1 in presence of Na₂S and Na₂SO₃ as sacrificial agents under simulated solar light irradiation. The enhanced photocatalytic performance of NZCN30 heterojunction has been supported well by photoluminescence and photoelectrochemical investigations, which shows the minimum recombination rate and high photoinduced current density, respectively. In addition, the existence of 2D-2D interfacial contact plays a major role in enhanced H₂ evolution by high face-to-face contact surface area for separation of photogenerated charge carriers in space which facilitate their transfer for H₂ generation. This work paves way for the development of 2D-2D heterojunctions for diverse applications.     

The synergy of thermal exfoliation and phosphorus doping in g-C3N4 for improved photocatalytic H2 generation

Photocatalytic H₂ generation has been believed to be a hopeful technology to deal with the current energy shortage issue. Among multifarious photocatalysts, graphitic carbon nitride (g-C₃N₄) has acquired enormous interests in virtue of its numerous advantages, such as peculiar physicochemical stability, favorable energy band structure and easy preparation. However, the insufficient light response range, low specific surface area, and inferior charge separation efficiency make its photocatalytic activity still unsatisfactory. In this work, the thermal exfoliation method was taken to prepare the thin g-C₃N₄ nanosheets with significantly improved specific surface area, which can afford more reaction sites and shorten the charge migration distance. Moreover, phosphorus (P) doping in g-C₃N₄ nanosheets can greatly expand its light absorption, improve the conductivity and charge-transfer capability. Due to the synergistic effect of these two strategies, the optimal H₂ generation performance of P-doped g-C₃N₄ nanosheets came up to 1146.8 μmol g^?1 h^?1, which improved 15, 2.94 and 2.62 times compared to those of original bulk g-C₃N₄, thermally exfoliated g-C₃N₄ and P-doped bulk g-C₃N₄, respectively. The synergistic effect will inspire the design of other photocatalytic systems to achieve the efficient photocatalytic H₂ generation activity.     

One-pot calcination preparation of graphene/g–C3N4–Co photocatalysts with enhanced visible light photocatalytic activity

Photocatalytic technology for hydrogen evolution from water splitting and pollutant degradation is one of the most sustainable methods. Here, the graphene/g–C₃N₄–Co composite materials have been prepared by one-pot calcination method. The results show that g-C₃N₄ grow on the surface of graphene and form a sandwich structure, meanwhile, the introduction of Co increases the active sites, which promotes the photocatalytic performance. The influences of graphene and Co content on photocatalytic activity were also studied by UV–visible spectrophotometry (DRS), photoluminescence spectroscopy (PL), photocurrent, degradation MB, and hydrogen production. The apparent reaction rate constant k of graphene/g–C₃N₄–Co (3%) is 0.946 h⁻¹, which is 4.90 and 2.18 times faster than g-C₃N₄ and graphene/g-C₃N₄, respectively. And the hydrogen production rate of graphene/g–C₃N₄–Co (3%) (892.3 μmol h⁻¹ g⁻¹) is 3.53 and 1.61 times higher than g-C₃N₄ and graphene/g-C₃N₄, respectively.     

An efficient exfoliation method to obtain graphitic carbon nitride nanosheets with superior visible-light photocatalytic activity

Graphitic carbon nitride (g-C₃N₄) has a promising application in the photocatalytic field due to its large aspect ratio and the favorable band gap energy. Herein, g-C₃N₄ nanosheets (g-C₃N₄ NS) with high photoactivity are obtained with the aid of isopropanol (IPA) in the synthesis process. The introduced IPA causes a more intense oxidation in the exfoliation process and the obtained g-C₃N₄ NS owns its unique properties of a broaden absorption range of visible light, an enlarged surface area and the irregular surface. As a result, the g-C₃N₄ NS has good photocatalytic activity in the degradation of organic pollutant. Moreover, the photocatalytic hydrogen evolution rate of g-C₃N₄ NS is three times as that of g-C₃N₄ NS* synthesized without IPA using the same method.     

In-situ synthesis of ternary heterojunctions via g-C3N4 coupling with noble-metal-free NiS and CdS with efficient visible-light-induced photocatalytic H2 evolution and mechanism insight

The two-dimensional (2D) graphitic carbon nitride (g-C₃N₄) nanosheets based composites are prepared in the form of the NiS/g-C₃N₄, CdS/g-C₃N₄ and CdS/NiS/g-C₃N₄ using a facile and reliable method of chemical deposition. The TEM and HRTEM images demonstrated a spectacular representation of the 2D lamellar microstructure of the g-C₃N₄ with adequately attached CdS and NiS nanoparticles. The changes in crystallinity and the surface elemental valence states of composites with the incorporation of two metal sulphides are studied, which confirmed the formation of composites. The photocatalytic response of the composites was estimated by photodegradation of Rhodamine B (C₂₈H₃₁ClN₂O₃–RhB), and the ternary composite CdS/NiS/g-C₃N₄ samples exhibited the superior photocatalytic performance. Further, the free radical capture and electron paramagnetic resonance (EPR) spectroscopy experiments identified the main active species that contributed to the photocatalytic reaction. Besides, the samples’ photocatalytic performance was evaluated by photocatalytic hydrogen production. The stability of the performance-optimized composite was determined by employing cyclic experiments over five cycles. The CdS/NiS/g-C₃N₄ showed the highest efficiency of hydrogen production i.e. about 423.37 μmol.g^?1.h^?1, which is 2.89 times that of the pristine g-C₃N₄. Finally, two types of heterojunction structures were proposed to interpret the enhanced photocatalytic efficiency.     

Facile synthesis of CeO2/g-C3N4 nanocomposites with significantly improved visible-light photocatalytic activity for hydrogen evolution

Ceria dioxide supported on graphitic carbon nitride (CeO₂/g-C₃N₄) composites were facilely synthesized to be application for photocatalytic hydrogen (H₂) generation in this present work. The physical and chemical properties of CeO₂/g-C₃N₄ nanocomposites were determined via a series of characterizations. The CeO₂/g-C₃N₄ composites prepared by facile thermal annealing and rotation-evaporation method exhibit excellent photocatalytic H₂ evolution with visible-light illumination. The best hydrogen generation rate of CeO₂/g-C₃N₄ composite with 1.5 wt% Pt is 0.83 mmol h⁻¹ g⁻¹, which is almost same as that of composite with 3 wt% Pt prepared by simple physical mixing method. The significantly developed photocatalytic activity of CeO₂/g-C₃N₄ composite is majorly ascribed to the stronger interfacial effects with the more visible-light absorbance and faster electron transfer. This work reveals that construction of the CeO₂/g-C₃N₄ composite with high disperse and close knit by the facile thermal annealing and rotation-evaporation method could be an effective method to achieve excellent photocatalytic hydrogen evolution performance.     

Chloroplast-granum-inspired porous nanorods composed of g-C3N4 ultrathin nanosheets as visible light photocatalysts for highly enhanced hydrogen production

Metal-free photocatalysts have attracted great attention in hydrogen production under visible light due to their low cost and abundance. Inspired by the structure of chloroplast-granum, here we prepare a new porous nanorod composed of F-doped g-C₃N₄ ultrathin nanosheet for photocatalytic hydrogen evolution. The obtained g-C₃N₄ (FCN-PNRs) show layer-by-layer stacked structure for highly efficient light hasting, exhibit F-doping for highly charge separation efficiency, and display porous structure for exposing a large amount of photocatalytic activity sites. These findings have been studied by various characterizations, such as Brunauer-Emmett-Teller, and Photoluminescence. As a result, the hydrogen production performance for the optimized FCN-PNRs photocatalyst reaches 2600 μmol h⁻¹ g⁻¹ under visible light, which is almost 16 times higher than bulk g-C₃N₄. This study not only reports a new chloroplast-granum-inspired g-C₃N₄ photocatalyst, but also provides new views to the fabrication and design of nature-inspired metal-free structures for catalysis applications.     

Influence of the nitrogen pots from graphitic carbon nitride with the presence of wrinkled silica-titania for photodegradation enhancement of 2-chlorophenol

An interlayer structure hybrid wrinkled silica titania (WST) loaded on graphitic carbon nitride (g-C₃N₄) was successfully constructed using facile microwave-assisted solid-state technique. The as-prepared materials were characterized using N₂ adsorption-desorption, XRD, FESEM, UV–Vis DRS, FTIR, and TEM analysis. The photocatalytic degradation of 2-chlorophenol (2-CP) towards visible light illumination (150 mW/cm²) is following the sequence: 10 wt% WST@CN (91%) > 5 wt% WST@CN (65%) > g-C₃N₄ (63%) > 15 wt% WST@CN (58%) ? WST (50%). The supreme photocatalytic performance of 10 wt% WST@CN was owing to the WST morphology that more concealed between stacked layer of g-C₃N₄, as a consequence of the stronger interaction between “nitrogen pots” of the g-C₃N₄ and Si/Ti species of the 10 wt% WST, and thus, enhanced the efficiency of charge separation. These criteria provide better charge carrier mobility for enhanced visible light driven photocatalytic performance. The kinetic studies revealed that the photocatalytic degradation of 2-CP using 10 wt% WST@CN obeyed a model of pseudo-first order, with the surface reaction being the rate determining step. Subsequently, the scavenger study confirmed that hydroxyl radicals that absorbed on the catalyst surface play a major role over 10 wt% WST@CN as emerged from the mechanism of Z-scheme. It is notable that the interfacial of WST@CN composite could appear as an excellent catalyst for its useful application for endocrine disruptive wastewater treatment.